Kelvin H. Bates

Gas Phase Production and Loss of Isoprene Epoxydiols

Isoprene epoxydiols (IEPOX) form in high yields from the OH-initiated oxidation of isoprene under low-NO conditions. These compounds contribute significantly to secondary organic aerosol formation. Their gas-phase chemistry has, however, remained largely unexplored. In this study, we characterize the formation of IEPOX isomers from the oxidation of isoprene by OH. We find that cis-β- and trans-β-IEPOX are the dominant isomers produced, and that they are created in an approximate ratio of 1:2 from the low-NO oxidation of isoprene. Three isomers of IEPOX, including cis-β- and trans-β, were synthesized and oxidized by OH in environmental chambers under high- and low-NO conditions. We find that IEPOX reacts with OH at 299 K with rate coefficients of (0.84 ± 0.07) × 10(-11), (1.52 ± 0.07) × 10(-11), and (0.98 ± 0.05) × 10(-11) cm(3) molecule(-1) s(-1) for the δ1, cis-β, and trans-β isomers. Finally, yields of the first-generation products of IEPOX + OH oxidation were measured, and a new mechanism of IEPOX oxidation is proposed here to account for the observed products. The substantial yield of glyoxal and methylglyoxal from IEPOX oxidation may help explain elevated levels of those compounds observed in low-NO environments with high isoprene emissions.

Kinetics and Products of the Reaction of the First-Generation Isoprene Hydroxy Hydroperoxide (ISOPOOH) with OH

The atmospheric oxidation of isoprene by the OH radical leads to the formation of several isomers of an unsaturated hydroxy hydroperoxide, ISOPOOH. Oxidation of ISOPOOH by OH produces epoxydiols, IEPOX, which have been shown to contribute mass to secondary organic aerosol (SOA). We present kinetic rate constant measurements for OH + ISOPOOH using synthetic standards of the two major isomers: (1,2)- and (4,3)-ISOPOOH. At 297 K, the total OH rate constant is 7.5 ± 1.2 × 10(-11) cm(3) molecule(-1) s(-1) for (1,2)-ISOPOOH and 1.18 ± 0.19 × 10(-10) cm(3) molecule(-1) s(-1) for (4,3)-ISOPOOH. Abstraction of the hydroperoxy hydrogen accounts for approximately 12% and 4% of the reactivity for (1,2)-ISOPOOH and (4,3)-ISOPOOH, respectively. The sum of all H-abstractions account for approximately 15% and 7% of the reactivity for (1,2)-ISOPOOH and (4,3)-ISOPOOH, respectively. The major product observed from both ISOPOOH isomers was IEPOX (cis-β and trans-β isomers), with a ∼ 2:1 preference for trans-β IEPOX and similar total yields from each ISOPOOH isomer (∼ 70-80%). An IEPOX global production rate of more than 100 Tg C each year is estimated from this chemistry using a global 3D chemical transport model, similar to earlier estimates. Finally, following addition of OH to ISOPOOH, approximately 13% of the reactivity proceeds via addition of O2 at 297 K and 745 Torr. In the presence of NO, these peroxy radicals lead to formation of small carbonyl compounds. Under HO2 dominated chemistry, no products are observed from these channels. We suggest that the major products, highly oxygenated organic peroxides, are lost to the chamber walls. In the atmosphere, formation of these compounds may contribute to organic aerosol mass.

Isoprene photochemistry over the Amazon rainforest

Significance For isolated regions of the planet, organic peroxy radicals produced as intermediates of atmospheric photochemistry have been expected to follow HO2 rather than NO pathways. Observational evidence, however, has been lacking. An accurate understanding of the relative roles of the two pathways is needed for quantitative predictions of the concentrations of particulate matter, oxidation capacity, and consequent environmental and climate impacts. The results herein, based on measurements, find that the ratio of the reaction rate of isoprene peroxy radicals with HO2 to that with NO is about unity for background conditions of Amazonia. The implication is that sufficient NO emissions are maintained by natural processes of the forest such that both HO2 and NO pathways are important, even in this nominally low-NO region. Isoprene photooxidation is a major driver of atmospheric chemistry over forested regions. Isoprene reacts with hydroxyl radicals (OH) and molecular oxygen to produce isoprene peroxy radicals (ISOPOO). These radicals can react with hydroperoxyl radicals (HO2) to dominantly produce hydroxyhydroperoxides (ISOPOOH). They can also react with nitric oxide (NO) to largely produce methyl vinyl ketone (MVK) and methacrolein (MACR). Unimolecular isomerization and bimolecular reactions with organic peroxy radicals are also possible. There is uncertainty about the relative importance of each of these pathways in the atmosphere and possible changes because of anthropogenic pollution. Herein, measurements of ISOPOOH and MVK + MACR concentrations are reported over the central region of the Amazon basin during the wet season. The research site, downwind of an urban region, intercepted both background and polluted air masses during the GoAmazon2014/5 Experiment. Under background conditions, the confidence interval for the ratio of the ISOPOOH concentration to that of MVK + MACR spanned 0.4–0.6. This result implies a ratio of the reaction rate of ISOPOO with HO2 to that with NO of approximately unity. A value of unity is significantly smaller than simulated at present by global chemical transport models for this important, nominally low-NO, forested region of Earth. Under polluted conditions, when the concentrations of reactive nitrogen compounds were high (>1 ppb), ISOPOOH concentrations dropped below the instrumental detection limit (<60 ppt). This abrupt shift in isoprene photooxidation, sparked by human activities, speaks to ongoing and possible future changes in the photochemistry active over the Amazon rainforest.

