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Squalene is a major skin oil lipid which can react with ozone forming a range of products including carbonyls, carboxylic acids, hydroxy ketones, secondary ozonides and hydroperoxides. Previous experimental studies have shown that the yield of these products depends on relative humidity. A new mechanism is developed which treats the reaction of ozone with carbon–carbon double bonds and the subsequent reactions of the Criegee intermediates forming a range of products in both condensed and gas phases. The mechanism is included in kinetic models for a variety of ozonolysis reaction systems including pure squalene particles, squalene and skin oil films, clothing, and skin covered by clothing. The models reproduce experimental measurements reasonably well using relatively consistent parameters, providing insights into the important reactions and processes controlling the concentrations of different species. In general, gas-phase secondary carbonyl product concentrations increase significantly as a function of relative humidity due to their formation from the reaction of Criegee intermediates with water, while carboxylic acids and hydroxy ketone concentrations decrease. For example, human exposure to gas-phase 6-methyl-5-hepten-2-one can increase by approximately a factor of two as the relative humidity increases from 10% to 95%. The model can also reproduce the decay of carboxylic acids in skin oil due to their reaction with Criegee intermediates. Discrepancies between some of the measurements and model outputs indicate that in addition to impacting chemistry, relative humidity may affect other processes such as partitioning to surfaces and condensed-phase diffusion.

Wildfire particulate matter contains high amounts of environmentally persistent free radicals and generates reactive oxygen species with implications for air quality and public health.

Emerging contaminants are of concern due to their rapidly increasing numbers and potential ecological and human health effects. In this study, the synergistic effects of the presence of multifunctional nitro, amino and carbon-carbon double bond (C═C) groups on the gas phase ozonolysis in O2 or at the air/solid interface were investigated using five simple model compounds. The gas phase ozonolysis rate constants at 296 K were (3.5 ± 0.9) × 10-20 cm3 molecule-1 s-1 for 2-methyl-1-nitroprop-1-ene and (6.8 ± 0.8) × 10-19 cm3 molecule-1 s-1 for 4-methyl-4-nitro-1-pentene, with lifetimes of 134 and 7 days in the presence of 100 ppb ozone in the atmosphere, respectively. The rate constants for gas phase E-N,N-dimethyl-1-propenylamine and N,N-dimethylallylamine reactions with ozone were too fast (>10-18 cm3 molecule-1 s-1) to be measured, implying lifetimes of less than 5 days. A multiphase kinetics model (KM-GAP) was used to probe the gas-solid kinetics of 1-dimethylamino-2-nitroethylene, yielding a rate constant for the surface reaction of 1.8 × 10-9 cm2 molecule-1 s-1 and in the bulk 1× 10-16 cm3 molecule-1 s-1. These results show that a nitro group attached to the C═C lowers the gas phase rate constant by 2-3 orders of magnitude compared to the simple alkenes, while amino groups have the opposite effect. The presence of both groups provides counterbalancing effects. Products with deleterious health effects including dimethylformamide and formaldehyde were identified by FTIR. The identified products differentiate whether the initial site of ozone attack is C═C and/or the amino group. This study provides a basis for predicting the environmental fates of emerging contaminants and shows that both the toxicity of both the parent compounds and the products should be taken into account in assessing their environmental impacts.

Smoke particles generated by burning biomass consist mainly of organic aerosol, referred to as biomass-burning organic aerosol (BBOA). BBOA influences the climate by scattering and absorbing solar radiation or acting as nuclei for cloud formation. The viscosity and the phase behavior (i.e. the number and type of phases present in a particle) are properties of BBOA that are expected to impact several climate-relevant processes but remain highly uncertain. We studied the phase behavior of BBOA using fluorescence microscopy, and showed that BBOA particles comprise two organic phases (a hydrophobic and a hydrophilic phase) across a wide range of atmospheric relative humidity (RH). We determined the viscosity of the two phases using a photobleaching method, and showed that the two phases possess different RH-dependent viscosities. The viscosity of the hydrophobic phase is largely independent of the RH from 0 to 95%. For temperatures less than 230 K, the hydrophobic phase is glassy (viscosity > 1012 Pa s) at RHs below 95%, with possible implications for heterogeneous reaction kinetics and cloud formation in the atmosphere. Using a kinetic multi-layer model (KM-GAP), we investigated the effect of two phases on the atmospheric lifetime of brown carbon within BBOA, which is a climate-warming agent. We showed that the presence of two phases can increase the lifetime of brown carbon in the planetary boundary layer and polar regions compared to previous modelling studies. Hence, liquid-liquid phase separation can lead to an increase in the predicted warming effect of BBOA on climate.

