Alkylperoxy radicals are responsible for the formation of oxygenated primary organic aerosol.

Organic aerosol (OA) is an air pollutant ubiquitous in urban atmospheres. Urban OA is usually apportioned into primary OA (POA), mostly emitted by mobile sources, and secondary OA (SOA), which forms in the atmosphere due to oxidation of gas-phase precursors from anthropogenic and biogenic sources. By performing coordinated measurements in the particle phase and the gas phase, we show that the alkylperoxy radical chemistry that is responsible for low-temperature ignition also leads to the formation of oxygenated POA (OxyPOA). OxyPOA is distinct from POA emitted during high-temperature ignition and is chemically similar to SOA. We present evidence for the prevalence of OxyPOA in emissions of a spark-ignition engine and a next-generation advanced compression-ignition engine, highlighting the importance of understanding OxyPOA for predicting urban air pollution patterns in current and future atmospheres.

Unimolecular Reactions of 2-Methyloxetanyl and 2-Methyloxetanylperoxy Radicals.

Alkyl-substituted cyclic ethers are intermediates formed in abundance during the low-temperature oxidation of hydrocarbons and biofuels via a chain-propagating step with ȮH. Subsequent reactions of cyclic ether radicals involve a competition between ring opening and reaction with O2, the latter of which enables pathways mediated by hydroperoxy-substituted carbon-centered radicals (Q̇OOH). Due to the resultant implications of competing unimolecular and bimolecular reactions on overall populations of ȮH, detailed insight into the chemical kinetics of cyclic ethers remains critical to high-fidelity numerical modeling of combustion. Cl-initiated oxidation experiments were conducted on 2-methyloxetane (an intermediate of n-butane oxidation) using multiplexed photoionization mass spectrometry (MPIMS), in tandem with calculations of stationary point energies on potential energy surfaces for unimolecular reactions of 2-methyloxetanyl and 2-methyloxetanylperoxy isomers. The potential energy surfaces were computed using the KinBot algorithm with stationary points calculated at the CCSD(T)-F12/cc-pVDZ-F12 level of theory. The experiments were conducted at 6 Torr and two temperatures (650 K and 800 K) under pseudo-first-order conditions to facilitate R + O2 reactions. Photoionization spectra were measured from 8.5 eV to 11.0 eV in 50-meV steps, and relative yields were quantified for species consistent with R → products and Q̇OOH → products. Species detected in the MPIMS experiments are linked to specific radicals of 2-methyloxetane. Species from R → products include methyl, ethene, formaldehyde, propene, ketene, 1,3-butadiene, and acrolein. Ion signals consistent with products from alkyl radical oxidation were detected, including for Q̇OOH-mediated species, which are also low-lying channels on their respective potential energy surfaces. In addition to species common to alkyl oxidation pathways, ring-opening reactions of Q̇OOH radicals derived from 2-methyloxetane produced ketohydroperoxide species (performic acid and 2-hydroperoxyacetaldehyde), which may impart additional chain-branching potential, and dicarbonyl species (3-oxobutanal and 2-methylpropanedial), which often serve as proxies for modeling reaction rates of ketohydroperoxides. The experimental and computational results underscore that reactions of cyclic ethers are inherently more complex than currently prescribed in chemical kinetic models utilized for combustion.

Multigram Synthesis of a Combustion-Relevant δ-Ketohydroperoxide through Sulfonylhydrazine Substitution.

A synthesis of a δ-ketohydroperoxide is described, addressing potential functional-group compatibilities in these elusive species relevant to combustion and atmospheric chemistries. The hydroperoxide is installed via sulfonylhydrazine substitution, which was found to be more effective than displacement of secondary halides. As part of this protocol, it was observed that 1,2-dimethoxyethane is an advantageous medium for the reaction, avoiding the formation of a tetrahydrofuran hydroperoxide side product. This discovery facilitated the multigram synthesis (6 steps, 41 % yield overall) and discrete characterization of the target δ-ketohydroperoxide.