Atmospheric fate of methyl vinyl ketone: peroxy radical reactions with NO and HO2.

First generation product yields from the OH-initiated oxidation of methyl vinyl ketone (3-buten-2-one, MVK) under both low and high NO conditions are reported. In the low NO chemistry, three distinct reaction channels are identified leading to the formation of (1) OH, glycolaldehyde, and acetyl peroxy R2a , (2) a hydroperoxide R2b , and (3) an α-diketone R2c . The α-diketone likely results from HOx-neutral chemistry previously only known to occur in reactions of HO2 with halogenated peroxy radicals. Quantum chemical calculations demonstrate that all channels are kinetically accessible at 298 K. In the high NO chemistry, glycolaldehyde is produced with a yield of 74 ± 6.0%. Two alkyl nitrates are formed with a combined yield of 4.0 ± 0.6%. We revise a three-dimensional chemical transport model to assess what impact these modifications in the MVK mechanism have on simulations of atmospheric oxidative chemistry. The calculated OH mixing ratio over the Amazon increases by 6%, suggesting that the low NO chemistry makes a non-negligible contribution toward sustaining the atmospheric radical pool.

Production and Fate of C4 Dihydroxycarbonyl Compounds from Isoprene Oxidation

Isoprene epoxydiols (IEPOX) are formed in high yield as second-generation products of atmospheric isoprene oxidation in pristine (low-NO) environments. IEPOX has received significant attention for its ability to form secondary organic aerosol, but the fate of IEPOX in the gas phase, and those of its oxidation products, remains largely unexplored. In this study, three dihydroxycarbonyl compounds with molecular formula of C4H8O3, putative products of IEPOX oxidation, are synthesized to determine their isomer-specific yields from IEPOX. We find that 3,4-dihydroxy-2-butanone (DHBO) comprises 43% and 36% of the products from cis- and trans-β-IEPOX, respectively, and is by far the most abundant C4H8O3 dihydroxycarbonyl compound produced by this mechanism. OH is found to react with DHBO with a rate coefficient of 1.10 × 10(-11) cm(3) molecule(-1) s(-1) at 297 K, forming two hydroxydicarbonyl compounds that share the molecular formula C4H6O3 with unitary yield. The results of this study are compared with field observations and used to propose a multigenerational mechanism of IEPOX oxidation. Finally, global simulations using GEOS-Chem, a chemical transport model, show that the C4H8O3 dihydroxycarbonyl compounds and their oxidation products are widespread in the atmosphere and estimate annual global production of C4H8O3 dihydroxycarbonyls to be 54 Tg y(-1), primarily as DHBO.

Contrasting cloud composition between coupled and decoupled marine boundary layer clouds

Marine stratocumulus clouds often become decoupled from the vertical layer immediately above the ocean surface. This study contrasts cloud chemical composition between coupled and decoupled marine stratocumulus clouds for dissolved nonwater substances. Cloud water and droplet residual particle composition were measured in clouds off the California coast during three airborne experiments in July–August of separate years (Eastern Pacific Emitted Aerosol Cloud Experiment 2011, Nucleation in California Experiment 2013, and Biological and Oceanic Atmospheric Study 2015). Decoupled clouds exhibited significantly lower air-equivalent mass concentrations in both cloud water and droplet residual particles, consistent with reduced cloud droplet number concentration and subcloud aerosol (D_p > 100 nm) number concentration, owing to detachment from surface sources. Nonrefractory submicrometer aerosol measurements show that coupled clouds exhibit higher sulfate mass fractions in droplet residual particles, owing to more abundant precursor emissions from the ocean and ships. Consequently, decoupled clouds exhibited higher mass fractions of organics, nitrate, and ammonium in droplet residual particles, owing to effects of long-range transport from more distant sources. Sodium and chloride dominated in terms of air-equivalent concentration in cloud water for coupled clouds, and their mass fractions and concentrations exceeded those in decoupled clouds. Conversely, with the exception of sea-salt constituents (e.g., Cl, Na, Mg, and K), cloud water mass fractions of all species examined were higher in decoupled clouds relative to coupled clouds. Satellite and Navy Aerosol Analysis and Prediction System-based reanalysis data are compared with each other, and the airborne data to conclude that limitations in resolving boundary layer processes in a global model prevent it from accurately quantifying observed differences between coupled and decoupled cloud composition.