Epoxide formation in the reactions of the nitrate radical with 2,3-dimethyl-2-butene, cis- and trans-2-butene and isoprene

Skov, Henrik; Benter, Thorsten; Schindler, R. N.; Hjorth, J.; Restelli, G.

doi:10.1016/1352-2310(94)90304-2

Cited by 46 publications

(43 citation statements)

References 14 publications

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“…6) compared to other product ions suggesting that it might also be formed from the further oxidation of a first-generation product. 2-methyl-2-vinyl-oxirane has been observed from isoprene-NO 3 reaction in previous studies at 20 mbar in helium (Berndt and Böge, 1997) and 20 Torr in argon (Skov et al, 1994), respectively. When operated in positive mode with H 3 O + as the reagent ion (products are observed at m/z=MW+1), CIMS shows a protonated molecule at m/z 85.…”

Section: Offline Chemical Analysismentioning

confidence: 96%

“…Multiple structural isomers are possible, consistent with the multiple chromatographic peaks observed in the extracted ion chromatograms; however, only one structural isomer is shown for simplicity. a These first-generation gas-phase products were previously observed by Skov et al (1994) and Kwok et al (1996); these gas-phase products were detected as the [M+CF 3 O] − ion by the CIMS instrument. b These are minor SOA products, confirming that the further oxidation of the C 5 -nitrooxycarbonyl and C 5 -hydroxycarbonyl first-generation products do not yield significant amounts of SOA.…”

Section: Proposed Mechanisms Of Soa Formationmentioning

confidence: 98%

“…When operated in positive mode with H 3 O + as the reagent ion (products are observed at m/z=MW+1), CIMS shows a protonated molecule at m/z 85. Although the epoxide yield is found to be <1% of the total reacted isoprene at atmospheric pressure (Skov et al, 1994), the signal at m/z 85 can arise in part from the epoxide. The further oxidation of the epoxide results in the formation of an epoxide peroxy radical, which can react with the isoprene peroxy radical to form the peroxide at m/z 393.…”

Section: Offline Chemical Analysismentioning

confidence: 99%

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Secondary organic aerosol (SOA) formation from reaction of isoprene with nitrate radicals (NO3)

et al. 2008

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Abstract. Secondary organic aerosol (SOA) formation from the reaction of isoprene with nitrate radicals (NO 3 ) is investigated in the Caltech indoor chambers. Experiments are performed in the dark and under dry conditions (RH<10%) using N 2 O 5 as a source of NO 3 radicals. For an initial isoprene concentration of 18.4 to 101.6 ppb, the SOA yield (defined as the ratio of the mass of organic aerosol formed to the mass of parent hydrocarbon reacted) ranges from 4.3% to 23.8%. By examining the time evolutions of gas-phase intermediate products and aerosol volume in real time, we are able to constrain the chemistry that leads to the formation of lowvolatility products. Although the formation of ROOR from the reaction of two peroxy radicals (RO 2 ) has generally been considered as a minor channel, based on the gas-phase and aerosol-phase data it appears that RO 2 +RO 2 reaction (self reaction or cross-reaction) in the gas phase yielding ROOR products is a dominant SOA formation pathway. A wide array of organic nitrates and peroxides are identified in the aerosol formed and mechanisms for SOA formation are proposed. Using a uniform SOA yield of 10% (corresponding to M o ∼ =10 µg m −3 ), it is estimated that ∼2 to 3 Tg yr −1 of SOA results from isoprene+NO 3 . The extent to which the results from this study can be applied to conditions in the atmosphere depends on the fate of peroxy radicals in the nighttime troposphere.

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Section: Offline Chemical Analysismentioning

confidence: 96%

Section: Proposed Mechanisms Of Soa Formationmentioning

confidence: 98%

Section: Offline Chemical Analysismentioning

confidence: 99%

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Secondary organic aerosol (SOA) formation from reaction of isoprene with nitrate radicals (NO3)

et al. 2008

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“…The signal at m/z 43 is a CH 3 CO + fragment ion that cannot be assigned to a specific parent molecule but MS/MS spectra from hydroxy-nitrates show an intense fragment at m/z 43 (Kwok et al, 1996). The signal at m/z 85 may be an additional hydroxy-nitrate signal [MH + -HNO 3 ] although the epoxide (C 5 H 8 O), which has been observed in low-pressure studies but is not thought likely at atmospheric pressure (Skov et al, 1994) would also be detected at that mass. Nitrooxy-carbonyls may give rise to a m/z 99 signal [MH + -HNO 2 ] in addition to the signal at m/z 146 and the ion signal at m/z 162 seems to be specific for the nitrooxy-peroxy-nitrates [MH + -HNO 2 ].…”

