&amp;lt;i&amp;gt;α&amp;lt;/i&amp;gt;-Pinene nitrates: synthesis, yields and atmospheric chemistry

X., S.; Rindelaub, Joel D.; McAvey, K. M.; Gagare, Pravin D.; Nault, Benjamin A.; Ramachandran, Prakash; Shepson, P. B.

doi:10.5194/acp-11-6337-2011

Cited by 11 publications

(7 citation statements)

References 49 publications

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“…S1 ), indicate that a substantial fraction of the NO x originated from soil 27 in the forest rather than from anthropogenic sources, to form aerosol nitrate. Nitrate radicals in the atmosphere are known to have a high reactivity to α-pinene and can subsequently form α-pinene nitrates 39 . Recently, chamber experimental and modelling studies have shown that the addition of nitrate functional groups inhibit CCN activation by reducing its miscibility with water 40 , 41 , which also supports the observed reduction in CCN activity for particles in the vicinity of a biogenic source area.…”

Section: Resultsmentioning

confidence: 99%

Evidence of a reduction in cloud condensation nuclei activity of water-soluble aerosols caused by biogenic emissions in a cool-temperate forest

Müller

Miyazaki

Tachibana

et al. 2017

Sci Rep

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Biogenic organic aerosols can affect cloud condensation nuclei (CCN) properties, and subsequently impact climate change. Large uncertainties exist in how the difference in the types of terrestrial biogenic sources and the abundance of organics relative to sulfate affect CCN properties. For the submicron water-soluble aerosols collected for two years in a cool-temperate forest in northern Japan, we show that the hygroscopicity parameter κCCN (0.44 ± 0.07) exhibited a distinct seasonal trend with a minimum in autumn (κCCN = 0.32–0.37); these κCCN values were generally larger than that of ambient particles, including water-insoluble fractions. The temporal variability of κCCN was controlled by the water-soluble organic matter (WSOM)-to-sulfate ratio (R2 > 0.60), where the significant reduction of κCCN in autumn was linked to the increased WSOM/sulfate ratio. Positive matrix factorization analysis indicates that α-pinene-derived secondary organic aerosol (SOA) substantially contributed to the WSOM mass (~75%) in autumn, the majority of which was attributable to emissions from litter/soil microbial activity near the forest floor. These findings suggest that WSOM, most likely α-pinene SOA, originated from the forest floor can significantly suppress the aerosol CCN activity in cool-temperate forests, which have implications for predicting climate effects by changes in biogenic emissions in future.

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Section: Resultsmentioning

confidence: 99%

Evidence of a reduction in cloud condensation nuclei activity of water-soluble aerosols caused by biogenic emissions in a cool-temperate forest

Müller

Miyazaki

Tachibana

et al. 2017

Sci Rep

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“…In pristine atmosphere, the effective rate of RO 2 with NO/HO 2 /R′O 2 could be very low, e.g., at ∼0.025 s –1 with 100 pptv (∼2.5 × 10 9 molecules cm –3 ) of NO/HO 2 /R′O 2 altogether, allowing the possibility for unimolecular isomerizations in RO 2 radicals. It is difficult to estimate the RONO 2 yields; e.g., molar yields of α-pinene nitrates ranged from 0.13 ± 0.035 to 0.26 ± 0.07. , For the time being, a yield of ∼0.20 at 298 K is assumed by referring to the values in α-pinene and other RO 2 radicals of similar sizes. Yields of RONO 2 would be higher at lower temperatures.…”

