Residential Wood Burning and Vehicle Emissions as Major Sources of Environmentally Persistent Free Radicals in Fairbanks, Alaska.

Environmentally persistent free radicals (EPFRs) play an important role in aerosol effects on air quality and public health, but their atmospheric abundance and sources are poorly understood. We measured EPFRs contained in PM2.5 collected in Fairbanks, Alaska, in winter 2022. We find that EPFR concentrations were enhanced during surface-based inversion and correlate strongly with incomplete combustion markers, including carbon monoxide and elemental carbon (R2 > 0.75). EPFRs exhibit moderately good correlations with PAHs, biomass burning organic aerosols, and potassium (R2 > 0.4). We also observe strong correlations of EPFRs with hydrocarbon-like organic aerosols, Fe and Ti (R2 > 0.6), and single-particle mass spectrometry measurements reveal internal mixing of PAHs, with potassium and iron. These results suggest that residential wood burning and vehicle tailpipes are major sources of EPFRs and nontailpipe emissions, such as brake wear and road dust, may contribute to the stabilization of EPFRs. Exposure to the observed EPFR concentrations (18 ± 12 pmol m-3) would be equivalent to smoking ∼0.4-1 cigarette daily. Very strong correlations (R2 > 0.8) of EPFR with hydroxyl radical formation in surrogate lung fluid indicate that exposure to EPFRs may induce oxidative stress in the human respiratory tract.

Distinct Temperature Trends in the Uptake of Gaseous n-Butylamine on Two Solid Diacids.

Uptake coefficients of n-butylamine (BA) on solid succinic (SA) and glutaric acids (GA) from 298 to 177 K were measured using a newly combined Knudsen cell temperature-programmed desorption apparatus. The uptake coefficients on SA increase monotonically from (1.9 ± 0.5) × 10-4 at 298 K to 0.14 ± 0.05 at 177 K (errors represent 2σ statistical errors, overall errors are estimated to be ±60%). This is consistent with a surface reaction mechanism to form solid aminium carboxylate. In contrast, the uptake coefficients on GA increase from 0.11 ± 0.04 at 298 K to 0.25 ± 0.04 at 248 K but then decrease to 0.030 ± 0.010 at 177 K. This unusual trend in temperature dependence of the uptake coefficient is due to formation of an ionic liquid (IL) layer upon the surface reaction of BA with GA, leading to a competition between the rate of desorption of BA and the rates of diffusion and reaction within the IL. Overall, the kinetic multi-layer model of aerosol surface and bulk chemistry (KM-SUB) satisfactorily reproduces these unique trends. This work provides mechanistic insight and predictive capability for the temperature-dependence of reactive uptake processes involving multiple phase changes upon surface reaction.

Elucidating gas-surface interactions relevant to atmospheric particle growth using combined temperature programmed desorption and temperature-dependent uptake.

Understanding growth mechanisms for particles in air is fundamental to developing a predictive capability for their impacts on human health, visibility, and climate. In the case of highly viscous semi-solid or solid particles, the likelihood of impinging gases being taken up to grow the particle will be influenced by the initial uptake coefficient and by the residence time of the adsorbed gas on the surface. Here, a new approach that combines Knudsen cell capabilities for gas uptake measurements with temperature programmed desorption (TPD) for binding energy measurements of gases is described. The application of this unique capability to the uptake of organic gases on silica demonstrates its utility and the combination of thermodynamic and kinetic data that can be obtained. Lower limits to the initial net uptake coefficients at 170 K are (3.0 ± 0.6) × 10-3, (4.9 ± 0.6) × 10-3 and (4.3 ± 0.8) × 10-3 for benzene, 1-chloropentane, and methanol, respectively, and are reported here for the first time. The uptake data demonstrated that the ideal gas lattice model was appropriate, which informed the analysis of the TPD data. From the thermal desorption measurements, desorption energies of 34.6 ± 2.5, 45.8 ± 5.5, and 40.0 ± 5.6 kJ mol-1 (errors are 1σ) are obtained for benzene, 1-chloropentane, and methanol, respectively, and show good agreement with previously reported measurements. A multiphase kinetics model was applied to quantify uptake, desorption, and diffusion through the particle multilayers and hence extract desorption kinetics. Implications for uptake of organics on silica surfaces in the atmosphere and the utility of this system for determining relationships between residence times of organic gases and particle surfaces of varying composition are discussed in the context of developing quantitative predictions for growth of aerosol particles in air.

