Stabilized Criegee intermediates react with organic acids in the gas phase and at the air-water interface to form a class of ester hydroperoxides, α-acyloxyalkyl hydroperoxides (αAAHPs). A number of recent studies have proposed the importance of αAAHPs to the formation and growth of secondary organic aerosol (SOA). The chemistry of αAAHPs has not been investigated due to a lack of commercially available chemical standards. In this work, the behavior of αAAHPs in condensed phases is investigated for the first time. Experiments were performed with two synthesized αAAHP species. αAAHPs decomposed rapidly in the aqueous phase, with the rate highly dependent on the solvent, temperature, solution pH, and other compounds present in the solution. The measured 1-order decomposition rate coefficient varied between 10 and 10 s under the conditions examined in this work. Elucidation of the reaction mechanism is complicated by byproducts arising from the synthetic procedure, but observations are consistent with a base-catalyzed hydrolysis of αAAHPs. The rapid hydrolysis of αAAHPs observed in this work implies their short lifetimes in ambient cloud and fog waters. Decomposition of αAAHPs likely gives rise to smaller peroxides, such as HO. The loss of αAAHPs is also relevant to filter extraction, which is commonly practiced in laboratory experiments, potentially explaining contradictory results reported in the existing literature regarding the importance of αAAHPs in SOA.

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Secondary organic aerosol (SOA) formation is studied in laboratory chambers, in which volatile organic compounds (VOCs) are oxidized to produce low-volatility compounds that condense into the aerosol phase. It has been established that such oxidized low-volatility compounds can partition into the chamber walls, which traditionally consist of Teflon film. Several studies exist in which the rates of uptake of individual vapor compounds to the chamber walls have been measured, but a unified theory capable of describing the range of experimental measurements has been lacking. Here, a two-layer model of observed short and long vapor–wall interaction time scales in Teflon-walled environmental chambers is presented and shown to be consistent with experimental data on the rate of wall deposition of more than 90 compounds. Semiempirical relationships between key parameters in the model and vapor molecular properties are derived, which can be used to predict the fate of gas-phase vapor in the chamber under dry conditions.

Dimeric compounds contribute significantly to the formation and growth of atmospheric secondary organic aerosol (SOA) derived from monoterpene oxidation. However, the mechanisms of dimer production, in particular the relevance of gas- vs. particle-phase chemistry, remain unclear. Here, through a combination of mass spectrometric, chromatographic, and synthetic techniques, we identify a suite of dimeric compounds (CHO) formed from concerted O and OH oxidation of β-pinene (i.e., accretion of O- and OH-derived products/intermediates). These dimers account for an appreciable fraction (5.9-25.4%) of the β-pinene SOA mass and are designated as extremely low-volatility organic compounds. Certain dimers, characterized as covalent dimer esters, are conclusively shown to form through heterogeneous chemistry, while evidence of dimer production via gas-phase reactions is also presented. The formation of dimers through synergistic O + OH oxidation represents a potentially significant, heretofore-unidentified source of low-volatility monoterpene SOA. This reactivity also suggests that the current treatment of SOA formation as a sum of products originating from the isolated oxidation of individual precursors fails to accurately reflect the complexity of oxidation pathways at play in the real atmosphere. Accounting for the role of synergistic oxidation in ambient SOA formation could help to resolve the discrepancy between the measured atmospheric burden of SOA and that predicted by regional air quality and global climate models.