We developed tgBoost a machine learning model to predict glass transition temperature (Tg) of organic species considering their molecular structure and functionality for better predictions of the phase state of secondary organic aerosols.

Reactive oxygen species (ROS) are among the species thought to be responsible for the adverse health effects of particulate matter (PM) inhalation. Field studies suggest that indoor sources of ROS contribute to measured ROS on PM in indoor air. We hypothesize that ozone reacts on indoor surfaces to form semi-volatile ROS, in particular organic peroxides (OPX), which partition to airborne particles. To test this hypothesis, we modeled ozone-induced formation of OPX, its decay and its partitioning to PM in a residential building and compared the results to field measurements. Simulations indicate that, while ROS of outdoor origin is the primary contributor to indoor ROS (in PM), a substantial fraction of ROS present in indoor PM is from ozone-surface chemistry. At an air change rate equal to 1/h, and an outdoor ozone mixing ratio of 35 ppb, 25% of the ROS concentration in air is due to indoor formation and partitioning of OPX to PM. For the same conditions, but with a modest indoor source of PM (1.5 mg h

Monte Carlo simulations suggest that organic aerosol repartitioning during transport indoors is often kinetically limited due to a low bulk diffusivity, but liquid and some semisolid particles can achieve equilibrium repartitioning during indoor particle lifetimes.

Information on the global distributions of secondary organic aerosol (SOA) phase state and mixing times within SOA is needed to predict the impact of SOA on air quality, climate, and atmospheric ch...

Evidence has accumulated that secondary organic aerosols (SOAs) exhibit complex morphologies with multiple phases that can adopt amorphous semisolid or glassy phase states. However, experimental analysis and numerical modeling on the formation and evolution of SOA still often employ equilibrium partitioning with an ideal mixing assumption in the particle phase. Here we apply the kinetic multilayer model of gas–particle partitioning (KM-GAP) to simulate condensation of semi-volatile species into a core–shell phase-separated particle to evaluate equilibration timescales of SOA partitioning. By varying bulk diffusivity and the activity coefficient of the condensing species in the shell, we probe the complex interplay of mass transfer kinetics and the thermodynamics of partitioning. We found that the interplay of non-ideality and phase state can impact SOA partitioning kinetics significantly. The effect of non-ideality on SOA partitioning is slight for liquid particles but becomes prominent in semisolid or solid particles. If the condensing species is miscible with a low activity coefficient in the viscous shell phase, the particle can reach equilibrium with the gas phase long before the dissolution of concentration gradients in the particle bulk. For the condensation of immiscible species with a high activity coefficient in the semisolid shell, the mass concentration in the shell may become higher or overshoot its equilibrium concentration due to slow bulk diffusion through the viscous shell for excess mass to be transferred to the core phase. Equilibration timescales are shorter for the condensation of lower-volatility species into semisolid shell; as the volatility increases, re-evaporation becomes significant as desorption is faster for volatile species than bulk diffusion in a semisolid matrix, leading to an increase in equilibration timescale. We also show that the equilibration timescale is longer in an open system relative to a closed system especially for partitioning of miscible species; hence, caution should be exercised when interpreting and extrapolating closed-system chamber experimental results to atmosphere conditions. Our results provide a possible explanation for discrepancies between experimental observations of fast particle–particle mixing and predictions of long mixing timescales in viscous particles and provide useful insights into description and treatment of SOA in aerosol models.

Reactive oxygen species (ROS) and environmentally persistent free radicals (EPFR) play an important role in chemical transformation of atmospheric aerosols and adverse aerosol health effects. This study investigated the effects of nitrogen oxides (NOx) during photooxidation of α-pinene and naphthalene on the EPFR content and ROS formation from secondary organic aerosols (SOA). Electron paramagnetic resonance (EPR) spectroscopy was applied to quantify EPFR content and ROS formation. While no EPFR were detected in α-pinene SOA, we found that naphthalene SOA contained about 0.7 pmol μg-1 of EPFR, and NOx has little influence on EPFR concentrations and oxidative potential. α-Pinene and naphthalene SOA generated under low NOx conditions form OH radicals and superoxide in the aqueous phase, which was lowered substantially by 50-80% for SOA generated under high NOx conditions. High-resolution mass spectrometry analysis showed the substantial formation of nitroaromatics and organic nitrates in a high NOx environment. The modeling results using the GECKO-A model that simulates explicit gas-phase chemistry and the radical 2D-VBS model that treats autoxidation predicted reduced formation of hydroperoxides and enhanced formation of organic nitrates under high NOx due to the reactions of peroxy radicals with NOx instead of their reactions with HO2. Consistently, the presence of NOx resulted in the decrease of peroxide contents and oxidative potential of α-pinene SOA.