Secondary Organic Aerosol from OH-Initiated Oxidation of Mixtures of d-Limonene and ß-Myrcene.

The chemical composition and physical properties of secondary organic aerosol (SOA) generated through OH-initiated oxidation of mixtures containing ß-myrcene, an acyclic monoterpene, and d-limonene, a cyclic monoterpene, were investigated to assess the extent of the chemical interactions between their oxidation products. The SOA samples were prepared in an environmental smog chamber, and their composition was analyzed offline using ultraperformance liquid chromatography coupled with electrospray ionization high-resolution mass spectrometry (UPLC-ESI-HRMS). Our results suggested that SOA containing ß-myrcene showed a higher proportion of oligomeric compounds with low volatility compared to that of SOA from d-limonene. The formula distribution and signal intensities of the mixed SOA could be accurately predicted by a linear combination of the mass spectra of the SOA from individual precursors. Effects of cross-reactions were observed in the distribution of isomeric oxidation products within the mixed SOA, as made evident by chromatographic analysis. On the whole, ß-myrcene and d-limonene appear to undergo oxidation by OH largely independently from each other, with only subtle effects from cross-reactions influencing the yields of specific oxidation products.

Ambient exposure to fine particulate matter with oxidative potential affects oxidative stress biomarkers in pregnancy.

Prenatal exposures to ambient particulate matter (PM2.5) from traffic may generate oxidative stress, and thus contribute to adverse birth outcomes. We investigated whether PM2.5 constituents from brake and tire wear affect levels of oxidative stress biomarkers (malondialdehyde (MDA), 8-hydroxy-2'-deoxyguanosine (8-OHdG)) using urine samples collected up to three times during pregnancy in 156 women recruited from antenatal clinics at the University of California Los Angeles. Land use regression models with co-kriging were employed to estimate average residential outdoor concentrations of black carbon (BC), PM2.5 mass, PM2.5 metal components, and three PM2.5 oxidative potential metrics during the 4-weeks prior to urine sample collection. 8-OHdG concentrations in mid-pregnancy increased by 24.8% (95% CI: 9.0, 42.8) and 14.3% (95% CI: 0.4%, 30.0%) per interquartile range (IQR) increase in PM2.5 mass and BC, respectively. The brake wear marker (barium) and the oxidative potential metrics were associated with increased MDA concentration in the 1st sample collected (10-17 gestational week), but 95% CIs included the null. Traffic-related air pollution contributed in early to mid-pregnancy to oxidative stress generation previously linked to adverse birth outcomes.

Ozone Loss on Painted Surfaces: Dependence on Relative Humidity, Aging, and Exposure to Reactive SVOCs.

Ozone and its oxidation products result in negative health effects when inhaled. Despite painted surfaces being the most abundant surface in indoor spaces, surface loss remains one of the largest uncertainties in the indoor ozone budget. Here, ozone uptake coefficients (γO3) on painted surfaces were measured in a flow-through reactor where 79% of the inner surfaces were removable painted glass sheets. Flat white paint initially had a high uptake coefficient (8.3 × 10-6) at 20% RH which plateaued to 1.1 × 10-6 as the paint aged in an indoor office over weeks. Increasing the RH from 0 to 75% increased γO3 by a factor of 3.0, and exposure to 134 ppb of α-terpineol for 1 h increased γO3 by a factor of 1.6 at 20% RH. RH also increases α-terpineol partitioning to paint, further increasing ozone loss, but the type of paint (flat, eggshell, satin, semigloss) had no significant effect. A kinetic multilayer model captures the dependence of γO3 on RH and the presence of α-terpineol, indicating the reacto-diffusive depth for O3 is 1 to 2 µm. Given the similarity of the kinetics on aged surfaces across many paint types and the sustained reactivity during aging, these results suggest a mechanism for catalytic loss.

Formation of persistent free radicals from epigallocatechin Gallate in tea processing and their implications on DNA damage and cell cytotoxicity.

Tea is widely consumed in both beverages and food. Epigallocatechin gallate (EGCG) is the most crucial active ingredient in tea. Currently, knowledges on transformation processes of EGCG during tea processing are lacking. Understanding the chemical reactions of EGCG and its products during tea processing is important for assessing the safety of tea-containing food. Here, we revealed the formation of persistent free radicals (PFRs) from EGCG under the influence of heating and light irradiation, which was substantiated with evidence. These PFRs exhibited stability for >30 min in simulated gastric fluid. Furthermore, we observed potential effects of these PFRs on DNA damage and cell cytotoxicity in vitro. By combining electron paramagnetic resonance spectrometer with Fourier transform ion cyclotron resonance mass spectrometry, we elucidated the pathways involved in free radical formation. These findings are expected to contribute to a comprehensive understanding of free radical chemistry in tea-containing food.

