Mechanistic and kinetics investigations of oligomer formation from Criegee intermediate reactions with hydroxyalkyl hydroperoxides

Chen, Long; Huang, Yu; Xue, Yonggang; Shen, Zhenxing; Cao, Junji; Wang, Wenliang

doi:10.5194/acp-19-4075-2019

Cited by 28 publications

(25 citation statements)

References 102 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Actually, we could not evaluate the effect of acidity on the formation of SOA accurately because the acidity of aerosols might impact a series of reactions, and the mechanisms and rates of these reactions at different pH levels were vague. It was noted that Chen et al (2008) found that in the aqueous-phase ozonolysis of methacrolein and methyl vinyl ketone, the yields of products were almost independent of pH, and Zhang et al (2009) also observed this phenomenon in the ozonolysis of α-pinene and β-pinene in the aqueous phase. Thus the effect of the particle acidity on the results might also be limited here, and the accurate estimates of this issue still need further research.…”

Section: Reasons For Different Performances Of Scis Under Different Rh Levelsmentioning

confidence: 97%

Quantification of the role of stabilized Criegee intermediates in the formation of aerosols in limonene ozonolysis

Gong

Chen

2021

Atmos. Chem. Phys.

View full text Add to dashboard Cite

Abstract. Stabilized Criegee intermediates (SCIs) have the potential to oxidize trace species and to produce secondary organic aerosols (SOAs), making them important factors in tropospheric chemistry. This study quantitatively investigates the performance of SCIs in SOA formation at different relative humidity (RH) levels, and the first- and second-generation oxidations of endo- and exocyclic double bonds ozonated in limonene ozonolysis are studied separately. Through regulating SCI scavengers, the yields and rate constants of SCIs in a reaction system were derived, and the quantities of SCIs were calculated. The quantity of SOAs decreased by more than 20 % under low-humidity conditions (10 % RH–50 % RH), compared to that under dry conditions, due to the reactions of SCIs with water, while the inhibitory effect of water on SOA formation was not observed under high-humidity conditions (60 % RH–90 % RH). When using excessive SCI scavengers to exclude SCI reactions, it was found that the effect of water on SOA formation with the presence of SCIs was different from that without the presence of SCIs, suggesting that SCI reactions were relevant to the non-monotonic impact of water. The fractions of the SCI contribution to SOAs were similar between dry and high-humidity conditions, where the SCI reactions accounted for ∼ 63 % and ∼ 73 % in SOA formation in the first- and second-generation oxidation; however, marked differences in SOA formation mechanisms were observed. SOA formation showed a positive correlation with the quantity of SCIs, and the SOA formation potential of SCIs under high-humidity conditions was more significant than that under dry and low-humidity conditions. It was estimated that 20 %–30 % of SCIs could be converted into SOAs under high-humidity conditions, while this value decreased by nearly half under dry and low-humidity conditions. The typical contribution of limonene-derived SCIs to SOA formation is calculated to be (8.21 ± 0.15) × 10−2 µg m−3 h−1 in forest, (4.26 ± 0.46) × 10−2 µg m−3 h−1 in urban areas, and (2.52 ± 0.28) × 10−1 µg m−3 h−1 in indoor areas. Water is an uncertainty in the role SCIs play in SOA formation, and the contribution of SCIs to SOA formation needs consideration even under high RH in the atmosphere.

show abstract

Section: Reasons For Different Performances Of Scis Under Different Rh Levelsmentioning

confidence: 97%

Quantification of the role of stabilized Criegee intermediates in the formation of aerosols in limonene ozonolysis

Gong

Chen

2021

Atmos. Chem. Phys.

View full text Add to dashboard Cite

show abstract

“…Furthermore, hydroxymethyl hydroperoxide (HMHP), hydroperoxymethyl formate (HPMF), and α-alkoxyalkyl hydroperoxiedes (AAAHs) are formed during sCI bimolecular reactions, exhibiting large molecular weights and low volatility; these molecules are thought to be closely related to the formation of SOA in the atmosphere. Quantum chemical calculations indicate that CH 2 OO can polymerize with the −OOH and −OH groups of hydroperoxides to form oligomers . Such oligomers may form organic cores in the atmosphere and facilitate the growth of SOA.…”