Secondary organic aerosol (SOA) plays a critical, yet uncertain, role in air quality and climate. Once formed, SOA is transported throughout the atmosphere and is exposed to solar UV light. Information on the viscosity of SOA, and how it may change with solar UV exposure, is needed to accurately predict air quality and climate. However, the effect of solar UV radiation on the viscosity of SOA and the associated implications for air quality and climate predictions is largely unknown. Here, we report the viscosity of SOA after exposure to UV radiation, equivalent to a UV exposure of 6 to 14 d at midlatitudes in summer. Surprisingly, UV-aging led to as much as five orders of magnitude increase in viscosity compared to unirradiated SOA. This increase in viscosity can be rationalized in part by an increase in molecular mass and oxidation of organic molecules constituting the SOA material, as determined by high-resolution mass spectrometry. We demonstrate that UV-aging can lead to an increased abundance of aerosols in the atmosphere in a glassy solid state. Therefore, UV-aging could represent an unrecognized source of nuclei for ice clouds in the atmosphere, with important implications for Earth’s energy budget. We also show that UV-aging increases the mixing times within SOA particles by up to five orders of magnitude throughout the troposphere with important implications for predicting the growth, evaporation, and size distribution of SOA, and hence, air pollution and climate.

The reactions of sulfur dioxide (SO 2 ) with surface-bound compounds on atmospheric aerosols lead to the formation of organic sulfur (OS) compounds, thereby affecting the air quality and climate. Here, we show that the heterogeneous reaction of SO 2 with authentic urban grime under near-ultraviolet sunlight irradiation leads to a large suite of various organic compounds including OS released in the gas phase. Calculations indicate that at the core area of Guangzhou, building surface uptake of SO 2 is 15 times larger than uptake of SO 2 on aerosol surfaces, yielding ~20 ng m −3 of OS that represents an important fraction of the observed OS compounds (60 to 200 ng m −3 ) in ambient aerosols of Chinese megacities. This chemical pathway occurring during daytime can contribute to the observed fraction of OS compounds in aerosols and improve the understanding of haze formation and urban air pollution.

The reactions of sulfur dioxide (SO

Rationale: Evidence linking outdoor air pollution with coronavirus disease (COVID-19) incidence and mortality is largely based on ecological comparisons between regions that may differ in factors s...

This paper investigates the effects of ionizers on the ozone concentration within vehicle cabins by using a series of measurements combined with a kinetic box model. Testing consisted of measuring ozone concentration during static tests where the ventilation of the test vehicle was turned on and off depending on the test. This testing was repeated for three different portable ionizers and two vehicles with built-in ionizers. Ionizer A produced ozone at a rate of ∼0.04 ppb s

Reactive oxygen species (ROS) play a critical role in the chemical transformation of atmospheric secondary organic aerosols (SOA) and aerosol health effects by causing oxidative stress in vivo. Acidity is an important physicochemical property of atmospheric aerosols, but its effects on the ROS formation from SOA have been poorly characterized. By applying the electron paramagnetic resonance spin-trapping technique and the Diogenes chemiluminescence assay, we find highly distinct radical yields and composition at different pH values in the range of 1-7.4 from SOA generated by oxidation of isoprene, α-terpineol, α-pinene, β-pinene, toluene, and naphthalene. We observe that isoprene SOA has substantial hydroxyl radical (•OH) and organic radical yields at neutral pH, which are 1.5-2 times higher compared to acidic conditions in total radical yields. Superoxide (O2 •-) is found to be the dominant species generated by all types of SOAs at lower pH. At neutral pH, α-terpineol SOA exhibits a substantial yield of carbon-centered organic radicals, while no radical formation is observed by aromatic SOA. Further experiments with model compounds show that the decomposition of organic peroxide leading to radical formation may be suppressed at lower pH due to acid-catalyzed rearrangement of peroxides. We also observe 1.5-3 times higher molar yields of hydrogen peroxide (H2O2) in acidic conditions compared to neutral pH by biogenic and aromatic SOA, likely due to enhanced decomposition of α-hydroxyhydroperoxides and quinone redox cycling, respectively. These findings are critical to bridge the gap in understanding ROS formation mechanisms and kinetics in atmospheric and physiological environments.

