Mechanistic and Kinetic Investigations on the Ozonolysis of Biomass Burning Products: Guaiacol, Syringol and Creosol

Chen, Xiaoxiao; Sun, Yanhui; Qi, Youxiao; Li, Lin; Xu, Fei; Zhao, Yan

doi:10.3390/ijms20184492

Cited by 12 publications

(14 citation statements)

References 37 publications

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“…Scheme shows the proposed ring-opening fragmentation reactions for VL and SA. VL, SA, and their hydroxylation products react with O 3 (g) forming primary ozonides, which then rearrange as Criegee intermediates , and react with water to form hydroperoxide intermediates that decompose, eliminating H 2 O 2 , into dicarboxylic acid monomethyl esters, as displayed in Scheme . For example, reaction R19 (Scheme ) shows that VL and SA generate 4-formyl muconic acid monomethyl ester ( m / z 183) and 4-formyl-2-methoxymuconic acid monomethyl ester ( m / z 213), respectively.…”

Section: Resultsmentioning

confidence: 99%

Oxidation of Phenolic Aldehydes by Ozone and Hydroxyl Radicals at the Air–Water Interface

Rana

Guzmán

2020

J. Phys. Chem. A

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Biomass burning releases highly reactive methoxyphenols into the atmosphere, which can undergo heterogeneous oxidation and act as precursors for secondary organic aerosol (SOA) formation. Understanding the reactivity of such methoxyphenols at the air−water interface is a matter of major atmospheric interest. Online electrospray ionization mass spectrometry (OESI-MS) is used here to study the oxidation of two methoxyphenols among three phenolic aldehydes, 4-hydroxybenzaldehyde, vanillin, and syringaldehyde, on the surface of water. The OESI-MS results together with cyclic voltammetry measurements at variable pH are integrated into a mechanism describing the heterogeneous oxidative processing of methoxyphenols by gaseous ozone (O 3 ) and hydroxyl radicals (HO • ). For a low molar ratio of O 3 ≤ 66 ppbv, the OESI-MS spectra show that the oxidation is dominated by in situ produced HO • and results in the production of polyhydroxymethoxyphenols. When the level of O 3 increases (i.e., ≥78 times), the ion count of polyhydroxymethoxyphenols increases, while new ring fragmentation products are generated, including conjugated aldehydes and double bonds as well as additional carboxylic acid groups. The interfacial reactivity of methoxyphenols with O 3 and HO • is enhanced as the number of methoxy (−OCH 3 ) groups increases (4-hydroxybenzaldehyde < vanillin < syringaldehyde). The experimental observations are summarized in two reaction pathways, leading to the formation of (1) hydroxylated methoxyphenols and (2) multifunctional carboxylic acids from fragmentation of the aromatic ring. The new highly oxygenated products with low volatility are excellent precursors for aqueous SOA formation.

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Section: Resultsmentioning

confidence: 99%

Oxidation of Phenolic Aldehydes by Ozone and Hydroxyl Radicals at the Air–Water Interface

Rana

Guzmán

2020

J. Phys. Chem. A

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“…The importance of phenolic oxidation for BB is evidenced by the rapidly growing literature (Bertrand et al, 2018;Chen et al, 2019;Coggon et al, 2019;Decker et al, 2019;Finewax et al, 2018;Gaston et al, 2016;Hartikainen et al, 2018;Iinuma et al, 2010;Lauraguais et al, 2014;Lin et al, 2015;Liu et al, 2019;Meng et al, 2020;Mohr et al, 2013;Palm et al, 2020;Selimovic et al, 2020;Wang and Li, 2021;Xie et al, 2017). Both OH and NO3 oxidation of phenolics leads to nitrophenolics, which have been shown to significantly contribute to SOA production (Palm et al, 2020 final products without detailed examination of intermediates.…”

Section: Phenolic Oxidation and Nitrophenolic Productionmentioning

confidence: 99%

Nighttime and Daytime Dark Oxidation Chemistry in Wildfire Plumes: An Observation and Model Analysis of FIREX-AQ Aircraft Data

