Atmospheric Fate of Methacrolein. 2. Formation of Lactone and Implications for Organic Aerosol Production

Kjaergaard, Henrik G.; Knap, Hasse C.; Ørnsø, Kristian Baruël; Jørgensen, Solvejg; Crounse, J. D.; Wennberg, P. O.

doi:10.1021/jp210853h

Cited by 59 publications

(82 citation statements)

References 46 publications

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“…This translates to a calculated 0% yield of HMML in the HMPPN + OH reaction (100% reacts with O 2 ). In comparison, Kjaergaard et al 17 estimated the decomposition of A* to HMML is fast under the conditions they studied (k (A*-HMML) B 4 Â 10 9 s À1 ), translating to a 61-74% HMML yield from MPAN (2% is stabilized to A). The theoretical-derived kinetic results are consistent with observations for these C 4 APN-derived alkyl radicals.…”

Section: Resultsmentioning

confidence: 95%

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Mechanism of the hydroxyl radical oxidation of methacryloyl peroxynitrate (MPAN) and its pathway toward secondary organic aerosol formation in the atmosphere

Nguyen

Bates

Crounse

et al. 2015

Phys. Chem. Chem. Phys.

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Methacryloyl peroxynitrate (MPAN), the acyl peroxynitrate of methacrolein, has been suggested to be an important secondary organic aerosol (SOA) precursor from isoprene oxidation. Yet, the mechanism by which MPAN produces SOA through reaction with the hydroxyl radical (OH) is unclear. We systematically evaluate three proposed mechanisms in controlled chamber experiments and provide the first experimental support for the theoretically-predicted lactone formation pathway from the MPAN + OH reaction, producing hydroxymethyl-methyl-a-lactone (HMML). The decomposition of the MPAN-OH adduct yields HMML + NO 3 (B75%) and hydroxyacetone + CO + NO 3 (B25%), out-competing its reaction with atmospheric oxygen. The production of other proposed SOA precursors, e.g., methacrylic acid epoxide (MAE), from MPAN and methacrolein are negligible (o2%). Furthermore, we show that the beta-alkenyl moiety of MPAN is critical for lactone formation. Alkyl radicals formed cold via H-abstraction by OH do not decompose to HMML, even if they are structurally identical to the MPAN-OH adduct. The SOA formation from HMML, from polyaddition of the lactone to organic compounds at the particle interface or in the condensed phase, is close to unity under dry conditions. However, the SOA yield is sensitive to particle liquid water and solvated ions. In hydrated inorganic particles, HMML reacts primarily with H 2 O to produce the monomeric 2-methylglyceric acid (2MGA) or with aqueous sulfate and nitrate to produce the associated organosulfate and organonitrate, respectively. 2MGA, a tracer for isoprene SOA, is semivolatile and its accommodation in aerosol water decreases with decreasing pH. Conditions that enhance the production of neutral 2MGA suppress SOA mass from the HMML channel. Considering the liquid water content and pH ranges of ambient particles, 2MGA will exist largely as a gaseous compound in some parts of the atmosphere.

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Section: Resultsmentioning

confidence: 95%

“…2 shows three possible pathways leading to SOA production that have been proposed by independent works. 13,17,18 The initial step of the MPAN photooxidation is OH addition to the double bond, primarily generating the energetically hot tertiary alkyl radical of MPAN (A*, Fig. 2).…”

Section: Introductionmentioning

confidence: 99%

Mechanism of the hydroxyl radical oxidation of methacryloyl peroxynitrate (MPAN) and its pathway toward secondary organic aerosol formation in the atmosphere

Nguyen

Bates

Crounse

et al. 2015

Phys. Chem. Chem. Phys.

Self Cite

120

150

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“…MACR can be oxidized to produce peroxymethacrylic nitric anhydride (MPAN), which is a precursor to methacrylic acid epoxide (MAE) and hydroxymethylmethyl-α-lactone (HMML), and these compounds can undergo reactive uptake to produce PM (Kjaergaard et al, 2012;Lin et al, 2013;Worton et al, 2013;Nguyen et al, 2015). Glyoxal produced from isoprene oxidation can contribute to PM production (Volkamer et al, 2007;Ervens and Volkamer, 2010;McNeill et al, 2012;Marais et al, 2016).…”

Section: Molecular Tracersmentioning

confidence: 99%

Influence of urban pollution on the production of organic particulate matter from isoprene epoxydiols in central Amazonia

