Kinetics and Product Yields of the OH Initiated Oxidation of Hydroxymethyl Hydroperoxide

Hydroxymethyl hydroperoxide (HMHP), formed in the reaction of the C1 Criegee intermediate with water, is among the most abundant organic peroxides in the atmosphere. Although reaction with OH is thought to represent one of the most important atmospheric removal processes for HMHP, this reaction has been largely unstudied in the laboratory. Here, we present measurements of the kinetics and products formed in the reaction of HMHP with OH. HMHP was oxidized by OH in an environmental chamber; the decay of the hydroperoxide and the formation of formic acid and formaldehyde were monitored over time using CF3O- chemical ionization mass spectrometry (CIMS) and laser induced fluorescence (LIF). The loss of HMHP by reaction with OH is measured relative to the loss of 1,2-butanediol [k1;2-butanediol+OH = (27:0 5:6) 10- exp12 cm3 molecule-1s-1]. We find that HMHP reacts with OH at 295 K with a rate coefficient of (7.1 1.5) 10-12 cm3 molecule-1s-1, with the formic acid to formaldehyde yield in a ratio of 0:880:21 and independent of NO concentration (31010 1.51013 molecule cm-3). We suggest that, exclusively, abstraction of the methyl hydrogen of HMHP results in formic acid while abstraction of the hydroperoxy hydrogen results in formaldehyde. We further evaluate the relative importance of HMHP sinks and use global simulations from GEOS-Chem to estimate that HMHP oxidation by OH contributes 1.7 Tg yr-1 (1-3%) of global annual formic acid production

Kinetics and Product Yields of the OH Initiated Oxidation of Hydroxymethyl Hydroperoxide

Hydroxymethyl hydroperoxide (HMHP), formed in the reaction of the C1 Criegee intermediate with water, is among the most abundant organic peroxides in the atmosphere. Although reaction with OH is thought to represent one of the most important atmospheric removal processes for HMHP, this reaction has been largely unstudied in the laboratory. Here, we present measurements of the kinetics and products formed in the reaction of HMHP with OH. HMHP was oxidized by OH in an environmental chamber; the decay of the hydroperoxide and the formation of formic acid and formaldehyde were monitored over time using CF_3O– chemical ionization mass spectrometry (CIMS) and laser-induced fluorescence (LIF). The loss of HMHP by reaction with OH is measured relative to the loss of 1,2-butanediol [k_(1,2-butanediol+OH) = (27.0 ± 5.6) × 10^(–12) cm^3 molecule^(–1)s^(–1)]. We find that HMHP reacts with OH at 295 K with a rate coefficient of (7.1 ± 1.5) × 10^(–12) cm^3molecule^(–1)s^(–1), with the formic acid to formaldehyde yield in a ratio of 0.88 ± 0.21 and independent of NO concentration (3 × 10^(10) – 1.5 × 10^(13) molecules cm^(–3)). We suggest that, exclusively, abstraction of the methyl hydrogen of HMHP results in formic acid, while abstraction of the hydroperoxy hydrogen results in formaldehyde. We further evaluate the relative importance of HMHP sinks and use global simulations from GEOS-Chem to estimate that HMHP oxidation by OH contributes 1.7 Tg yr^(–1) (1–3%) of global annual formic acid production

Emissions of Glyoxal and Other Carbonyl Compounds from Agricultural Biomass Burning Plumes Sampled by Aircraft

We report enhancements of glyoxal and methylglyoxal relative to carbon monoxide and formaldehyde in agricultural biomass burning plumes intercepted by the NOAA WP-3D aircraft during the 2013 Southeast Nexus and 2015 Shale Oil and Natural Gas Nexus campaigns. Glyoxal and methylglyoxal were measured using broadband cavity enhanced spectroscopy, which for glyoxal provides a highly selective and sensitive measurement. While enhancement ratios of other species such as methane and formaldehyde were consistent with previous measurements, glyoxal enhancements relative to carbon monoxide averaged 0.0016 ± 0.0009, a factor of 4 lower than values used in global models. Glyoxal enhancements relative to formaldehyde were 30 times lower than previously reported, averaging 0.038 ± 0.02. Several glyoxal loss processes such as photolysis, reactions with hydroxyl radicals, and aerosol uptake were found to be insufficient to explain the lower measured values of glyoxal relative to other biomass burning trace gases, indicating that glyoxal emissions from agricultural biomass burning may be significantly overestimated. Methylglyoxal enhancements were three to six times higher than reported in other recent studies, but spectral interferences from other substituted dicarbyonyls introduce an estimated correction factor of 2 and at least a 25% uncertainty, such that accurate measurements of the enhancements are difficult

Kinetics and Product Yields of the OH Initiated Oxidation of Hydroxymethyl Hydroperoxide

Hydroxymethyl hydroperoxide (HMHP), formed in the reaction of the C₁ Criegee intermediate with water, is among the most abundant organic peroxides in the atmosphere. Although reaction with OH is thought to represent one of the most important atmospheric removal processes for HMHP, this reaction has been largely unstudied in the laboratory. Here, we present measurements of the kinetics and products formed in the reaction of HMHP with OH. HMHP was oxidized by OH in an environmental chamber; the decay of the hydroperoxide and the formation of formic acid and formaldehyde were monitored over time using CF₃O^– chemical ionization mass spectrometry (CIMS) and laser-induced fluorescence (LIF). The loss of HMHP by reaction with OH is measured relative to the loss of 1,2-butanediol [<i>k</i>_{1,2‑butanediol+OH} = (27.0 ± 5.6) × 10^–12 cm³ molecule^–1s^–1]. We find that HMHP reacts with OH at 295 K with a rate coefficient of (7.1 ± 1.5) × 10^–12 cm³ molecule^–1s^–1, with the formic acid to formaldehyde yield in a ratio of 0.88 ± 0.21 and independent of NO concentration (3 × 10¹⁰ – 1.5 × 10¹³ molecules cm^–3). We suggest that, exclusively, abstraction of the methyl hydrogen of HMHP results in formic acid, while abstraction of the hydroperoxy hydrogen results in formaldehyde. We further evaluate the relative importance of HMHP sinks and use global simulations from GEOS-Chem to estimate that HMHP oxidation by OH contributes 1.7 Tg yr^–1 (1–3%) of global annual formic acid production