The persistence of smoke VOCs indoors: Partitioning, surface cleaning, and air cleaning in a smoke-contaminated house.

Wildfires are increasing in frequency, raising concerns that smoke can permeate indoor environments and expose people to chemical air contaminants. To study smoke transformations in indoor environments and evaluate mitigation strategies, we added smoke to a test house. Many volatile organic compounds (VOCs) persisted days following the smoke injection, providing a longer-term exposure pathway for humans. Two time scales control smoke VOC partitioning: a faster one (1.0 to 5.2 hours) that describes the time to reach equilibrium between adsorption and desorption processes and a slower one (4.8 to 21.2 hours) that describes the time for indoor ventilation to overtake adsorption-desorption equilibria in controlling the air concentration. These rates imply that vapor pressure controls partitioning behavior and that house ventilation plays a minor role in removing smoke VOCs. However, surface cleaning activities (vacuuming, mopping, and dusting) physically removed surface reservoirs and thus reduced indoor smoke VOC concentrations more effectively than portable air cleaners and more persistently than window opening.

Ventilation in a Residential Building Brings Outdoor NOx Indoors with Limited Implications for VOC Oxidation from NO3 Radicals.

Energy-efficient residential building standards require the use of mechanical ventilation systems that replace indoor air with outdoor air. Transient outdoor pollution events can be transported indoors via the mechanical ventilation system and other outdoor air entry pathways and impact indoor air chemistry. In the spring of 2022, we observed elevated levels of NOx (NO + NO2) that originated outdoors, entering the National Institute of Standards and Technology (NIST) Net-Zero Energy Residential Test Facility through the mechanical ventilation system. Using measurements of NOx, ozone (O3), and volatile organic compounds (VOCs), we modeled the effect of the outdoor-to-indoor ventilation of NOx pollution on the production of nitrate radical (NO3), a potentially important indoor oxidant. We evaluated how VOC oxidation chemistry was affected by NO3 during NOx pollution events compared to background conditions. We found that nitric oxide (NO) pollution introduced indoors titrated O3 and inhibited the modeled production of NO3. NO ventilated indoors also likely ceased most gas-phase VOC oxidation chemistry during plume events. Only through the artificial introduction of O3 to the ventilation duct during a NOx pollution event (i.e., when O3 and NO2 concentrations were high relative to typical conditions) were we able to measure NO3-initiated VOC oxidation products, indicating that NO3 was impacting VOC oxidation chemistry.

The Sea Spray Chemistry and Particle Evolution study (SeaSCAPE): overview and experimental methods.

Marine aerosols strongly influence climate through their interactions with solar radiation and clouds. However, significant questions remain regarding the influences of biological activity and seawater chemistry on the flux, chemical composition, and climate-relevant properties of marine aerosols and gases. Wave channels, a traditional tool of physical oceanography, have been adapted for large-scale ocean-atmosphere mesocosm experiments in the laboratory. These experiments enable the study of aerosols under controlled conditions which isolate the marine system from atmospheric anthropogenic and terrestrial influences. Here, we present an overview of the 2019 Sea Spray Chemistry and Particle Evolution (SeaSCAPE) study, which was conducted in an 11 800 L wave channel which was modified to facilitate atmospheric measurements. The SeaSCAPE campaign sought to determine the influence of biological activity in seawater on the production of primary sea spray aerosols, volatile organic compounds (VOCs), and secondary marine aerosols. Notably, the SeaSCAPE experiment also focused on understanding how photooxidative aging processes transform the composition of marine aerosols. In addition to a broad range of aerosol, gas, and seawater measurements, we present key results which highlight the experimental capabilities during the campaign, including the phytoplankton bloom dynamics, VOC production, and the effects of photochemical aging on aerosol production, morphology, and chemical composition. Additionally, we discuss the modifications made to the wave channel to improve aerosol production and reduce background contamination, as well as subsequent characterization experiments. The SeaSCAPE experiment provides unique insight into the connections between marine biology, atmospheric chemistry, and climate-relevant aerosol properties, and demonstrates how an ocean-atmosphere-interaction facility can be used to isolate and study reactions in the marine atmosphere in the laboratory under more controlled conditions.

Heterogeneous Nucleation Drives Particle Size Segregation in Sequential Ozone and Nitrate Radical Oxidation of Catechol.