Assessing the Oxidative Potential of Outdoor PM2.5 in Wintertime Fairbanks, Alaska.

The oxidative potential (OP) of outdoor PM2.5 in wintertime Fairbanks, Alaska, is investigated and compared to those in wintertime Atlanta and Los Angeles. Approximately 40 filter samples collected in January-February 2022 at a Fairbanks residential site were analyzed for OP utilizing dithiothreitol-depletion (OPDTT) and hydroxyl-generation (OPOH) assays. The study-average PM2.5 mass concentration was 12.8 µg/m3, with a 1 h average maximum of 89.0 µg/m3. Regression analysis, correlations with source tracers, and contrast between cold and warmer events indicated that OPDTT was mainly sensitive to copper, elemental carbon, and organic aerosol from residential wood burning, and OPOH to iron and organic aerosol from vehicles. Despite low photochemically-driven oxidation rates, the water-soluble fraction of OPDTT was unusually high at 77%, mainly from wood burning emissions. In contrast to other locations, the Fairbanks average PM2.5 mass concentration was higher than Atlanta and Los Angeles, whereas OPDTT in Fairbanks and Atlanta were similar, and Los Angeles had the highest OPDTT and OPOH. Site differences were observed in OP when normalized by both the volume of air sampled and the particle mass concentration, corresponding to exposure and the intrinsic health-related properties of PM2.5, respectively. The sensitivity of OP assays to specific aerosol components and sources can provide insights beyond the PM2.5 mass concentration when assessing air quality.

Indoor-Outdoor Oxidative Potential of PM2.5 in Wintertime Fairbanks, Alaska: Impact of Air Infiltration and Indoor Activities.

The indoor air quality of a residential home during winter in Fairbanks, Alaska, was investigated and contrasted with outdoor levels. Twenty-four-hour average indoor and outdoor filter samples were collected from January 17 to February 25, 2022, in a residential area with high outdoor PM2.5 concentrations. The oxidative potential of PM2.5 was determined using the dithiothreitol-depletion assay (OPDTT). For the unoccupied house, the background indoor-to-outdoor (I/O) ratio of mass-normalized OP (OPmDTT), a measure of the intrinsic health-relevant properties of the aerosol, was less than 1 (0.53 ± 0.37), implying a loss of aerosol toxicity as air was transported indoors. This may result from transport and volatility losses driven by the large gradients in temperature (average outdoor temperature of -19°C/average indoor temperature of 21 °C) or relative humidity (average outdoor RH of 78%/average indoor RH of 11%), or both. Various indoor activities, including pellet stove use, simple cooking experiments, incense burning, and mixtures of these activities, were conducted. The experiments produced PM2.5 with a highly variable OPmDTT. PM2.5 from cooking emissions had the lowest OP values, while pellet stove PM2.5 had the highest. Correlations between volume-normalized OPDTT (OPvDTT), relevant to exposure, and indoor PM2.5 mass concentration during experiments were much lower compared to those in outdoor environments. This suggests that mass concentration alone can be a poor indicator of possible adverse effects of various indoor emissions. These findings highlight the importance of considering both the quantity of particles and sources (chemical composition), as health metrics for indoor air quality.

Overview of the Alaskan Layered Pollution and Chemical Analysis (ALPACA) Field Experiment.

The Alaskan Layered Pollution And Chemical Analysis (ALPACA) field experiment was a collaborative study designed to improve understanding of pollution sources and chemical processes during winter (cold climate and low-photochemical activity), to investigate indoor pollution, and to study dispersion of pollution as affected by frequent temperature inversions. A number of the research goals were motivated by questions raised by residents of Fairbanks, Alaska, where the study was held. This paper describes the measurement strategies and the conditions encountered during the January and February 2022 field experiment, and reports early examples of how the measurements addressed research goals, particularly those of interest to the residents. Outdoor air measurements showed high concentrations of particulate matter and pollutant gases including volatile organic carbon species. During pollution events, low winds and extremely stable atmospheric conditions trapped pollution below 73 m, an extremely shallow vertical scale. Tethered-balloon-based measurements intercepted plumes aloft, which were associated with power plant point sources through transport modeling. Because cold climate residents spend much of their time indoors, the study included an indoor air quality component, where measurements were made inside and outside a house to study infiltration and indoor sources. In the absence of indoor activities such as cooking and/or heating with a pellet stove, indoor particulate matter concentrations were lower than outdoors; however, cooking and pellet stove burns often caused higher indoor particulate matter concentrations than outdoors. The mass-normalized particulate matter oxidative potential, a health-relevant property measured here by the reactivity with dithiothreiol, of indoor particles varied by source, with cooking particles having less oxidative potential per mass than pellet stove particles.

