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Wildfires are a source of primary aerosols and precursors for secondary aerosols to the atmosphere. In this work, we discover that the evolution of these aerosols depends strongly on the coupled effects of dilution, photooxidation, and partitioning.

We use observations from dual high-resolution mass spectrometers to characterize ecosystem-atmosphere fluxes of reactive carbon across an extensive range of volatile organic compounds (VOCs) and test how well that exchange is represented in current chemical transport models. Measurements combined proton-transfer reaction mass spectrometry (PTRMS) and iodide chemical ionization mass spectrometry (ICIMS) over a Colorado pine forest; together, these techniques have been shown to capture the majority of ambient VOC abundance and reactivity. Total VOC mass and associated OH reactivity fluxes were dominated by emissions of 2-methyl-3-buten-2-ol, monoterpenes, and small oxygenated VOCs, with a small number of compounds detected by PTRMS driving the majority of both net and upward exchanges. Most of these dominant species are explicitly included in chemical models, and we find here that GEOS-Chem accurately simulates the net and upward VOC mass and OH reactivity fluxes under clear sky conditions. However, large upward terpene fluxes occurred during sustained rainfall, and these are not captured by the model. Far more species contributed to the downward fluxes than are explicitly modeled, leading to a major underestimation of this key sink of atmospheric reactive carbon. This model bias mainly reflects missing and underestimated concentrations of depositing species, though inaccurate deposition velocities also contribute. The deposition underestimate is particularly large for assumed isoprene oxidation products, organic acids, and nitrates—species that are primarily detected by ICIMS. Ecosystem-atmosphere fluxes of ozone reactivity were dominated by sesquiterpenes and monoterpenes, highlighting the importance of these species for predicting near-surface ozone, oxidants, and aerosols.

The evolution of organic aerosol (OA) and brown carbon (BrC) in wildfire plumes, including the relative contributions of primary versus secondary sources, has been uncertain in part because of limited knowledge of the precursor emissions and the chemical environment of smoke plumes. We made airborne measurements of a suite of reactive trace gases, particle composition, and optical properties in fresh western US wildfire smoke in July through August 2018. We use these observations to quantify primary versus secondary sources of biomass-burning OA (BBPOA versus BBSOA) and BrC in wildfire plumes. When a daytime wildfire plume dilutes by a factor of 5 to 10, we estimate that up to one-third of the primary OA has evaporated and subsequently reacted to form BBSOA with near unit yield. The reactions of measured BBSOA precursors contribute only 13 ± 3% of the total BBSOA source, with evaporated BBPOA comprising the rest. We find that oxidation of phenolic compounds contributes the majority of BBSOA from emitted vapors. The corresponding particulate nitrophenolic compounds are estimated to explain 29 ± 15% of average BrC light absorption at 405 nm (BrC Abs(405)) measured in the first few hours of plume evolution, despite accounting for just 4 ± 2% of average OA mass. These measurements provide quantitative constraints on the role of dilution-driven evaporation of OA and subsequent radical-driven oxidation on the fate of biomass-burning OA and BrC in daytime wildfire plumes and point to the need to understand how processing of nighttime emissions differs.

Despite increasing incidence of wildfires in the United States, wildfire smoke is poorly characterized, with little known about particle composition and emission rates. Chemistry in transported plu...

Small cumulus clouds over the western United States were measured via airborne instruments during the wildfire season in summer of 2018. Statistics of the sampled clouds are presented and compared ...

Reactive nitrogen (Nr) within smoke plumes plays important roles in the production of ozone, the formation of secondary aerosols, and deposition of fixed N to ecosystems. The Western Wildfire Experiment for Cloud Chemistry, Aerosol Absorption, and Nitrogen (WE-CAN) field campaign sampled smoke from 23 wildfires throughout the western U.S. during summer 2018 using the NSF/NCAR C-130 research aircraft. We empirically estimate Nr normalized excess mixing ratios and emission factors from fires sampled within 80 min of estimated emission and explore variability in the dominant forms of Nr between these fires. We find that reduced N compounds comprise a majority (39%-80%; median = 66%) of total measured reactive nitrogen (ΣNr) emissions. The smoke plumes sampled during WE-CAN feature rapid chemical transformations after emission. As a result, within minutes after emission total measured oxidized nitrogen (ΣNOy) and measured total ΣNHx (NH3 + pNH4) are more robustly correlated with modified combustion efficiency (MCE) than NOx and NH3 by themselves. The ratio of ΣNHx/ΣNOy displays a negative relationship with MCE, consistent with previous studies. A positive relationship with total measured ΣNr suggests that both burn conditions and fuel N content/volatilization differences contribute to the observed variability in the distribution of reduced and oxidized Nr. Additionally, we compare our in situ field estimates of Nr EFs to previous lab and field studies. For similar fuel types, we find ΣNHx EFs are of the same magnitude or larger than lab-based NH3 EF estimates, and ΣNOy EFs are smaller than lab NOx EFs.