Section: Product Identificationmentioning

confidence: 99%

A product study of the isoprene+NO3 reaction

et al. 2009

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Abstract. Oxidation of isoprene through reaction with NO 3 radicals is a significant sink for isoprene that persists after dark. The main products of the reaction are multifunctional nitrates. These nitrates constitute a significant NO x sink in the nocturnal boundary layer and they likely play an important role in formation of secondary organic aerosol. Products of the isoprene+NO 3 reaction will, in many locations, be abundant enough to affect nighttime radical chemistry and to persist into daytime where they may represent a source of NO x . Product formation in the isoprene + NO 3 reaction was studied in a smog chamber at Purdue University. Isoprene nitrates and other hydrocarbon products were observed using Proton Transfer Reaction-Mass Spectrometry (PTR-MS) and reactive nitrogen products were observed using Thermal Dissociation-Laser Induced Fluorescence (TD-LIF). The organic nitrate yield is found to be 65±12% of which the majority was nitrooxy carbonyls and the combined yield of methacrolein and methyl vinyl ketone (MACR+MVK) is found to be ∼10%. PTR-MS measurements of nitrooxy carbonyls and TD-LIF measurements of total organic nitrates agreed well. The PTR-MS also observed a series of minor oxidation products which were tentatively identified and their yields quantified These other oxidation products are used as additional constraints on the reaction mechanism.

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“…The reaction is known to produce unsaturated organic nitrates with a yield of approximately 80% as first-generation products (Barnes et al, 1990). These nitrates consist of unsaturated hydroxy-, hydroperoxy-and carbonyl nitrates (Kwok et al, 1996;Skov et al, 1992Skov et al, , 1994Tuazon et al, 1999;Berndt and Boge, 1997), with a recent study also showing evidence for formation of dinitrates and oligomers (Ng et al, 2008). The subsequent fates of such compounds are poorly understood and are an important uncertainty in isoprene oxidation models (Fan and Zhang, 2004;Paulson and Seinfeld, 1992).…”

Section: Introductionmentioning

confidence: 99%

Nocturnal isoprene oxidation over the Northeast United States in summer and its impact on reactive nitrogen partitioning and secondary organic aerosol

et al. 2009

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Abstract. Isoprene is the largest single VOC emission to the atmosphere. Although it is primarily oxidized photochemically during daylight hours, late-day emissions that remain in the atmosphere at sunset undergo oxidation by NO 3 in regionally polluted areas with large NO x levels. A recent aircraft study examined isoprene and its nocturnal oxidants in a series of night flights across the Northeast US, a region with large emissions of both isoprene and NO x . Substantial amounts of isoprene that were observed after dark were strongly anticorrelated with measured NO 3 and were the most important factor determining the lifetime of this radical. The products of photochemical oxidation of isoprene, methyl vinyl ketone and methacrolein, were more uniformly distributed, and served as tracers for the presence of isoprene at sunset, prior to its oxidation by NO 3 . A determination of the mass of isoprene oxidized in darkness showed it to be a large fraction (>20%) of emitted isoprene. Organic nitrates produced from the NO 3 +isoprene reaction, though not directly measured, were estimated to account for 2-9% of total reactive nitrogen. The mass of isoprene oxidized by NO 3 was comparable to and correlated with the organic aerosol Correspondence to: S. S. Brown (steven.s.brown@noaa.gov) loading for flights with relatively low organic aerosol background. The contribution of nocturnal isoprene oxidation to secondary organic aerosol was determined in the range 1-17%, and isoprene SOA mass derived from NO 3 was calculated to exceed that due to OH by approximately 50%.

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Epoxide formation in the reactions of the nitrate radical with 2,3-dimethyl-2-butene, cis- and trans-2-butene and isoprene

Cited by 46 publications

References 14 publications

Secondary organic aerosol (SOA) formation from reaction of isoprene with nitrate radicals (NO<sub>3</sub>)

Secondary organic aerosol (SOA) formation from reaction of isoprene with nitrate radicals (NO<sub>3</sub>)

A product study of the isoprene+NO<sub>3</sub> reaction

Nocturnal isoprene oxidation over the Northeast United States in summer and its impact on reactive nitrogen partitioning and secondary organic aerosol

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Epoxide formation in the reactions of the nitrate radical with 2,3-dimethyl-2-butene, cis- and trans-2-butene and isoprene

Cited by 46 publications

References 14 publications

Secondary organic aerosol (SOA) formation from reaction of isoprene with nitrate radicals (NO&lt;sub&gt;3&lt;/sub&gt;)

Secondary organic aerosol (SOA) formation from reaction of isoprene with nitrate radicals (NO&lt;sub&gt;3&lt;/sub&gt;)

A product study of the isoprene+NO&lt;sub&gt;3&lt;/sub&gt; reaction

Nocturnal isoprene oxidation over the Northeast United States in summer and its impact on reactive nitrogen partitioning and secondary organic aerosol

Contact Info

Product

Resources

About

Secondary organic aerosol (SOA) formation from reaction of isoprene with nitrate radicals (NO<sub>3</sub>)

Secondary organic aerosol (SOA) formation from reaction of isoprene with nitrate radicals (NO<sub>3</sub>)

A product study of the isoprene+NO<sub>3</sub> reaction