Reactive Oxygen Species Formation and Peroxide and Carbonyl Decomposition in Aqueous Photolysis of Secondary Organic Aerosols.

The mechanism and kinetics of reactive oxygen species (ROS) formation when atmospheric secondary organic aerosol (SOA) is exposed to solar radiation are poorly understood. In this study, we combined an in situ UV-vis irradiation system with electron paramagnetic resonance (EPR) spectroscopy to characterize the photolytic formation of ROS in aqueous extracts of SOA formed by the oxidation of isoprene, α-pinene, α-terpineol, and toluene. We observed substantial formation of free radicals, including •OH, superoxide (HO2•), and organic radicals (R•/RO•) upon irradiation. Compared to dark conditions, the radical yield was enhanced by a factor of ∼30 for •OH and by a factor of 2-10 for superoxide radicals, and we observed the emergence of organic radicals. Total peroxide measurements showed substantial decreases of peroxide contents after photoirradiation, indicating that organic peroxides can be an important source of the observed radicals. A liquid chromatography interfaced with high-resolution mass spectrometry was used to detect a number of organic radicals in the form of adducts with a spin trap, BMPO. The types of detected radicals and aqueous photolysis of model compounds indicated that photolysis of carbonyls by Norrish type I mechanisms plays an important role in the organic radical formation. The photolytic ROS formation serves as the driving force for cloud and fog processing of SOA.

Unexpected hydroxyl radical production in brewed tea under sunlight.

Tea is one of the world's most popular and widely consumed beverages. It is a common pastime to enjoy a cup of tea in the sunshine. However, little attention has been given to understanding the possible photochemical reactions occurring beneath the calm surface of brewed tea. Epigallocatechin gallate (EGCG), which is widely used in food and beverages, is the most significant active ingredient found in tea. In this study, we investigated the presence of free radicals in both an aqueous EGCG solution and brewed tea under simulated sunlight conditions. To our surprise, we unexpectedly observed the production of hydroxyl radicals (•OH) in brewed tea. It was found that sunlight irradiation played a critical role in the formation of •OH, independent of the presence of metal ions. Furthermore, we demonstrated that the •OH generated from the EGCG aqueous solution induced cell cytotoxicity and DNA damage in vitro. Considering the crucial role of •OH in various fields, including human health and the environment, it is important to further explore the practical implications of •OH production in brewed tea under sunlight. In summary, our study unveils the unexpected formation of •OH in brewed tea and emphasizes the significance of sunlight-induced reactions. The observed cytotoxic and DNA-damaging effects of •OH emphasize the importance of understanding the potential health consequences associated with tea consumption. Further research in this area will contribute to a better understanding of the broader implications of •OH production in brewed tea under sunlight.

Composition of indoor organic surface films in residences: simulating the influence of sources, partitioning, particle deposition, and air exchange.

Indoor surfaces are coated with organic films that modulate thermodynamic interactions between the surfaces and room air. Recently published models can simulate film formation and growth via gas-surface partitioning, but none have statistically investigated film composition. The Indoor Model of Aerosols, Gases, Emissions, and Surfaces (IMAGES) was used here to simulate ten years of nonreactive film growth upon impervious indoor surfaces within a Monte Carlo procedure representing a sub-set of North American residential buildings. Film composition was resolved into categories reflecting indoor aerosol (gas + particle phases) factors from three sources: outdoor-originating, indoor-emitted, and indoor-generated secondary organic material. In addition to gas-to-film partitioning, particle deposition was modeled as a vector for organics to enter films, and it was responsible for a majority of the film mass after ∼1000 days of growth for the median simulation and is likely the main source of LVOCs within films. Therefore, the organic aerosol factor possessing the most SVOCs contributes most strongly to the composition of early films, but as the film ages, films become more dominated by the factor with the highest particle concentration. Indoor-emitted organics (e.g. from cooking) often constituted at least a plurality of the simulated mass in developed films, but indoor environments are diverse enough that any major organic material source could be the majority contributor to film mass, depending on building characteristics and indoor activities. A sensitivity analysis suggests that rapid film growth is most likely in both newer, more air-tight homes and older homes near primary pollution sources.