The heterogeneous reaction of ozone and iodide is both an important source of atmospheric iodine and dry deposition pathway of ozone in marine environments. While the iodine generated from this reaction is primarily in the form of HOI and I

Large surface area-to-volume ratios indoors cause heterogeneous interactions to be especially important. Semi-volatile organic compounds can deposit on impermeable indoor surfaces forming thin organic films. We developed a new model to simulate the initial film formation by treating gas-phase diffusion and turbulence through a surface boundary layer and multi-layer reversible adsorption on rough surfaces, as well as subsequent film growth by resolving bulk diffusion and chemical reactions in a film. The model was applied with consistent parameters to reproduce twenty-one sets of film formation measurements due to multi-layer adsorption of multiple phthalates onto different indoor-relevant surfaces, showing that the films should initially be patchy with the formation of pyramid-like structures on the surface. Sensitivity tests showed that highly turbulent conditions can lead to the film growing by more than a factor of two compared to low turbulence conditions. If surface films adopt an ultra-viscous state with bulk diffusion coefficients of less than 10-18 cm2 s-1 , a significant decrease in film growth is expected. The presence of chemical reactions in the film has the potential to increase the rate of film growth by nearly a factor of two.

Organic aerosol can adopt a wide range of viscosities, from liquid to glass, depending on the local humidity. In highly viscous droplets, the evaporation rates of organic components are suppressed to varying degrees, yet water evaporation remains fast. Here, we examine the coevaporation of semivolatile organic compounds (SVOCs), along with their solvating water, from aerosol particles levitated in a humidity-controlled environment. To better replicate the composition of secondary aerosol, nonvolatile organics were also present, creating a three-component diffusion problem. Kinetic modeling reproduced the evaporation accurately when the SVOCs were assumed to obey the Stokes-Einstein relation, and water was not. Crucially, our methodology uses previously collected data to constrain the time-dependent viscosity, as well as water diffusion coefficients, allowing it to be predictive rather than postdictive. Throughout the study, evaporation rates were found to decrease as SVOCs deplete from the particle, suggesting path function type behavior.

Polycyclic aromatic hydrocarbons (PAHs) are carcinogenic air pollutants. The dispersion of PAHs in the atmosphere is influenced by gas–particle partitioning and chemical loss. These processes are closely interlinked and may occur at vastly differing timescales, which complicates their mathematical description in chemical transport models. Here, we use a kinetic model that explicitly resolves mass transport and chemical reactions in the gas and particle phases to describe and explore the dynamic and non-equilibrium interplay of gas–particle partitioning and chemical losses of PAHs on soot particles. We define the equilibration timescale τeq of gas–particle partitioning as the e-folding time for relaxation of the system to the partitioning equilibrium. We find this metric to span from seconds to hours depending on temperature, particle surface area, and the type of PAH. The equilibration time can be approximated using a time-independent equation, τeq≈1kdes+kads, which depends on the desorption rate coefficient kdes and adsorption rate coefficient kads, both of which can be calculated from experimentally accessible parameters. The model reveals two regimes in which different physical processes control the equilibration timescale: a desorption-controlled and an adsorption-controlled regime. In a case study with the PAH pyrene, we illustrate how chemical loss can perturb the equilibrium particulate fraction at typical atmospheric concentrations of O3 and OH. For the surface reaction with O3, the perturbation is significant and increases with the gas-phase concentration of O3. Conversely, perturbations are smaller for reaction with the OH radical, which reacts with pyrene on both the surface of particles and in the gas phase. Global and regional chemical transport models typically approximate gas–particle partitioning with instantaneous-equilibration approaches. We highlight scenarios in which these approximations deviate from the explicitly coupled treatment of gas–particle partitioning and chemistry presented in this study. We find that the discrepancy between solutions depends on the operator-splitting time step and the choice of time step can help to minimize the discrepancy. The findings and techniques presented in this work not only are relevant for PAHs but can also be applied to other semi-volatile substances that undergo chemical reactions and mass transport between the gas and particle phase.

