Hydrotrioxide (ROOOH) formation in the atmosphere

Berndt, Torsten; Chen, Jing; Kjærgaard, Eva R.; Møller, Kristian H.; Tilgner, Andreas; Hoffmann, Erik; Herrmann, Hartmut; Crounse, J. D.; Wennberg, P. O.; Kjaergaard, Henrik G.

doi:10.1126/science.abn6012

Cited by 24 publications

(33 citation statements)

References 65 publications

(40 reference statements)

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“…183 For the isoprene−OH oxidation system, the molar yield of ROOOH was estimated to be around 1%, with an averaged lifetime of minutes to hours. 183 Given their high oxygenation level, relatively high reactivity in the atmosphere, and the capacity of producing singlet molecular oxygen ( 1 O 2 ), 183 impacts from ROOOH on atmospheric oxidation capacity, new particle formation, global climate, and adverse health outcomes are waiting to be investigated in the future.…”

Section: Other Formation Pathways For Posmentioning

confidence: 99%

Organic Peroxides in Aerosol: Key Reactive Intermediates for Multiphase Processes in the Atmosphere

et al. 2023

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Organic peroxides (POs) are organic molecules with one or more peroxide (−O−O−) functional groups. POs are commonly regarded as chemically labile termination products from gas-phase radical chemistry and therefore serve as temporary reservoirs for oxidative radicals (HO x and RO x ) in the atmosphere. Owing to their ubiquity, active gasparticle partitioning behavior, and reactivity, POs are key reactive intermediates in atmospheric multiphase processes determining the life cycle (formation, growth, and aging), climate, and health impacts of aerosol. However, there remain substantial gaps in the origin, molecular diversity, and fate of POs due to their complex nature and dynamic behavior. Here, we summarize the current understanding on atmospheric POs, with a focus on their identification and quantification, state-of-the-art analytical developments, molecular-level formation mechanisms, multiphase chemical transformation pathways, as well as environmental and health impacts. We find that interactions with SO 2 and transition metal ions are generally the fast PO transformation pathways in atmospheric liquid water, with lifetimes estimated to be minutes to hours, while hydrolysis is particularly important for α-substituted hydroperoxides. Meanwhile, photolysis and thermolysis are likely minor sinks for POs. These multiphase PO transformation pathways are distinctly different from their gas-phase fates, such as photolysis and reaction with OH radicals, which highlights the need to understand the multiphase partitioning of POs. By summarizing the current advances and remaining challenges for the investigation of POs, we propose future research priorities regarding their origin, fate, and impacts in the atmosphere.

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Section: Other Formation Pathways For Posmentioning

confidence: 99%

Organic Peroxides in Aerosol: Key Reactive Intermediates for Multiphase Processes in the Atmosphere

et al. 2023

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“…Besides the environmental conditions, the prior studies reported that the product of the reaction of RO 2 with OH, trioxides (ROOOH), might lead to an OH interference signal. The reactions of RO 2 radicals with OH radicals might be competitive with other sinks for RO 2 radicals (Fittschen, 2019;Fittschen et al, 2019;Berndt et al, 2022). Fittschen et al (2019) reported that the OH interference signals might come from the ROOOH heterogeneous decomposition on the walls of the FAGE cell or the entrance nozzle, but they also noted that the ROOOH interference is highly dependent on the design and measurement conditions of different FAGE instruments.…”

Section: The Oh and Ho 2 Measurementsmentioning

confidence: 99%

Radical chemistry in the Pearl River Delta: observations and modeling of OH and HO₂ radicals in Shenzhen in 2018

Gao

et al. 2022

Atmos. Chem. Phys.