et al. 2017

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Abstract. The atmospheric chemistry of isoprene contributes to the production of a substantial mass fraction of the particulate matter (PM) over tropical forests. Isoprene epoxydiols (IEPOX) produced in the gas phase by the oxidation of isoprene under HO 2 -dominant conditions are subsequently taken up by particles, thereby leading to production of secondary organic PM. The present study investigates possible perturbations to this pathway by urban pollution. The measurement site in central Amazonia was located 4 to 6 h downwind of Manaus, Brazil. Measurements took place from February through March 2014 of the wet season, as part of the GoAmazon2014/5 experiment. Mass spectra of organic PM collected with an Aerodyne Aerosol Mass Spectrometer were analyzed by positive-matrix factorization. One resolved statistical factor ("IEPOX-SOA factor") was associated with PM production by the IEPOX pathway. The IEPOX-SOA factor loadings correlated with independently measured mass concentrations of tracers of IEPOX-derived PM, namely C 5 -alkene triols and 2-methyltetrols (R = 0.96 and 0.78, respectively). The factor loading, as well as the ratio f of the loading to organic PM mass concentration, decreased under polluted compared to background conditions. For an increase in NO y concentration from 0.5 to 2 ppb, the factor loading and f decreased by two to three fold. Overall, sulfate concentration explained 37 % of the variability in the factor loading. After segregation of factor loading into subsets based on NO y concentration, the sulfate concentration explained up to 75 % of the variability. Considering both factors, the data sets show that the suppressing effects of increased NO concentrations dominated over the enhancing effects of higher sulfate concentrations. The pollution from Manaus elevated NO y concentrations more significantly than sulfate concenPublished by Copernicus Publications on behalf of the European Geosciences Union. 6612 S. S. de Sá et al.: Influence of urban pollution on the production of organic particulate matter trations relative to background conditions. In this light, increased emissions of nitrogen oxides, as anticipated for some scenarios of Amazonian economic development, could significantly alter pathways of PM production that presently prevail over the tropical forest, implying changes to air quality and regional climate.

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“…These uncertainties stem from, for example, the large range in reported yields for isoprene nitrates (4-15 %) (Paulot et al, 2009a), disagreements up to 90 % in reported MAC and MVK yields from the low-NO pathway (Liu et al, 2013, and references therein), various proposed sources of SOA from the high-NO pathway Kjaergaard et al, 2012;Lin et al, 2013), missing contributions to SOA mass from the low-NO pathway , uncharacterized fates of oxidized species like HPALDs (which may have isomer dependence), incomplete understanding of oxygen incorporation (Peeters et al, 2009;Crounse et al, 2013), and under-characterized impact of RO 2 lifetimes on chamber results . The OH oxidation of α-pinene (Eddingsaas et al, 2012) and other monoterpenes is less well characterized than that of isoprene, but, in general, proceeds through analogous steps.…”

Section: Oh Oxidationmentioning

confidence: 99%

“…19,24,26,and 30): experiments aimed specifically at studying chemistry leading to SOA formation have overlapping goals with those described above. One focus was the evaluation of the SOA-formation route from APNs by the proposed dioxo ketone, lactone, and epoxide mechanisms Kjaergaard et al, 2012;Lin et al, 2013), none of which has yet been validated by independent studies. However, the proposed epoxide chemistry has been integrated into some studies published soon after the proposal by Lin et al (2013) (Worton et al, 2013;Pye et al, 2013).…”

Section: Experimental Designmentioning

confidence: 99%

Overview of the Focused Isoprene eXperiment at the California Institute of Technology (FIXCIT): mechanistic chamber studies on the oxidation of biogenic compounds

et al. 2014

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Abstract. The Focused Isoprene eXperiment at the California Institute of Technology (FIXCIT) was a collaborative atmospheric chamber campaign that occurred during January 2014. FIXCIT is the laboratory component of a synergistic field and laboratory effort aimed toward (1) better understanding the chemical details behind ambient observations relevant to the southeastern United States, (2) advancing the knowledge of atmospheric oxidation mechanisms of important biogenic hydrocarbons, and (3) characterizing the behavior of field instrumentation using authentic standards. Approximately 20 principal scientists from 14 academic and government institutions performed parallel measurements at a forested site in Alabama and at the atmospheric chambers at Caltech. During the 4 week campaign period, a series of chamber experiments was conducted to investigate the dark-and photo-induced oxidation of isoprene, α-pinene, methacrolein, pinonaldehyde, acylperoxy nitrates, isoprene hydroxy nitrates (ISOPN), isoprene hydroxy hydroperoxides (ISOPOOH), and isoprene epoxydiols (IEPOX) in a highly controlled and atmospherically relevant manner. Pinonaldehyde and isomer-specific standards of ISOPN, ISOPOOH, and IEPOX were synthesized and contributed by campaign participants, which enabled explicit exploration into the oxidation mechanisms and instrument responses for these important atmospheric compounds. The present overview describes the goals, experimental design, instrumental techniques, and preliminary observations from the campaign. This work provides context for forthcoming publications affiliated with the FIXCIT campaign. Insights from FIXCIT are anticipated to aid significantly in interpretation of field data and the revision of mechanisms currently implemented in regional and global atmospheric models.

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Atmospheric Fate of Methacrolein. 2. Formation of Lactone and Implications for Organic Aerosol Production

Cited by 59 publications

References 46 publications

Mechanism of the hydroxyl radical oxidation of methacryloyl peroxynitrate (MPAN) and its pathway toward secondary organic aerosol formation in the atmosphere

Mechanism of the hydroxyl radical oxidation of methacryloyl peroxynitrate (MPAN) and its pathway toward secondary organic aerosol formation in the atmosphere

Influence of urban pollution on the production of organic particulate matter from isoprene epoxydiols in central Amazonia

Overview of the Focused Isoprene eXperiment at the California Institute of Technology (FIXCIT): mechanistic chamber studies on the oxidation of biogenic compounds

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