Correction: Iodine emission from the reactive uptake of ozone to simulated seawater.

Correction for 'Iodine emission from the reactive uptake of ozone to simulated seawater' by Stephanie R. Schneider et al., Environ. Sci.: Processes Impacts, 2023, 25, 254-263, https://doi.org/10.1039/D2EM00111J.

Fine Particulate Matter Metal Composition, Oxidative Potential, and Adverse Birth Outcomes in Los Angeles.

BACKGROUND: Although many studies have linked prenatal exposure to PM2.5 to adverse birth outcomes, little is known about the effects of exposure to specific constituents of PM2.5 or mechanisms that contribute to these outcomes. OBJECTIVES: Our objective was to investigate effects of oxidative potential and PM2.5 metal components from non-exhaust traffic emissions, such as brake and tire wear, on the risk of preterm birth (PTB) and term low birth weight (TLBW). METHODS: For a birth cohort of 285,614 singletons born in Los Angeles County, California, in the period 2017-2019, we estimated speciated PM2.5 exposures modeled from land use regression with cokriging, including brake and tire wear related metals (barium and zinc), black carbon, and three markers of oxidative potential (OP), including modeled reactive oxygen species based on measured iron and copper (ROS), OH formation (OPOH), and dithiothreitol (DTT) loss (OPDTT). Using logistic regression, we estimated odds ratios (OR) and 95% confidence intervals (CI) for PTB and TLBW with speciated PM2.5 exposures and PM2.5 mass as continuous variables scaled by their interquartile range (IQR). RESULTS: For both metals and oxidative potential metrics, we estimated increased risks for PTB (ORs ranging from 1.01 to 1.03) and TLBW (ORs ranging from 1.02 to 1.05) per IQR exposure increment that were robust to adjustment for PM2.5 mass. Associations for PM2.5 mass, black carbon, metal components, and oxidative potential (especially ROS and OPOH) with adverse birth outcomes were stronger in Hispanic, Black, and mixed-race or Native American women. DISCUSSION: Our results indicate that exposure to PM2.5 metals from brake and tire wear and particle components that contribute to oxidative potential were associated with an increased risk of PTB and TLBW in Los Angeles County, particularly among Hispanic, Black, and mixed-race or Native American women. Thus, reduction of PM2.5 mass only may not be sufficient to protect the most vulnerable pregnant women and children from adverse effects due to traffic source exposures. https://doi.org/10.1289/EHP12196.

Phase Behavior and Viscosity in Biomass Burning Organic Aerosol and Climatic Impacts.

Smoke particles generated by burning biomass consist mainly of organic aerosol termed 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 at room temperature 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%. We use the Vogel-Fulcher-Tamman equation to extrapolate our results to colder and warmer temperatures, and based on the extrapolation, the hydrophobic phase is predicted to be glassy (viscosity >1012 Pa s) for temperatures less than 230 K and RHs below 95%, with possible implications for heterogeneous reaction kinetics and cloud formation in the atmosphere. Using a kinetic multilayer 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 modeling studies. Hence, the presence of two phases can lead to an increase in the predicted warming effect of BBOA on the climate.

Within-city spatial variations in long-term average outdoor oxidant gas concentrations and cardiovascular mortality: Effect modification by oxidative potential in the Canadian Census Health and Environment Cohort.

Health effects of oxidant gases may be enhanced by components of particulate air pollution that contribute to oxidative stress. Our aim was to examine if within-city spatial variations in the oxidative potential of outdoor fine particulate air pollution (PM2.5) modify relationships between oxidant gases and cardiovascular mortality. Methods: We conducted a retrospective cohort study of participants in the Canadian Census Health and Environment Cohort who lived in Toronto or Montreal, Canada, from 2002 to 2015. Cox proportional hazards models were used to estimate associations between outdoor concentrations of oxidant gases (Ox, a redox-weighted average of nitrogen dioxide and ozone) and cardiovascular deaths. Analyses were performed across strata of two measures of PM2.5 oxidative potential and reactive oxygen species concentrations (ROS) adjusting for relevant confounding factors. Results: PM2.5 mass concentration showed little within-city variability, but PM2.5 oxidative potential and ROS were more variable. Spatial variations in outdoor Ox were associated with an increased risk of cardiovascular mortality [HR per 5 ppb = 1.028, 95% confidence interval (CI): 1.001, 1.055]. The effect of Ox on cardiovascular mortality was stronger above the median of each measure of PM2.5 oxidative potential and ROS (e.g., above the median of glutathione-based oxidative potential: HR = 1.045, 95% CI: 1.009, 1.081; below median: HR = 1.000, 95% CI: 0.960, 1.043). Conclusion: Within-city spatial variations in PM2.5 oxidative potential may modify long-term cardiovascular health impacts of Ox. Regions with elevated Ox and PM2.5 oxidative potential may be priority areas for interventions to decrease the population health impacts of outdoor air pollution.