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Abstract. The ambient radical concentrations were measured continuously by laser-induced fluorescence during the STORM (STudy of the Ozone foRmation Mechanism) campaign at the Shenzhen site, located in the Pearl River Delta in China, in the autumn of 2018. The diurnal maxima were 4.5×106 cm−3 for OH radicals and 4.2×108 cm−3 for HO2 radicals (including an estimated interference of 23 %–28 % from RO2 radicals during the daytime), respectively. The state-of-the-art chemical mechanism underestimated the observed OH concentration, similar to the other warm-season campaigns in China. The OH underestimation was attributable to the missing OH sources, which can be explained by the X mechanism. Good agreement between the observed and modeled OH concentrations was achieved when an additional numerical X equivalent to 0.1 ppb NO concentrations was added into the base model. The isomerization mechanism of RO2 derived from isoprene contributed approximately 7 % to the missing OH production rate, and the oxidation of isoprene oxidation products (MACR and MVK) had no significant impact on the missing OH sources, demonstrating further exploration of unknown OH sources is necessary. A significant HO2 heterogeneous uptake was found in this study, with an effective uptake coefficient of 0.3. The model with the HO2 heterogeneous uptake can simultaneously reproduce the OH and HO2 concentrations when the amount of X changed from 0.1 to 0.25 ppb. The ROx primary production rate was dominated by photolysis reactions, in which the HONO, O3, HCHO, and carbonyls photolysis accounted for 29 %, 16 %, 16 %, and 11 % during the daytime, respectively. The ROx termination rate was dominated by the reaction of OH+NO2 in the morning, and thereafter the radical self-combination gradually became the major sink of ROx in the afternoon. As the sum of the respective oxidation rates of the pollutants via reactions with oxidants, the atmospheric oxidation capacity was evaluated, with a peak of 11.8 ppb h−1 around noontime. The ratio of P(O3)net to AOCVOCs, which indicates the yield of net ozone production from VOC oxidation, trended to increase and then decrease as the NO concentration increased. The median ratios ranged within 1.0–4.5, with the maximum existing when the NO concentration was approximately 1 ppb. The nonlinear relationship between the yield of net ozone production from VOC oxidation and NO concentrations demonstrated that optimizing the NOx and VOC control strategies is critical to controlling ozone pollution effectively in the future.

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“…Therefore, oxidation of nicotine forms P1, P2, P4, P5, and P6 with fractional yields of 0.55, 0.25, 0.12, 0.03, and 0.05 if initiated by OH radical (with fractions of R1, R3, and R6 based on ROCBS-QB3 barrier heights) or forms P1, P2, and P4 with fractional yields of 0.62, 0.32, and 0.06 if initiated by ozone (with fractions of R1 and R6 based on RCCSD(T)/aVDZ barrier heights). Rapid hydrogen atom transfers (HATs) activated by the amine-N-center are also found in recent studies on atmospheric oxidation of amines. − …”

Section: Resultsmentioning

confidence: 86%

Rapid Gas-Phase Autoxidation of Nicotine in the Atmosphere

Yang

Wang

2022

J. Phys. Chem. A

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Nicotine is the most abundant alkaloid chemical in smoke emission. In this work, we investigated the gas-phase oxidation mechanism of nicotine initiated by its reactions with the OH radical and ozone. Both initiation reactions start dominantly by hydrogen atom abstractions from the C1, C3, and −CH 3 groups of the methylpyrrolidinyl group and form radicals nicotinyl-1, nicotinyl-3, and nicotinyl-6, respectively. The nicotinyl radicals would recombine rapidly with O 2 , forming RO 2 with rapid intramolecular hydrogenatom transfers (HATs) with rate coefficients from 4 s −1 to greater than 10 4 s −1 . The rapid HATs in peroxy radicals suggest rapid autoxidation of nicotine in the gas phase. Formation of HCNO and HC(O)NH 2 , being observed in previous studies, arises likely from secondary reactions or photolysis of intermediate products.

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Hydrotrioxide (ROOOH) formation in the atmosphere

Cited by 24 publications

References 65 publications

Organic Peroxides in Aerosol: Key Reactive Intermediates for Multiphase Processes in the Atmosphere

Organic Peroxides in Aerosol: Key Reactive Intermediates for Multiphase Processes in the Atmosphere

Radical chemistry in the Pearl River Delta: observations and modeling of OH and HO₂ radicals in Shenzhen in 2018

Rapid Gas-Phase Autoxidation of Nicotine in the Atmosphere

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Hydrotrioxide (ROOOH) formation in the atmosphere

Cited by 24 publications

References 65 publications

Organic Peroxides in Aerosol: Key Reactive Intermediates for Multiphase Processes in the Atmosphere

Organic Peroxides in Aerosol: Key Reactive Intermediates for Multiphase Processes in the Atmosphere

Radical chemistry in the Pearl River Delta: observations and modeling of OH and HO2 radicals in Shenzhen in 2018

Rapid Gas-Phase Autoxidation of Nicotine in the Atmosphere

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Radical chemistry in the Pearl River Delta: observations and modeling of OH and HO₂ radicals in Shenzhen in 2018