Section: Oxidantsmentioning

confidence: 99%

Important Oxidants and Their Impact on the Environmental Effects of Aerosols

Tong

Wang

et al. 2021

J. Phys. Chem. A

View full text Add to dashboard Cite

Oxidants are central species in the atmosphere, where they not only determine secondary particle formation but also impact human health and climate change. In general, they are unstable, highly reactive, and recyclable and have been studied in field observations, laboratory studies, and model simulations. The most widely investigated oxidants, such as OH radicals, O 3 , and Cl atom, HONO, NO 3 , N 2 O 5 , and Criegee Intermediates (CIs) have attracted more attention recently. Furthermore, secondary particles formed in the oxidations processes impact the particle physicochemical properties, such as hygroscopicity and optical properties and therefore impact the atmospheric radiation balance. Therefore, the newest investigation results of important oxidants (HONO, NO 3 , N 2 O 5 , and CIs) are reviewed in this manuscript, and the environmental effects of secondary particles formed through corresponding oxidation processes are also stated. Furthermore, some perspectives are further discussed in the article.

show abstract

“…When the rate constant of limonene-derived SCIs reaction with 2-butanol was assumed as 10 −15 cm 3 molecule −1 s −1 , it was estimated that with the lowest concentration of AA used in experiments, the ratio of the amount of SCIs reacted with 2-butanol to the amount of SCIs reacted with AA was 0.125, which was considered to be not important enough to influence the results. Besides, products formed from SCIs reaction with AA and water might further react with SCIs and impacted aerosols formation (Chen et al, 2019). However, due to the short lifetime and low concentration of SCIs in system, the concentration of SCIs was a limiting factor in bimolecular reactions of SCIs with other products.…”

Section: Analysis On Reaction Mechanismsmentioning

confidence: 99%

Quantification of the role of stabilized Criegee intermediates in the formation of aerosols in limonene ozonolysis

Gong¹,

Chen²

2020

Preprint

View full text Add to dashboard Cite

Abstract. Stabilized Criegee intermediates (SCIs) have the potential to oxidize trace species and to produce secondary organic aerosols (SOA), making them important factors in tropospheric chemistry. This study quantitatively investigates the performance of SCIs in SOA formation at different relative humidity (RH), and the first- and second-generation oxidations of endo- and exo-cyclic double bonds ozonated in limonene ozonolysis are studied separately. Through regulating SCIs scavengers, the yields and rate constants of SCIs in reaction system were derived, and the amounts of SCIs were calculated. The amount of SOA decreased by more than 20 % under low-humidity conditions (10–50 % RH), compared to that under dry conditions due to the reactions of SCIs with water, while the inhibitory effect of water on SOA formation was not observed under high-humidity conditions (60–90 % RH). When using excessive SCIs scavengers to exclude SCIs reactions, it was found that the effect of water on SOA formation with the presence of SCIs was different from that without the presence of SCIs, suggesting that SCIs reactions were relevant to the non-monotonic impact of water. The fractions of SCIs contribution to SOA were similar between dry and high-humidity conditions, where the SCIs reactions accounted for ~ 63 % and ~ 73 % in SOA formation in the first- and second-generation oxidation, however, marked differences in SOA formation mechanisms were observed. SOA formation showed a positive correlation with the amount of SCIs, and the SOA formation potential of SCIs under high-humidity conditions was more significant than that under dry and low-humidity conditions. It was estimated that 20–30 % of SCIs could convert into SOA under high-humidity conditions, while this value decreased nearly by half under dry and low-humidity conditions. The contributions of limonene-derived SCIs to SOA in atmosphere were evaluated, and it was estimated that the contribution of SCIs to SOA was the lowest under low-humidity conditions. Under high-humidity conditions, the contribution of limonene-derived SCIs to SOA was (8.21 ± 0.15) × 10−2 μg m−3 h−1 in forest, (6.66 ± 0.12) × 10−2 μg m−3 h−1 in urban area, and (3.95 ± 0.72) × 10−1 μg m−3 h−1 in indoor area. Water was an uncertainty on the role of SCIs playing in SOA formation, and the contribution of SCIs to SOA formation needed consideration even under high RH in the atmosphere.

show abstract

Mechanistic and kinetics investigations of oligomer formation from Criegee intermediate reactions with hydroxyalkyl hydroperoxides

Cited by 28 publications

References 102 publications

Quantification of the role of stabilized Criegee intermediates in the formation of aerosols in limonene ozonolysis

Quantification of the role of stabilized Criegee intermediates in the formation of aerosols in limonene ozonolysis

Important Oxidants and Their Impact on the Environmental Effects of Aerosols

Quantification of the role of stabilized Criegee intermediates in the formation of aerosols in limonene ozonolysis

Contact Info

Product

Resources

About