Liquid chromatography/negative electrospray ionization mass spectrometry [LC/()ESI-MS] is routinely employed to characterize the identity and abundance of molecular products in secondary organic aerosol (SOA) derived from monoterpene oxidation. Due to a lack of authentic standards, however, commercial terpenoic acids (e.g., cis-pinonic acid) are typically used as surrogates to quantify both monomeric and dimeric SOA constituents. Here, we synthesize a series of enantiopure, pinene-derived carboxylic acid and dimer ester homologues. We find that the ()ESI efficiencies of the dimer esters are 19-36 times higher than that of cis-pinonic acid, demonstrating that the mass contribution of dimers to monoterpene SOA has been significantly overestimated in past studies. Using the measured ()ESI efficiencies of the carboxylic acids and dimer esters as more representative surrogates, we determine that molecular products measureable by LC/()ESI-MS account for only 21.8  2.6% and 18.9  3.2% of the mass of SOA formed from ozonolysis of -pinene and -pinene, respectively. The 28-36 identified monomers (C 7-10 H 10-18 O 3-6) constitute 15.6-20.5% of total SOA mass, whereas only 1.3-3.3% of the SOA mass is attributable to the 46-62 identified dimers (C 15-19 H 24-32 O 4-11). The distribution of identified pinene and -pinene SOA molecular products is examined as a function of carbon number (n C), average carbon oxidation state (C), and volatility (C*). The observed order-of-magnitude OS difference in ()ESI efficiency between monomers and dimers is expected to be broadly applicable to other biogenic and anthropogenic SOA systems analyzed via () or (+) LC/ESI-MS under various LC conditions, and demonstrates that the use of unrepresentative surrogates can lead to substantial systematic errors in quantitative LC/ESI-MS analyses of SOA.

Gas and aqueous phases are essential media for atmospheric chemistry and aerosol formation. Numerous studies have focused on aqueous-phase reactions as well as coupled gas/aqueous-phase mass transport and reaction. Few studies have directly addressed processes occurring at the air-water interface, especially involving surface-active compounds. We report here the application of field-induced droplet ionization mass spectrometry (FIDI-MS) to chemical reactions occurring at the atmospheric air-water interface. We determine the air-water interfacial OH radical reaction rate constants for sodium dodecyl sulfate (SDS), a common surfactant, and pinonic acid (PA), a surface-active species and proxy for biogenic atmospheric oxidation products, as 2.87 × 10 and 9.38 × 10 cm molec s, respectively. In support of the experimental data, a comprehensive gas-surface-aqueous multiphase transport and reaction model of general applicability to atmospheric interfacial processes is developed. Through application of the model, PA is shown to be oxidized exclusively at the air-water interface of droplets with a diameter of 5 μm under typical ambient OH levels. In the absence of interfacial reaction, aqueous- rather than gas-phase oxidation is the major PA sink. We demonstrate the critical importance of air-water interfacial chemistry in determining the fate of surface-active species.

Detailed characterization of the aerosol content of wildfire smoke plumes is typically performed through in situ aircraft observations, which have limited temporal and spatial coverage. Extending such observations to regional or global scales requires new remote sensing approaches, such as retrievals that make use of spectropolarimetric, multiangle imaging. In this work measurements made during the Imaging Polarimetric Assessment and Characterization of Tropospheric Particulate Matter (ImPACT‐PM) field campaign in a smoke plume near the town of Lebec in Southern California by the Navy Center for Interdisciplinary Remotely Piloted Aircraft Studies Twin Otter aircraft on 8 July 2016 are used in conjunction with near‐coincident measurements from the Airborne Multiangle SpectroPolarimetric Imager (AirMSPI) on the National Aeronautics and Space Administration ER‐2 high‐altitude research aircraft to assess the sensitivity of spectropolarimetric measurements to the black carbon content of the plume. Tracking visible features in the smoke through the sequence of AirMSPI observations allowed the height of the plume to be estimated through geometric techniques. Then, by constraining the fractional amounts of the aerosol constituents with the in situ data, radiative closure was obtained through simulations performed with a polarimetric radiative transfer code, demonstrating the ability to constrain the black carbon mass fraction to approximately 5%, given the uncertainties in the AirMSPI measurements and the assumption of external mixing of aerosol components. The AirMSPI retrieval, made using a limited set of observations from the 470 nm polarimetric spectral band alone, was also generally consistent with operational retrievals of aerosol optical depth and surface reflectance made by the Multi‐Angle Implementation of Atmospheric Correction algorithm at 1 km resolution.

Filter-based thermal desorption (F-TD) techniques, such as the filter inlet for gases and aerosols (FIGAERO), are widely employed to investigate the molecular composition and physicochemical properties of secondary organic aerosol (SOA). Here, we 1