Particle phase state is a property of atmospheric aerosols that has important implications for the formation, evolution, and gas/particle partitioning of secondary organic aerosol (SOA). In this work, we use a size-resolved chemistry and microphysics model (Statistical Oxidation Model coupled to the TwO Moment Aerosol Sectional (SOM-TOMAS)), updated to include an explicit treatment of particle phase state, to constrain the bulk diffusion coefficient (Db) of SOA produced from α-pinene ozonolysis. By leveraging data from laboratory experiments performed in the absence of a seed and under dry conditions, we find that the Db for SOA can be constrained ((1-7) × 10-15 cm2 s-1 in these experiments) by simultaneously reproducing the time-varying SOA mass concentrations and the evolution of the particle size distribution. Another version of our model that used the predicted SOA composition to calculate the glass-transition temperature, viscosity, and, ultimately, Db (∼10-15 cm2 s-1) of the SOA was able to reproduce the mass and size distribution measurements when we included oligomer formation (oligomers accounted for about a fifth of the SOA mass). Our work highlights the potential of a size-resolved SOA model to constrain the particle phase state of SOA using historical measurements of the evolution of the particle size distribution.

Significance Sea spray aerosol, produced through breaking waves, is one of the largest sources of environmental particles. Once in the atmosphere, sea spray aerosol influences cloud formation, serves as microenvironments for multiphase atmospheric chemical reactions, and impacts human health. All of these impacts are affected by aerosol acidity. Here we show that freshly emitted sea spray aerosol particles become highly acidic within minutes as they are transferred across the ocean−air interface. These results have important implications for atmospheric chemistry and climate, including aerosol/gas partitioning, heterogeneous reactions, and chemical speciation at the surface and within sea spray aerosol., Aerosols impact climate, human health, and the chemistry of the atmosphere, and aerosol pH plays a major role in the physicochemical properties of the aerosol. However, there remains uncertainty as to whether aerosols are acidic, neutral, or basic. In this research, we show that the pH of freshly emitted (nascent) sea spray aerosols is significantly lower than that of sea water (approximately four pH units, with pH being a log scale value) and that smaller aerosol particles below 1 μm in diameter have pH values that are even lower. These measurements of nascent sea spray aerosol pH, performed in a unique ocean−atmosphere facility, provide convincing data to show that acidification occurs “across the interface” within minutes, when aerosols formed from ocean surface waters become airborne. We also show there is a correlation between aerosol acidity and dissolved carbon dioxide but no correlation with marine biology within the seawater. We discuss the mechanisms and contributing factors to this acidity and its implications on atmospheric chemistry.

The vibrational overtone spectra of the acetylenic (Δυ = 4, 5) and methyl (Δυ = 5, 6) C-H stretch transitions of tert-butyl acetylene [(CH(3))(3)C-C≡C-H] were obtained using the phase shift cavity ring down (PS-CRD) technique at 295 K. The C-H stretch fundamental and overtone absorptions of the acetylenic (Δυ = 2 and 3) and methyl (Δυ = 2-4) C-H bonds have been obtained using a Fourier transform infrared and near-infrared spectrophotometer. Harmonic frequency ω(ν(1)) and anharmonicities x(ν(1)) and x(ν(1), ν(24)) are reported for the acetylenic C-H bond. Molecular orbital calculations of geometry and vibrational frequencies were performed. A harmonically coupled anharmonic oscillator (HCAO) model was used to determine the overtone energy levels and assign the absorption bands to vibrational transitions of methyl C-H bonds. Band strength values were obtained experimentally and compared with intensities calculated in terms of the HCAO model where only the C-H modes are considered. No adjustable parameters were used to get order of magnitude agreement with experimental intensities for all pure local mode C-H transitions.

The dynamics of the O((1)D) + Xe electronic quenching reaction was investigated in a crossed beam experiment at four collision energies. Marked large-scale oscillations in the differential cross sections were observed for the inelastic scattering products, O((3)P) and Xe. The shape and relative phases of the oscillatory structure depend strongly on collision energy. Comparison of the experimental results with time-independent scattering calculations shows qualitatively that this behavior is caused by Stueckelberg interferences, for which the quantum phases of the multiple reaction pathways accessible during electronic quenching constructively and destructively interfere.