Atmospheric Fate of Methyl Vinyl Ketone: Peroxy Radical Reactions with NO and HO<sub>2</sub>

Praske, Eric; Crounse, J. D.; Bates, Kelvin H.; Kurtén, Theo; Kjaergaard, Henrik G.; Wennberg, P. O.

doi:10.1021/jp5107058

Cited by 106 publications

(177 citation statements)

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“…This mechanism is based on Mao et al (2013b), but has been significantly revised to incorporate recent laboratory updates on isoprene oxidation by OH, ozone, and NO 3 (Schwantes et al, 2015;Bates et al, 2014Bates et al, , 2016St. Clair et al, 2016;Praske et al, 2015;Müller et al, 2014;Lee et al, 2014;Crounse et al, 2011). One major feature is the suppression of the δ-isoprene hydroxy peroxy radical (δ-ISOPO 2 ) and subsequent reaction pathways in the model, as these channels are considered to be of minor importance under ambient conditions Bates et al, 2014).…”

Section: Am3 Modelmentioning

confidence: 99%

“…The treatment of β-and δ-ISOPO 2 will not only affect the speciation of organic nitrates but also the production of ozone due to different NO x recycling efficiency in their secondary products. We also include updated chemistry for methylvinyl ketone (MVK; Praske et al, 2015), an updated yield of hydroxy hydroperoxides (ISOPOOH; Bates et al, 2016;St. Clair et al, 2016), fast photolysis of carbonyl organic nitrates , and an updated ozonolysis rate of ISOPNB .…”

Section: Am3 Modelmentioning

confidence: 99%

“…Clair et al, 2016), fast photolysis of carbonyl organic nitrates , and an updated ozonolysis rate of ISOPNB . In addition, we reduce the yield of organic nitrates (MACRN) from methacrolein (MACR) oxidation from 15 to 3 %, which is estimated from the measured yield of nitrates from MVK oxidation (Praske et al, 2015). Another major model revision involves the treatment of the nighttime oxidation of isoprene.…”

Section: Am3 Modelmentioning

confidence: 99%

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Decadal changes in summertime reactive oxidized nitrogen and surface ozone over the Southeast United States

Mao

Fiore

et al. 2018

Atmos. Chem. Phys.

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Published by Copernicus Publications on behalf of the European Geosciences Union. 2342 J. Li et al.: Decadal changes in summertime reactive oxidized nitrogen and surface ozone Abstract. Widespread efforts to abate ozone (O 3 ) smog have significantly reduced emissions of nitrogen oxides (NO x ) over the past 2 decades in the Southeast US, a place heavily influenced by both anthropogenic and biogenic emissions. How reactive nitrogen speciation responds to the reduction in NO x emissions in this region remains to be elucidated. Here we exploit aircraft measurements from ICARTT (JulyAugust 2004), SENEX (June-July 2013), and SEAC 4 RS (August-September 2013) and long-term ground measurement networks alongside a global chemistry-climate model to examine decadal changes in summertime reactive oxidized nitrogen (RON) and ozone over the Southeast US. We show that our model can reproduce the mean vertical profiles of major RON species and the total (NO y ) in both 2004 and 2013. Among the major RON species, nitric acid (HNO 3 ) is dominant (∼ 42-45 %), followed by NO x (31 %), total peroxy nitrates ( PNs; 14 %), and total alkyl nitrates ( ANs; 9-12 %) on a regional scale. We find that most RON species, including NO x , PNs, and HNO 3 , decline proportionally with decreasing NO x emissions in this region, leading to a similar decline in NO y . This linear response might be in part due to the nearly constant summertime supply of biogenic VOC emissions in this region. Our model captures the observed relative change in RON and surface ozone from 2004 to 2013. Model sensitivity tests indicate that further reductions of NO x emissions will lead to a continued decline in surface ozone and less frequent high-ozone events.

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Section: Am3 Modelmentioning

confidence: 99%

Section: Am3 Modelmentioning

confidence: 99%

Section: Am3 Modelmentioning

confidence: 99%

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Decadal changes in summertime reactive oxidized nitrogen and surface ozone over the Southeast United States

Mao

Fiore

et al. 2018

Atmos. Chem. Phys.

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“…So, for measured OH to be greater than modeled OH, there must be unknown OH sources, which could be either primary sources, such as photolysis of an unknown chemical species, or secondary sources, such as recycling of HO x to OH within the BVOC oxidation mechanisms. These discrepancies and the speculation about OH recycling have led to increased interest in the detailed chemical oxidation mechanisms for these BVOCs, particularly isoprene (Paulot et al 2009;Peeters et al 2009;Peeters and Müller 2010;Crounse et al 2011Crounse et al , 2012Crounse et al , 2013Praske et al 2015;St. Clair et al 2015).…”