Secondary organic aerosol formation via condensation of organic vapors onto existing aerosol transforms the chemical composition and size distribution of ambient aerosol, with implications for air quality and Earth's radiative balance. Gas-to-particle conversion is generally thought to occur on a continuum between equilibrium-driven partitioning of semivolatile molecules to the pre-existing mass size distribution and kinetic-driven condensation of low volatility molecules to the pre-existing surface area size distribution. However, we offer experimental evidence in contrast to this framework. When catechol is sequentially oxidized by O3 and NO3 in the presence of (NH4)2SO4 seed particles with a single size mode, we observe a bimodal organic aerosol mass size distribution with two size modes of distinct chemical composition with nitrocatechol from NO3 oxidation preferentially condensing onto the large end of the pre-existing size distribution (∼750 nm). A size-resolved chemistry and microphysics model reproduces the evolution of the two distinct organic aerosol size modes─heterogeneous nucleation to an independent, nitrocatechol-rich aerosol phase.

Particle Size Distribution Dynamics Can Help Constrain the Phase State of Secondary Organic Aerosol.

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.

Acidity across the interface from the ocean surface to 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.

Quantification of organic aerosol and brown carbon evolution in fresh wildfire plumes.

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 Abs405) 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.

Hazardous Air Pollutants in Fresh and Aged Western US Wildfire Smoke and Implications for Long-Term Exposure.

Wildfires have a significant adverse impact on air quality in the United States (US). To understand the potential health impacts of wildfire smoke, many epidemiology studies rely on concentrations of fine particulate matter (PM) as a smoke tracer. However, there are many gas-phase hazardous air pollutants (HAPs) identified by the Environmental Protection Agency (EPA) that are also present in wildfire smoke plumes. Using observations from the Western Wildfire Experiment for Cloud Chemistry, Aerosol Absorption, and Nitrogen (WE-CAN), a 2018 aircraft-based field campaign that measured HAPs and PM in western US wildfire smoke plumes, we identify the relationships between HAPs and associated health risks, PM, and smoke age. We find the ratios between acute, chronic noncancer, and chronic cancer HAPs health risk and PM in smoke decrease as a function of smoke age by up to 72% from fresh (<1 day of aging) to old (>3 days of aging) smoke. We show that acrolein, formaldehyde, benzene, and hydrogen cyanide are the dominant contributors to gas-phase HAPs risk in smoke plumes. Finally, we use ratios of HAPs to PM along with annual average smoke-specific PM to estimate current and potential future smoke HAPs risks.

Electronic quenching of O((1)D) by Xe: Oscillations in the product angular distribution and their dependence on collision energy.

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.

Disruption of Wnt/ß-Catenin Signaling and Telomeric Shortening Are Inextricable Consequences of Tankyrase Inhibition in Human Cells.

Maintenance of chromosomal ends (telomeres) directly contributes to cancer cell immortalization. The telomere protection enzymes belonging to the tankyrase (Tnks) subfamily of poly(ADP-ribose) polymerases (PARPs) have recently been shown to also control transcriptional response to secreted Wnt signaling molecules. Whereas Tnks inhibitors are currently being developed as therapeutic agents for targeting Wnt-related cancers and as modulators of Wnt signaling in tissue-engineering agendas, their impact on telomere length maintenance remains unclear. Here, we leveraged a collection of Wnt pathway inhibitors with previously unassigned mechanisms of action to identify novel pharmacophores supporting Tnks inhibition. A multifaceted experimental approach that included structural, biochemical, and cell biological analyses revealed two distinct chemotypes with selectivity for Tnks enzymes. Using these reagents, we revealed that Tnks inhibition rapidly induces DNA damage at telomeres and telomeric shortening upon long-term chemical exposure in cultured cells. On the other hand, inhibitors of the Wnt acyltransferase Porcupine (Porcn) elicited neither effect. Thus, Tnks inhibitors impact telomere length maintenance independently of their affects on Wnt/ß-catenin signaling. We discuss the implications of these findings for anticancer and regenerative medicine agendas dependent upon chemical inhibitors of Wnt/ß-catenin signaling.

Vibrational overtone spectroscopy, energy levels, and intensities of (CH3)3C-C≡C-H.

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.