Metal components in fine particulate matter (PM2.5) from nontailpipe emissions may play an important role in underlying the adverse respiratory effects of PM2.5. We investigated the associations between long-term exposure to iron (Fe) and copper (Cu) in PM2.5 and their combined impact on reactive oxygen species (ROS) generation in human lungs, and the incidence of asthma, chronic obstructive pulmonary disease (COPD), COPD mortality, pneumonia mortality, and respiratory mortality. We conducted a population-based cohort study of ∼0.8 million adults in Toronto, Canada. Land-use regression models were used to estimate the concentrations of Fe, Cu, and ROS. Outcomes were ascertained using validated health administrative databases. We found positive associations between long-term exposure to Fe, Cu, and ROS and the risks of all five respiratory outcomes. The associations were more robust for COPD, pneumonia mortality, and respiratory mortality than for asthma incidence and COPD mortality. Stronger associations were observed for ROS than for either Fe or Cu. In two-pollutant models, adjustment for nitrogen dioxide somewhat attenuated the associations while adjustment for PM2.5 had little influence. Long-term exposure to Fe and Cu in PM2.5 and estimated ROS concentration in lung fluid was associated with increased incidence of respiratory diseases, suggesting the adverse respiratory effects of nontailpipe emissions.

Atmospheric aerosols can exist in amorphous semi-solid or glassy phase states whose viscosity varies with atmospheric temperature and relative humidity. The temperature and humidity dependence of viscosity has been hypothesized to be predictable from the combination of a water–organic binary mixing rule of the glass transition temperature, a glass-transition-temperature-scaled viscosity fragility parameterization, and a water uptake parameterization. This work presents a closure study between predicted and observed viscosity for sucrose and citric acid. Viscosity and glass transition temperature as a function of water content are compiled from literature data and used to constrain the fragility parameterization. New measurements characterizing viscosity of sub-100 nm particles using the dimer relaxation method are presented. These measurements extend the available data of temperature- and humidity-dependent viscosity to −28 ∘C. Predicted relationships agree well with observations at room temperature and with measured isopleths of constant viscosity at ∼107 Pa s at temperatures warmer than −28 ∘C. Discrepancies at colder temperatures are observed for sucrose particles. Simulations with the kinetic multi-layer model of gas–particle interactions suggest that the observed deviations at colder temperature for sucrose can be attributed to kinetic limitations associated with water uptake at the timescales of the dimer relaxation experiments. Using the available information, updated equilibrium phase-state diagrams (-80∘C

To predict important secondary organic aerosol (SOA) properties, information on viscosity or diffusion rates within SOA is needed. Ozonolysis of β-caryophyllene is an important SOA source; however,...

Molecular composition, viscosity, and liquid–liquid phase separation (LLPS) were investigated for secondary organic aerosol (SOA) derived from synthetic mixtures of volatile organic compounds (VOCs) representing emission profiles for Scots pine trees under healthy and aphid-herbivory stress conditions. Model “healthy plant SOA” and “stressed plant SOA” were generated in a 5 m3 environmental smog chamber by photooxidation of the mixtures at 50% relative humidity (RH). SOA from photooxidation of α-pinene was also prepared for comparison. Molecular composition was determined with high resolution mass spectrometry, viscosity was determined with the poke-flow technique, and liquid–liquid phase separation was investigated with optical microscopy. The stressed plant SOA had increased abundance of higher molecular weight species, reflecting a greater fraction of sesquiterpenes in the stressed VOC mixture compared to the healthy plant VOC mixture. LLPS occurred in both the healthy and stressed plant SOA; however, stressed plant SOA exhibited phase separation over a broader humidity range than healthy plant SOA, with LLPS persisting down to 23 ± 11% RH. At RH ≤25%, both stressed and healthy plant SOA viscosity exceeded 108 Pa s, a value similar to that of tar pitch. At 40% and 50% RH, stressed plant SOA had the highest viscosity, followed by healthy plant SOA and then α-pinene SOA in descending order. The observed peak abundances in the mass spectra were also used to estimate the SOA viscosity as a function of RH and volatility. The predicted viscosity of the healthy plant SOA was lower than that of the stressed plant SOA driven by both the higher glass transition temperatures and lower hygroscopicity of the organic molecules making up stressed plant SOA. These findings suggest that plant stress influences the physicochemical properties of biogenic SOA. Furthermore, a complex mixture of VOCs resulted in a higher SOA viscosity compared to SOA generated from α-pinene alone at ≥25% RH, highlighting the importance of studying properties of SOA generated from more realistic multi-component VOC mixtures.

