Water Dramatically Accelerates the Decomposition of α-Hydroxyalkyl-Hydroperoxides in Aerosol Particles

Qiu, Junting; Ishizuka, Shinnosuke; Tonokura, Kenichi; Colussi, A. J.; Enami, Shinichi

doi:10.1021/acs.jpclett.9b01953

Cited by 35 publications

(107 citation statements)

References 66 publications

(144 reference statements)

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“…It was found that α-acyloxyalkyl-hydroperoxides decomposed promptly when the pH was larger than 5 in the aqueous phase. The aqueous decomposition of α-hydroxyalkyl-hydroperoxides was also reported to be accelerated by acids, and the rate coefficients of decay increased with decreasing pH (Qiu et al, 2020a). These studies implied that acids, acting as catalysts, promoted the decomposition processes of some compounds in liquid particles and might reduce the quantity of SOAs.…”

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

confidence: 90%

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

Gong

Chen

2021

Atmos. Chem. Phys.

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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.

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

confidence: 90%

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

Gong

Chen

2021

Atmos. Chem. Phys.

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“…Hydrogen peroxide (H 2 O 2 ) is a crucial oxidant in liquid-and aerosol-phase chemistry (Reeves and Penkett, 2003). Additionally, it serves as a temporary reservoir species that cycles and redistributes the HO x radicals (Lee et al, 2000;Tong et al, 2016;Crowley et al, 2018).…”

Section: Introductionmentioning

confidence: 99%

Partitioning of hydrogen peroxide in gas-liquid and gas-aerosol phases

et al. 2020

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Abstract. Hydrogen peroxide (H2O2) is a vital oxidant in the atmosphere and plays critical roles in the oxidation chemistry of both liquid and aerosol phases. The partitioning of H2O2 between the gas and liquid phases, or the aerosol phase, could affect its abundance in these condensed phases and eventually the formation of secondary components. However, the partitioning processes of H2O2 in gas-liquid and gas-aerosol phases are still unclear, especially in the ambient atmosphere. In this study, field observations of gas-, liquid-, and aerosol-phase H2O2 were carried out in the urban atmosphere of Beijing during the summer and winter of 2018. The effective field-derived mean value of Henry's law constant (HAm, 2.1×105 M atm−1) was 2.5 times of the theoretical value in pure water (HAt, 8.4×104 M atm−1) at 298±2 K. The effective derived gas-aerosol partitioning coefficient (KPm, 3.8×10-3 m3 µg−1) was 4 orders of magnitude higher on average than the theoretical value (KPt, 2.8×10-7 m3 µg−1) at 270±4 K. Beyond following Henry's law or Pankow's absorptive partitioning theory, the partitioning of H2O2 in the gas-liquid and gas-aerosol phases in the ambient atmosphere was also influenced by certain physical and chemical reactions. The average concentration of liquid-phase H2O2 in rainwater during summer was 44.12±26.49 µM. In 69 % of the collected rain samples, the measured level of H2O2 was greater than the predicted value in pure water calculated by Henry's law. In these samples, 41 % of the measured H2O2 was from gas-phase partitioning, while most of the rest may be from residual H2O2 in raindrops. In winter, the level of aerosol-phase H2O2 was 0.093±0.085 ng µg−1, which was much higher than the predicted value based on Pankow's absorptive partitioning theory. The contribution of partitioning of the gas-phase H2O2 to the aerosol-phase H2O2 formation was negligible. The decomposition/hydrolysis rate of aerosol-phase organic peroxides could account for 11 %–74 % of the consumption rate of aerosol-phase H2O2, and the value depended on the composition of organic peroxides in the aerosol particles. Furthermore, the heterogeneous uptake of HO2 and H2O2 on aerosols contributed to 22 % and 2 % of the aerosol-phase H2O2 consumption, respectively.

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“…"Educt" factors contain water-labile compounds which are stable under dry conditions but undergo chemical reactions in the presence of water. Likely aqueous-phase reactions are the fragmentation (hydrolysis) of organic (hydro)peroxides Zhao et al, 2018;Qiu et al, 2019) or accretion reactions. Examples for these "educt" factors were SV2, SV4, AV2, and AV4.…”

Section: Interpretation Of the Evolution Of Ncrsmentioning

confidence: 99%

Evolution of volatility and composition in sesquiterpene-mixed and α-pinene secondary organic aerosol particles during isothermal evaporation

Buchholz

Ylisirniö

Barreira

et al. 2021

Preprint

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Abstract. Efforts have been spent on investigating the isothermal evaporation of α-pinene SOA particles at ranges of conditions and decoupling the impacts of viscosity and volatility on evaporation. However, little is known about the evaporation behavior of SOA particles from biogenic organic compounds other than α-pinene. In this study, we investigated the isothermal evaporation behaviors of α-pinene (αpin) and sesquiterpene mixture (SQTmix) SOA particles under a series of relative humidity (RH) conditions. With a set of in-situ instruments, we monitored the evolution of particle size, volatility, and composition during evaporation. Our finding demonstrates that the SQTmix SOA particles evaporated slower than the αpin ones at any set of RH (expressed with the volume fraction remaining (VFR)), which is primarily due to their lower volatility and possibly aided by higher viscosity under dry conditions. We further applied positive matrix factorization (PMF) to thermal desorption data containing volatility and composition information. Analyzing the net change ratios (NCRs) of each PMF-resolved factor, we can quantitatively compare how each sample factor evolves with increasing evaporation time/RH. When sufficient particulate water content was present in either SOA system, the most volatile sample factor was primarily lost via evaporation and changes in other sample factors were mainly governed by aqueous-phase processes. The evolution of each sample factor of SQTmix SOA particles was controlled by a single type of process, whereas for αpin SOA particles it was regulated by multiple processes. As indicated by the coevolution of VFR and NCR, the effect of aqueous-phase processes could vary from one to another according to particle type, sample factors and evaporation timescale.

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Water Dramatically Accelerates the Decomposition of α-Hydroxyalkyl-Hydroperoxides in Aerosol Particles

Cited by 35 publications

References 66 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

Partitioning of hydrogen peroxide in gas-liquid and gas-aerosol phases

Evolution of volatility and composition in sesquiterpene-mixed and α-pinene secondary organic aerosol particles during isothermal evaporation

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