Section: Results and Discussionmentioning

confidence: 99%

Atmospheric Oxidation Mechanism of Sabinene Initiated by the Hydroxyl Radicals

Wang

2018

J. Phys. Chem. A

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The atmospheric oxidation mechanism of sabinene initiated by the OH radical has been studied using quantum chemistry calculations at the CBS-QB3 level and reaction kinetic calculations using transition state theory and unimolecular rate theory coupled with collisional energy transfer. The oxidation is initiated by OH radical additions to the CH 2 C< bond with a branching ratio of ∼(92−96)%, while all the hydrogen atom abstractions count for ∼(4−8)% of branching ratio, which was estimated by comparing the rate coefficients of the reactions of sabinene and sabinaketon with the OH radical. Addition of OH to the C< carbon forms radical adduct Ra, while addition of OH to the terminal CH 2  carbon forms radical adduct Rb, which would break the three-membered ring promptly and almost completely to radical Re. RRKM-ME calculations obtained fractional yields of 0.40, 0.09, and 0.51 for radicals syn-Ra, anti-Ra, and Re, respectively, at 298 K and 760 Torr. In the atmosphere, the syn/anti-Ra radical would ultimately transform to sabinaketone in the presence of ppbv levels of NO, while in the transformation of the Re radical, both bimolecular reactions and unimolecular H-migrations could occur competitively for the peroxy radicals formed. The H-migrations in peroxy radicals result in the formation of unsaturated multifunctional compounds containing >CO, −OH, and/or −OOH groups. Formation of sabinaketone from syn-and anti-Ra and formation of acetone from Re are predicted with yields of ∼0.37 and ∼0.38 in the presence of high NO, being larger than while in reasonable agreement with the experimental values of 0.19−0.23 and of 0.21−0.27, respectively.

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“…Atmospheric ON formation occurs by either OH radical-initiated photochemical reactions or NO 3 radical-initiated nocturnal reactions of anthropogenic and biogenic volatile organic compounds. These reactions can produce ON compounds with vapor pressures low enough to condense and form SOA. − In one such study, the formation of a series of ON compounds from reactions of α-pinene with NO 3 radicals was observed . In another study, the photochemistry of the hydroxyl radical oxidation of α-pinene under high NO x conditions was studied and the formation of a range of ON compounds from α-pinene in the presence of nitric oxide (NO) was reported .…”

Section: Introductionmentioning

confidence: 99%

Heterogeneous Reactions of α-Pinene on Mineral Surfaces: Formation of Organonitrates and α-Pinene Oxidation Products

Hettiarachchi

Grassian

2022

J. Phys. Chem. A

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Organonitrates (ON) are important components of secondary organic aerosols (SOAs). α-Pinene (C 10 H 16 ), the most abundant monoterpene in the troposphere, is a precursor for the formation of several of these compounds. ON from α-pinene can be produced in the gas phase via photochemical processes and/or following reactions with oxidizers including hydroxyl radical and ozone. Gas-phase nitrogen oxides (NO 2 , NO 3 ) are N sources for ON formation. Although gas-phase reactions of α-pinene that yield ON are fairly well understood, little is known about their formation through heterogeneous and multiphase pathways. In the current study, surface reactions of α-pinene with nitrogen oxides on hematite (α-Fe 2 O 3 ) and kaolinite (SiO 2 Al 2 O 3 (OH) 4 ) surfaces, common components of mineral dust, have been investigated. α-Pinene oxidizes upon adsorption on kaolinite, forming pinonaldehyde, which then dimerizes on the surface. Furthermore, α-pinene is shown to react with adsorbed nitrate species on these mineral surfaces producing multiple ON and other oxidation products. Additionally, gas-phase oxidation products of α-pinene on mineral surfaces are shown to more strongly adsorb on the surface compared to α-pinene. Overall, this study reveals the complexity of reactions of prevalent organic compounds such as α-pinene with adsorbed nitrate and nitrogen dioxide, revealing new heterogeneous reaction pathways for SOA formation that is mineralogy specific.

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<i>α</i>-Pinene nitrates: synthesis, yields and atmospheric chemistry

Cited by 11 publications

References 49 publications

Evidence of a reduction in cloud condensation nuclei activity of water-soluble aerosols caused by biogenic emissions in a cool-temperate forest

Evidence of a reduction in cloud condensation nuclei activity of water-soluble aerosols caused by biogenic emissions in a cool-temperate forest

Atmospheric Oxidation Mechanism of Sabinene Initiated by the Hydroxyl Radicals

Heterogeneous Reactions of α-Pinene on Mineral Surfaces: Formation of Organonitrates and α-Pinene Oxidation Products

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