Section: Introductionmentioning

confidence: 99%

Testing Atmospheric Oxidation in an Alabama Forest

Feiner

Brune

Miller

et al. 2016

Journal of the Atmospheric Sciences

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The chemical species emitted by forests create complex atmospheric oxidation chemistry and influence global atmospheric oxidation capacity and climate. The Southern Oxidant and Aerosol Study (SOAS) provided an opportunity to test the oxidation chemistry in a forest where isoprene is the dominant biogenic volatile organic compound. Hydroxyl (OH) and hydroperoxyl (HO 2 ) radicals were two of the hundreds of atmospheric chemical species measured, as was OH reactivity (the inverse of the OH lifetime). OH was measured by laser-induced fluorescence (LIF) and by taking the difference in signals without and with an OH scavenger that was added just outside the instrument's pinhole inlet. To test whether the chemistry at SOAS can be simulated by current model mechanisms, OH and HO 2 were evaluated with a box model using two chemical mechanisms: Master Chemical Mechanism, version 3.2 (MCMv3.2), augmented with explicit isoprene chemistry and MCMv3.3.1. Measured and modeled OH peak at about 10 6 cm 23 and agree well within combined uncertainties. Measured and modeled HO 2 peak at about 27 pptv and also agree well within combined uncertainties. Median OH reactivity cycled between about 11 s 21 at dawn and about 26 s 21 during midafternoon. A good test of the oxidation chemistry is the balance between OH production and loss rates using measurements; this balance was observed to within uncertainties. These SOAS results provide strong evidence that the current isoprene mechanisms are consistent with measured OH and HO 2 and, thus, capture significant aspects of the atmospheric oxidation chemistry in this isoprene-rich forest.

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“…This was shown for the acetylperoxy radical with an OH yield of 50 % Winiberg et al, 2016). In a recent study by Praske et al (2015), product yields from the reaction of MVK derived peroxy radicals with HO 2 were investigated. Similar to the acetylperoxy radical, product yields demonstrated that only one third of the reaction yields hydroxyperoxides and that two additional reaction channels exist, both of which could lead to the reformation of OH.…”

Section: Introductionmentioning

confidence: 92%

Investigation of the oxidation of methyl vinyl ketone (MVK) by OH radicals in the atmospheric simulation chamber SAPHIR

Fuchs¹,

Albrecht²,

Acir

et al. 2018

Atmos. Chem. Phys.

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Abstract. The photooxidation of methyl vinyl ketone (MVK) was investigated in the atmospheric simulation chamber SAPHIR for conditions at which organic peroxy radicals (RO 2 ) mainly reacted with NO ("high NO" case) and for conditions at which other reaction channels could compete ("low NO" case). Measurements of trace gas concentrations were compared to calculated concentration time series applying the Master Chemical Mechanism (MCM version 3.3.1). Product yields of methylglyoxal and glycolaldehyde were determined from measurements. For the high NO case, the methylglyoxal yield was (19 ± 3) % and the glycolaldehyde yield was (65 ± 14) %, consistent with recent literature studies. For the low NO case, the methylglyoxal yield reduced to (5 ± 2) % because other RO 2 reaction channels that do not form methylglyoxal became important. Consistent with literature data, the glycolaldehyde yield of (37 ± 9) % determined in the experiment was not reduced as much as implemented in the MCM, suggesting additional reaction channels producing glycolaldehyde. At the same time, direct quantification of OH radicals in the experiments shows the need for an enhanced OH radical production at low NO conditions similar to previous studies investigating the oxidation of the parent VOC isoprene and methacrolein, the second major oxidation product of isoprene. For MVK the model-measurement discrepancy was up to a factor of 2. Product yields and OH observations were consistent with assumptions of additional RO 2 plus HO 2 reaction channels as proposed in literature for the major RO 2 species formed from the reaction of MVK with OH. However, this study shows that also HO 2 radical concentrations are underestimated by the model, suggesting that additional OH is not directly produced from RO 2 radical reactions, but indirectly via increased HO 2 . Quantum chemical calculations show that HO 2 could be produced from a fast 1,4-H shift of the second most important MVK derived RO 2 species (reaction rate constant 0.003 s −1 ). However, additional HO 2 from this reaction was not sufficiently large to bring modelled HO 2 radical concentrations into agreement with measurements due to the small yield of this RO 2 species. An additional reaction channel of the major RO 2 species with a reaction rate constant of (0.006 ± 0.004) s −1 would be required that produces concurrently HO 2 radicals and glycolaldehyde to achieve modelmeasurement agreement. A unimolecular reaction similar to the 1,5-H shift reaction that was proposed in literature for RO 2 radicals from MVK would not explain product yields for conditions of experiments in this study. A set of H-migration reactions for the main RO 2 radicals were investigated by quantum chemical and theoretical kinetic methodologies, but did not reveal a contributing route to HO 2 radicals or glycolaldehyde.

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Atmospheric Fate of Methyl Vinyl Ketone: Peroxy Radical Reactions with NO and HO₂

Cited by 106 publications

References 59 publications

Decadal changes in summertime reactive oxidized nitrogen and surface ozone over the Southeast United States

Decadal changes in summertime reactive oxidized nitrogen and surface ozone over the Southeast United States

Testing Atmospheric Oxidation in an Alabama Forest

Investigation of the oxidation of methyl vinyl ketone (MVK) by OH radicals in the atmospheric simulation chamber SAPHIR

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Atmospheric Fate of Methyl Vinyl Ketone: Peroxy Radical Reactions with NO and HO2

Cited by 106 publications

References 59 publications

Decadal changes in summertime reactive oxidized nitrogen and surface ozone over the Southeast United States

Decadal changes in summertime reactive oxidized nitrogen and surface ozone over the Southeast United States

Testing Atmospheric Oxidation in an Alabama Forest

Investigation of the oxidation of methyl vinyl ketone (MVK) by OH radicals in the atmospheric simulation chamber SAPHIR

Contact Info

Product

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Atmospheric Fate of Methyl Vinyl Ketone: Peroxy Radical Reactions with NO and HO₂