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Heterogeneous Reactions of α-Pinene on Mineral Surfaces: Formation of Organonitrates and α-Pinene Oxidation Products.

ABSTRACT: Organonitrates (ON) are important components of secondary organic aerosols (SOAs). α-Pinene (C₁₀H₁₆), the most abundant monoterpene in the troposphere, is a precursor for the formation of several of these compounds. ON from α-pinene can be produced in the gas phase via photochemical processes and/or following reactions with oxidizers including hydroxyl radical and ozone. Gas-phase nitrogen oxides (NO₂, NO₃) are N sources for ON formation. Although gas-phase reactions of α-pinene that yield ON are fairly well understood, little is known about their formation through heterogeneous and multiphase pathways. In the current study, surface reactions of α-pinene with nitrogen oxides on hematite (α-Fe₂O₃) and kaolinite (SiO₂Al₂O₃(OH)₄) surfaces, common components of mineral dust, have been investigated. α-Pinene oxidizes upon adsorption on kaolinite, forming pinonaldehyde, which then dimerizes on the surface. Furthermore, α-pinene is shown to react with adsorbed nitrate species on these mineral surfaces producing multiple ON and other oxidation products. Additionally, gas-phase oxidation products of α-pinene on mineral surfaces are shown to more strongly adsorb on the surface compared to α-pinene. Overall, this study reveals the complexity of reactions of prevalent organic compounds such as α-pinene with adsorbed nitrate and nitrogen dioxide, revealing new heterogeneous reaction pathways for SOA formation that is mineralogy specific.

SUBMITTER: Hettiarachchi E

PROVIDER: S-EPMC9251774 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:The formation of atmospheric cloud droplets due to secondary organic aerosol (SOA) particles is important for quantifying the Earth's radiative balance under future, possibly warmer, climates, yet is only poorly understood. While cloud activation may be parametrized using the surface tension depression that coincides with surfactant partitioning to the gas-droplet interface, the extent to which cloud activation is influenced by both the chemical structure and reactivity of the individual molecules comprising this surfactant pool is largely unknown. We report herein considerable differences in the surface tension depression of aqueous pendant droplets that contain synthetically prepared ozonolysis products derived from α-pinene and β-caryophyllene, the most abundant of the monoterpenes and sesquiterpenes, respectively, that are emitted over the planet's vast forest ecosystems. Oxidation products derived from β-caryophyllene were found to exhibit significantly higher surface activity than those prepared from α-pinene, with the critical supersaturation required for cloud droplet activation reduced by 50% for β-caryophyllene aldehyde at 1 mM. These considerable reductions in the critical supersaturation were found to coincide with free energies of adsorption that exceed ∼25 kJ/mol, or just one hydrogen bond equivalent, depending on the ammonium sulfate and oxidation product concentration in the solution. Additional experiments showed that aldehyde-containing oxidation products exist in equilibrium with hydrated forms in aqueous solution, which may modulate their bulk solubility and surface activity. Equilibration time scales on the order of 10-5 to 10-4 s calculated for micrometer-sized aerosol particles indicate instantaneous surface tension depression in the activation processes leading to cloud formation in the atmosphere. Our findings highlight the underlying importance of molecular structure and reactivity when considering cloud condensation activity in the presence of SOA particles.

Project description:Recent ambient atmospheric measurements have detected highly oxygenated organic molecules (HOMs) at many sites and are a consequence of autoxidation processes occurring at ambient temperatures. Monoterpenes in particular have a propensity to autoxidize although they exhibit a wide range of HOM yields, which may be due to a variety of reasons including reactions with different oxidants like OH and O3, differing hydrogen (H) atom transfer or peroxy radical cyclization rates, numbers of available reaction pathways, and/or energy loss processes for activated HO-monoterpene or O3-monoterpene adducts. In this work, the autoxidation mechanisms of (+)-α-pinene, (+)-β-pinene, and (+)-limonene following initial OH oxidation and three successive O2 additions are examined using density functional theory (DFT) to understand what accounts for the disparity. Rates of different potential autoxidation pathways initiated by OH addition or abstraction reactions are quantified using transition-state theory (TST) and master equation approaches using the lowest-energy conformers. OH abstraction reactions do not appreciably influence HOM production in the pinenes and limit autoxidation for limonene because the subsequent autoxidation reactions are slow while OH addition reactions are found to be the main route to HOMs for all three monoterpenes. Generally, faster autoxidation rates are computed in later unimolecular reactions that produce RO7 radicals after OH addition (∼10 s-1 or greater) than rates for RO5 peroxy radical production (0.2-7 s-1). Mechanistic pathways that form RO7 peroxy radicals are similar for all three monoterpenes with a particular bicyclo RO7 radical involving a five-membered peroxide ring being favored for all three monoterpenes. The molar yields of RO7 radicals are 4.6% (+10.0/-2.4), 3.8% (+9.1/-2.6), and 7.6% (+13.1/-4.9) for α-pinene, β-pinene, and limonene, respectively, at 298 K and 1 ppb of NO and only significantly decline at NO concentrations exceeding 10 ppb. The higher yield for limonene relative to the pinenes is predominantly a consequence of the initial oxidation step: OH adducts of the bicyclic pinenes have to use the excess energy after OH addition to break one of the rings and make the molecule more flexible for autoxidation although this process is inefficient, while one of the prominent OH adducts for monocyclic limonene does not have to do this and may add O2 immediately before autoxidizing further. These insights may be used to guide a better representation of these processes in atmospheric models because they affect particulate matter (PM), NOx, and ozone concentrations via enhanced production of low-volatility species, less early-generation NOx cycling, and altered organic nitrate production.

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Heterogeneous Reactions of α-Pinene on Mineral Surfaces: Formation of Organonitrates and α-Pinene Oxidation Products.

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