Background Exposure to fine particulate (PM2.5) air pollution is associated with increased cardiovascular disease (CVD), but less is known about its specific components, such as metals originating from non-tailpipe emissions. We investigated the associations of long-term exposure to metal components [iron (Fe) and copper (Cu)] in PM2.5 with CVD incidence. Methods We conducted a population-based cohort study in Toronto, Canada. Exposures to Fe and Cu in PM2.5 and their combined impact on the concentration of reactive oxygen species (ROS) in lung fluid were estimated using land use regression models. Incidence of acute myocardial infarction (AMI), congestive heart failure (CHF) and CVD death was ascertained using health administrative datasets. We used mixed-effects Cox regression models to examine the associations between the exposures and health outcomes. A series of sensitivity analyses were conducted, including indirect adjustment for individual-level cardiovascular risk factors (e.g. smoking), and adjustment for PM2.5 and nitrogen dioxide (NO2). Results In single-pollutant models, we found positive associations between the three exposures and all three outcomes, with the strongest associations detected for the estimated ROS. The associations of AMI and CHF were sensitive to indirect adjustment, but remained robust for CVD death in all sensitivity analyses. In multi-pollutant models, the associations of the three exposures generally remained unaltered. Interestingly, adjustment for ROS did not substantially change the associations between PM2.5 and CVD, but attenuated the associations of NO2. Conclusions Long-term exposure to Fe and Cu in PM2.5 and their combined impact on ROS were consistently associated with increased CVD death.

Nitrous acid (HONO) is an important gaseous pollutant contributing to indoor air pollution because it causes adverse health effects and is the main source of hydroxyl radicals (OH). Here, we present direct measurements of HONO produced through light-induced heterogeneous reactions of NO2 with grime adsorbed on glass window. The uptake coefficients of NO2 [γ(NO2)] on the glass plates from the kitchen increased markedly from (2.3 ± 0.1) × 10-6 at 0% RH to (4.1 ± 0.5) × 10-6 at 90% RH. We report a significant quantity of daytime HONO produced in the kitchen, compared to the living room and bedroom. Kinetic modeling suggests that phase state and bulk diffusivity play important roles in the NO2 uptake; the best fit to the measured uptake coefficients is obtained with fixed diffusion coefficients. Photon scattering may be occurring at the surface of the films, leading to enhanced photon-excitation rates of polycyclic aromatic hydrocarbons. By taking these effects into account, the results from this study indicate that the HONO yields obtained in this study can explain the missing HONO in the photochemical models describing the indoor air chemistry.

Organic aerosol emitted from cooking is a major concern for indoor air quality. During the House Observations of Microbial and Environmental Chemistry (HOMEChem) campaign, we simulated cooking, cleaning and occupancy activities in a realistic residential setting and measured resulting gas- and particle-phase emissions using a High-Resolution Time-of-Flight Chemical Ionization Mass Spectrometer with a Filter Inlet for Gases and Aerosols (FIGAERO-HR-ToF-CIMS). We identified ∼480 molecular formulas for compounds emitted on cooking-centered days and attributed them to potential sources including cooking, commercial, personal care products, and occupancy. Compounds with molecular formulas containing carbon, hydrogen, and oxygen atoms only (CHO group) composed most of the CIMS-measured molar fraction at 74-85%, with nitrogen-containing molecular formulas (CHNO group) being the second largest contributor (12-19%). We investigated the volatility of identified species based on FIGAERO-CIMS data in three ways: (1) using the maximum desorption temperature from one-dimensional thermograms, Tmax, (2) calculating gas-particle partitioning, Fp, (3) using a molecular corridor parameterization to estimate saturation concentrations based on molecular formulas. We used the kinetic multi-layer model of gas-particle interactions in aerosols and clouds (KM-GAP) to calculate equilibration timescales and found that under sampling conditions (T = 323 K), it can take up to 14 seconds for equilibrium conditions to be met, whereas sampling residence times are approximately 3 seconds. The chemical diversity and wide range of volatilities of species sampled during cooking-centered events highlight the importance of understanding aerosol emissions and partitioning in indoor spaces where people spend most of their time.

Hydroxyl (OH) radicals are highly reactive species that can oxidize most pollutant gases. In this study, high concentrations of OH radicals were found when people were exposed to ozone in a climate-controlled chamber. OH concentrations calculated by two methods using measurements of total OH reactivity, speciated alkenes, and oxidation products were consistent with those obtained from a chemically explicit model. Key to establishing this human-induced oxidation field is 6-methyl-5-hepten-2-one (6-MHO), which forms when ozone reacts with the skin-oil squalene and subsequently generates OH efficiently through gas-phase reaction with ozone. A dynamic model was used to show the spatial extent of the human-generated OH oxidation field and its dependency on ozone influx through ventilation. This finding has implications for the oxidation, lifetime, and perception of chemicals indoors and, ultimately, human health.