Observation of Hydroxycarbonyls from the OH Radical-Initiated Reaction of Isoprene

Kwok, Eric S. C.; Atkinson, Roger; Arey, Janet

doi:10.1021/es00009a046

Cited by 105 publications

(145 citation statements)

References 8 publications

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“…We expect their main appearance at this ion mass [MH + -HNO 3 ]. m/z 83 may also be generated from the C 5 -hydroxy-carbonyls [MH + -H 2 O] but previous work (Kwok et al, 1995;Zhao et al, 2004) indicates that detection of C 5 -hydroxycarbonyls at m/z 101 dominates over that at m/z 83 and we therefore conclude that the m/z = 83 signal is dominated by nitrooxy-carbonyls. We attribute the ion signal at m/z 146 to nitrooxy-carbonyls but note that it may also be produced In addition to the ion signals reported by Kwok et al (1996), we also observed signals at m/z 31, 43, 85, 87, 132 and 162.…”

Section: Product Identificationmentioning

confidence: 62%

A product study of the isoprene+NO<sub>3</sub> 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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Section: Product Identificationmentioning

confidence: 62%

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

et al. 2009

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“…These products ( Fig. 1) and their yields have received considerable laboratory study (Tuazon and Atkinson, 1990b;Paulson et al, 1992;Miyoshi et al, 1994;Kwok et al, 1995;Sprengnether et al, 2002;Zhao et al, 2004;Fan and Zhang, 2004). The distribution of such products depends on the fate of the hydroxy-peroxy (RO 2 ) radical: products from the RO 2 +NO reaction include methacrolein, methyl vinyl ketone, and hydroxynitrates, whereas hydroxyhydroperoxides are formed from RO 2 +HO 2 .…”

Section: Gas-phase Oxidationmentioning

confidence: 99%

A review of Secondary Organic Aerosol (SOA) formation from isoprene

2009

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Abstract. Recent field and laboratory evidence indicates that the oxidation of isoprene, (2-methyl-1,3-butadiene, C 5 H 8 ) forms secondary organic aerosol (SOA). Global biogenic emissions of isoprene (600 Tg yr −1 ) are sufficiently large that the formation of SOA in even small yields results in substantial production of atmospheric particulate matter, likely having implications for air quality and climate. Here we present a review of field measurements, experimental work, and modeling studies aimed at understanding the mechanisms, yield, and atmospheric importance of isoprene-derived SOA. SOA yields depend on a number of factors, including organic aerosol loading (M o ), NO x level (RO 2 chemistry), and, because of the importance of multigenerational chemistry, the degree of oxidation. These dependences are not always included in SOA modules used in atmospheric transport models, and instead most yield parameterizations rely on a single set of chamber experiments (carried out over a limited range of conditions); this may lead to very different estimates of the atmospheric importance of isoprene SOA. New yield parameterizations, based on all available laboratory data (M o =0-50 µg m −3 ), are presented here, so that SOA formation may be computed as a function of M o , NO x level, and temperature. Current research needs and future research directions are identified.

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“…25 Dibble has reported another potential pathway for the (E)-OHC 5 H 7 OH isomer from theoretical studies, which leads to the formation of a C 5 -dihydroxycarbonyl compound. 25 However, no product study has observed this species, 29 and we have concluded that the yield of this channel would be negligible; 55 hence we have not included this channel in our model. Dibble has also reported another potential fate of the Z-δ-hydroxyalkylalkoxy radical when it reacts with another oxygen molecule following electron delocalization.…”

Section: +34mentioning

confidence: 99%

Isomer-Selective Study of the OH-Initiated Oxidation of Isoprene in the Presence of O₂ and NO: 2. The Major OH Addition Channel

et al. 2010

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We report the first isomeric-selective study of the dominant isomeric pathway in the OH-initiated oxidation of isoprene in the presence of O 2 and NO using the laser photolysis-laser induced fluorescence (LP-LIF) technique. The photolysis of monodeuterated/nondeuterated 2-iodo-2-methylbut-3-en-1-ol results exclusively in the dominant OH-isoprene addition product, providing important insight into the oxidation mechanism. On the basis of kinetic analysis of OH cycling experiments, we have determined the rate constant for O 2 addition to the hydroxyalkyl radical to be 1.0 -0.5 +1.7 × 10 -12 cm 3 s -1 , and we find a value of 8.1 -2.3 +3.4 × 10 -12 cm 3 s -1 for the overall reaction rate constant of the resulting hydroxyperoxy radical with NO. We also report the first clear experimental evidence of the (E) form of the δ-hydroxyalkoxy channel through isotopic labeling experiments and quantify its branching ratio to be (10 ( 3)%. This puts a rigorous upper limit on the branching of the (E)-δ-hydroxyalkoxy radical channel. Since our measured isomeric-selective rate constants for the dominant outer channel in OH-initiated isoprene chemistry are similar to the overall rate constants derived from nonisomeric kinetics, we predict that the remaining outer addition channel will have similar reactivity.

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Observation of Hydroxycarbonyls from the OH Radical-Initiated Reaction of Isoprene

Cited by 105 publications

References 8 publications

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

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

A review of Secondary Organic Aerosol (SOA) formation from isoprene

Isomer-Selective Study of the OH-Initiated Oxidation of Isoprene in the Presence of O₂ and NO: 2. The Major OH Addition Channel

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Observation of Hydroxycarbonyls from the OH Radical-Initiated Reaction of Isoprene

Cited by 105 publications

References 8 publications

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

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

A review of Secondary Organic Aerosol (SOA) formation from isoprene

Isomer-Selective Study of the OH-Initiated Oxidation of Isoprene in the Presence of O2 and NO: 2. The Major OH Addition Channel

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

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

Isomer-Selective Study of the OH-Initiated Oxidation of Isoprene in the Presence of O₂ and NO: 2. The Major OH Addition Channel