Decker¹,

Robinson²,

Barsanti³

et al. 2021

Preprint

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Abstract. Wildfires are increasing in size across the western U.S., leading to increases in human smoke exposure and associated negative health impacts. The impact of biomass burning (BB) smoke, including wildfires, on regional air quality depends on emissions, transport, and chemistry, including oxidation of emitted BB volatile organic compounds (BBVOCs) by the hydroxyl radical (OH), nitrate radical (NO3), and ozone (O3). During the daytime, when light penetrates the plumes, BBVOCs are oxidized mainly by O3 and OH. In contrast, at night, or in optically dense plumes, BBVOCs are oxidized mainly by O3 and NO3. This work focuses on the transition between daytime and nighttime oxidation, which has significant implications for the formation of secondary pollutants and loss of nitrogen oxides (NOx = NO + NO2), and has been understudied. We present wildfire plume observations made during FIREX-AQ (Fire Influence on Regional to Global Environments and Air Quality), a field campaign involving multiple aircraft, ground, satellite, and mobile platforms that took place in the United States in the summer of 2019 to study both wildfire and agricultural burning emissions and atmospheric chemistry. We use observations from two research aircraft, the NASA DC-8 and the NOAA Twin Otter, with a detailed chemical box model, including updated phenolic mechanisms, to analyze smoke sampled during mid-day, sunset, and nighttime. Aircraft observations suggest a range of NO3 production rates (0.1–1.5 ppbv h−1) in plumes transported both mid-day and after dark. Modeled initial instantaneous reactivity toward BBVOCs for NO3, OH, and O3 is 80.1 %, 87.7 %, 99.6 %, respectively. Initial NO3 reactivity is 10–104 times greater than typical values in forested or urban environments and reactions with BBVOCs account for ≥ 98 % of NO3 loss in sunlit plumes (jNO2 up to 4 x 10–3 s–1), while conventional photochemical NO3 loss through reaction with NO and photolysis are minor pathways. Alkenes and furans are mostly oxidized by OH and O3 (11–43 %, 54–88 % for alkenes; 18–55 %, 39–76 %, for furans, respectively), but phenolic oxidation is split between NO3, O3, and OH (26–52 %, 22–43 %, 16–33 %, respectively). Nitrate radical oxidation accounts for 26–52 % of phenolic chemical loss in sunset plumes and in an optically thick plume. Nitrocatechol yields varied between 33 % and 45 %, and NO3 chemistry in BB plumes emitted late in the day is responsible for 72–92 % (84 % in an optically thick mid-day plume) of nitrocatechol formation and controls nitrophenolic formation overall. As a result, overnight nitrophenolic formation pathways account for 56 ± 2 % of NOx loss by sunrise the following day. In all but one overnight plume we model, there is remaining NOx (13 %–57 %) and BBVOCs (8 %–72 %) at sunrise.

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“…During the atmospheric transportation process, methoxyphenols could inevitably undergo chemical transformation via reactions with gas-phase oxidants, the rate constants of which determine their atmospheric lifetimes and effectiveness as stable tracers of wood-burning emissions . In the past ten years, the atmospheric reactivity of methoxyphenols toward O 3 , Cl atoms, NO 3 radicals, and OH radicals has attracted increasing attention from the academic community. − However, there is a lack of a systematic summary of previous results about the chemical reactivity of methoxyphenols. Therefore, this review is the first to provide a comprehensive assessment of the published results about the atmospheric reactivity of methoxyphenols toward gas-phase oxidants and mainly concentrates on their kinetics, mechanisms, and secondary organic aerosol (SOA) formation.…”

Section: Introductionmentioning

confidence: 99%

Atmospheric Reactivity of Methoxyphenols: A Review

Liu

Chen

2022

Environ. Sci. Technol.

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Methoxyphenols emitted from lignin pyrolysis are widely used as potential tracers for biomass burning, especially for wood burning. In the past ten years, their atmospheric reactivity has attracted increasing attention from the academic community. Thus, this work provides an extensive review of the atmospheric reactivity of methoxyphenols, including their gas-phase, particle-phase, and aqueous-phase reactions, as well as secondary organic aerosol (SOA) formation. Emphasis was placed on kinetics, mechanisms, and SOA formation. The reactions of methoxyphenols with OH and NO3 radicals were the predominant degradation pathways, which also had significant SOA formation potentials. The reaction mechanism of methoxyphenols with O3 is the cycloaddition of O3 to the benzene ring or unsaturated CC bond, while H-abstraction and radical adduct formation are the main degradation channels of methoxyphenols by OH and NO3 radicals. Based on the published studies, knowledge gaps were pointed out. Future studies including experimental simulations and theoretical calculations of other representative kinds of methoxyphenols should be systematically carried out under complex pollution conditions. In addition, the ecotoxicity of their degradation products and their contribution to SOA formation from the atmospheric aging of biomass-burning plumes should be seriously assessed.

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Mechanistic and Kinetic Investigations on the Ozonolysis of Biomass Burning Products: Guaiacol, Syringol and Creosol

Cited by 12 publications

References 37 publications

Oxidation of Phenolic Aldehydes by Ozone and Hydroxyl Radicals at the Air–Water Interface

Oxidation of Phenolic Aldehydes by Ozone and Hydroxyl Radicals at the Air–Water Interface

Nighttime and Daytime Dark Oxidation Chemistry in Wildfire Plumes: An Observation and Model Analysis of FIREX-AQ Aircraft Data

Atmospheric Reactivity of Methoxyphenols: A Review

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