Effective mass accommodation for partitioning of organic compounds into surface films with different viscosities.

Indoor surfaces can act as reservoirs and reaction media influencing the concentrations and type of species that people are exposed to indoors. Mass accommodation and partitioning are impacted by the phase state and viscosity of indoor surface films. We developed the kinetic multi-layer model KM-FILM to simulate organic film formation and growth, but it is computationally expensive to couple such comprehensive models with indoor air box models. Recently, a novel effective mass accommodation coefficient (αeff) was introduced for efficient and effective treatments of gas-particle partitioning. In this study, we extended this approach to a film geometry with αeff as a function of penetration depth into the film, partitioning coefficient, bulk diffusivity, and condensed-phase reaction rate constant. Comparisons between KM-FILM and the αeff method show excellent agreement under most conditions, but with deviations before the establishment of quasi-equilibrium within the penetration depth. We found that the deposition velocity of species and overall film growth are impacted by bulk diffusivity in highly viscous films (Db ∼<10-15 cm2 s-1). Reactions that lead to non-volatile products can increase film thicknesses significantly, with the extent of film growth being dependent on the gas-phase concentration, rate coefficient, partitioning coefficient and diffusivity. Amorphous semisolid films with Db > ∼10-17-10-19 cm2 s-1 can be efficient SVOC reservoirs for compounds with higher partitioning coefficients as they can be released back to the gas phase over extended periods of time, while glassy solid films would not be able to act as reservoirs as gas-film partitioning is impeded.

Photoenhanced Radical Formation in Aqueous Mixtures of Levoglucosan and Benzoquinone: Implications to Photochemical Aging of Biomass-Burning Organic Aerosols.

The photochemical aging of biomass-burning organic aerosols (BBOAs) by exposure to sunlight changes the chemical composition over its atmospheric lifetime, affecting the toxicological and climate-relevant properties of BBOA particles. This study used electron paramagnetic resonance (EPR) spectroscopy with a spin-trapping agent, 5-tert-butoxycarbonyl-5-methyl-1-pyrroline-N-oxide (BMPO), high-resolution mass spectrometry, and kinetic modeling to study the photosensitized formation of reactive oxygen species (ROS) and free radicals in mixtures of benzoquinone and levoglucosan, known BBOA tracer molecules. EPR analysis of irradiated benzoquinone solutions showed dominant formation of hydroxyl radicals (•OH), which are known products of reaction of triplet-state benzoquinone with water, also yielding semiquinone radicals. In addition, hydrogen radicals (H•) were also observed, which were not detected in previous studies. They were most likely generated by photochemical decomposition of semiquinone radicals. The irradiation of mixtures of benzoquinone and levoglucosan led to substantial formation of carbon- and oxygen-centered organic radicals, which became prominent in mixtures with a higher fraction of levoglucosan. High-resolution mass spectrometry permitted direct observation of BMPO-radical adducts and demonstrated the formation of •OH, semiquinone radicals, and organic radicals derived from oxidation of benzoquinone and levoglucosan. Mass spectrometry also detected superoxide radical adducts (BMPO-OOH) that did not appear in the EPR spectra. Kinetic modeling of the processes in the irradiated mixtures successfully reproduced the time evolution of the observed formation of the BMPO adducts of •OH and H• observed with EPR. The model was then applied to describe photochemical processes that would occur in mixtures of benzoquinone and levoglucosan in the absence of BMPO, predicting the generation of HO2• due to the reaction of H• with dissolved oxygen. These results imply that photoirradiation of aerosols containing photosensitizers induces ROS formation and secondary radical chemistry to drive photochemical aging of BBOA in the atmosphere.