Search

IntroductionOxidative stress mediated by reactive oxygen species (ROS) is a key process for adverse aerosol health effects. Secondary organic aerosols (SOA) account for a major fraction of particulate matter with aerodynamic diameter ≤2.5 µm (PM2.5). PM2.5 inhalation and deposition into the respiratory tract causes the formation of ROS by chemical reactions and phagocytosis of macrophages in the epithelial lining fluid (ELF), but their relative contributions are not well quantified and their link to oxidative stress remains uncertain. The specific aims of this project were (1) elucidating the chemical mechanism and quantifying the formation kinetics of ROS in the ELF by SOA; (2) quantifying the relative importance of ROS formation by chemical reactions and macrophages in the ELF.MethodsSOA particles were generated using reaction chambers from oxidation of various precursors including isoprene, terpenes, and aromatic compounds with or without nitrogen oxides (NOx). We collected size-segregated PM at two highway sites in Anaheim, CA, and Long Beach, CA, and at an urban site in Irvine, CA, during two wildfire events. The collected particles were extracted into water or surrogate ELF that contained lung antioxidants. ROS generation was quantified using electron paramagnetic resonance (EPR) spectroscopy with a spin-trapping technique. PM oxidative potential (OP) was also quantified using the dithiothreitol assay. In addition, kinetic modeling was applied for analysis and interpretation of experimental data. Finally, we quantified cellular superoxide release by RAW264.7 macrophage cells upon exposure to quinones and isoprene SOA using a chemiluminescence assay as calibrated with an EPR spin-probing technique. We also applied cellular imaging techniques to study the cellular mechanism of superoxide release and oxidative damage on cell membranes.ResultsSuperoxide radicals (·O2-) were formed from aqueous reactions of biogenic SOA generated by hydroxy radical (·OH) photooxidation of isoprene, β-pinene, α-terpineol, and d-limonene. The temporal evolution of ·OH and ·O2- formation was elucidated by kinetic modeling with a cascade of aqueous reactions, including the decomposition of organic hydroperoxides (ROOH), ·OH oxidation of primary or secondary alcohols, and unimolecular decomposition of α-hydroxyperoxyl radicals. Relative yields of various types of ROS reflected the relative abundance of ROOH and alcohols contained in SOA, which generated under high NOx conditions, exhibited lower ROS yields. ROS formation by SOA was also affected by pH. Isoprene SOA had higher ·OH and organic radical yields at neutral than at acidic pH. At low pH ·O2- was the dominant species generated by all types of SOA. At neutral pH, α-terpineol SOA exhibited a substantial yield of carbon-centered organic radicals (R·), while no radical formation was observed by aromatic SOA.Organic radicals in the ELF were formed by mixtures of Fe2+ and SOA generated from photooxidation of isoprene, α-terpineol, and toluene. The molar yields of organic radicals by SOA were 5-10 times higher in ELF than in water. Fe2+ enhanced organic radical yields by a factor of 20-80. Ascorbate mediated redox cycling of iron ions and sustained organic peroxide decomposition, as supported by kinetic modeling reproducing time- and concentration-dependence of organic radical formation, as well as by additional experiments observing the formation of Fe2+ and ascorbate radicals in mixtures of ascorbate and Fe3+. ·OH and superoxide were found to be efficiently scavenged by antioxidants.Wildfire PM mainly generated ·OH and R· with minor contributions from superoxide and oxygen-centered organic radicals (RO·). PM OP was high in wildfire PM, exhibiting very weak correlation with radical forms of ROS. These results were in stark contrast with PM collected at highway and urban sites, which generated much higher amounts of radicals dominated by ·OH radicals that correlated well with OP. By combining field measurements of size-segregated chemical composition, a human respiratory tract model, and kinetic modeling, we quantified production rates and concentrations of different types of ROS in different regions of the ELF by considering particle-size-dependent respiratory deposition. While hydrogen peroxide (H2O2) and ·O2- production were governed by Fe and Cu ions, ·OH radicals were mainly generated by organic compounds and Fenton-like reactions of metal ions. We obtained mixed results for correlations between PM OP and ROS formation, providing rationale and limitations of the use of oxidative potential as an indicator for PM toxicity in epidemiological and toxicological studies.Quinones and isoprene SOA activated nicotinamide adenine dinucleotide phosphate (NADPH) oxidase in macrophages, releasing massive amounts of superoxide via respiratory burst and overwhelming the superoxide formation by aqueous chemical reactions in the ELF. The threshold dose for macrophage activation was much smaller for quinones compared with isoprene SOA. The released ROS caused lipid peroxidation to increase cell membrane fluidity, inducing oxidative damage and stress. Further increases of doses led to the activation of antioxidant response elements, reducing the net cellular superoxide production. At very high doses and long exposure times, chemical production became comparably important or dominant if the escalation of oxidative stress led to cell death.ConclusionsThe mechanistic understandings and quantitative information on ROS generation by SOA particles provided a basis for further elucidation of adverse aerosol health effects and oxidative stress by PM2.5. For a comprehensive assessment of PM toxicity and health effects via oxidative stress, it is important to consider both chemical reactions and cellular processes for the formation of ROS in the ELF. Chemical composition of PM strongly influences ROS formation; further investigations are required to study ROS formation from various PM sources. Such research will provide critical information to environmental agencies and policymakers for the development of air quality policy and regulation.

Neonicotinoids (NNs) are commonly found throughout the environment on surfaces such as seeds, soil, vegetation, and blowing dust particles. However, there is a paucity of data on the kinetics and oxidation products formed on contact with the atmosphere which limits understanding of their potentially far-reaching impacts. In this study, in situ attenuated total reflectance (ATR) FTIR spectroscopy was used to investigate the OH oxidation of thin films of three solid NNs, imidacloprid (IMD), dinotefuran (DNF) and clothianidin (CLD) at 295 ± 3 K. The experimentally measured reaction probabilities based on initial rates of NN loss are (1.6 ± 0.8) × 10-2 for IMD, (1.5 ± 0.6) × 10-2 for DNF and (0.9 ± 0.2) × 10-2 for CLD (±1s), suggesting initial NN lifetimes with respect to OH of 10-17 days. The kinetics were interpreted using a multiphase kinetics model, KM-SUB, which showed that the OH uptake and reaction occurred primarily in the surface layer. Products identified by mass spectrometry included carbonyl-, alcohol- and olefin-containing species formed via hydrogen abstraction from aliphatic C-H groups. Additionally, carbonyl-containing desnitro and urea derivative products were observed from secondary reactions of the initially formed photodegradation products. Reaction with OH will contribute to NN loss both during the day as well as at night when there are non-photolytic sources of this radical. Thus, OH reactions with both the parent neonicotinoid and its photodegradation products should be considered in assessing their environmental impacts.

Understanding impacts of secondary organic aerosol (SOA) in air requires a molecular-level understanding of particle growth via interactions between gases and particle surfaces. The interactions of three gaseous organic nitrates with selected organic substrates were measured at 296 K using attenuated total reflection Fourier transform infrared spectroscopy. The organic substrates included a long chain alkane (triacontane, TC), a keto-acid (pinonic acid, PA), an amorphous ester oligomer (poly(ethylene adipate) di-hydroxy terminated, PEA), and laboratory-generated SOA from α-pinene ozonolysis. There was no uptake of the organic nitrates on the non-polar TC substrate, but significant uptake occurred on PEA, PA, and α-pinene SOA. Net uptake coefficients (γ) at the shortest reaction times accessible in these experiments ranged from 3 × 10-4 to 9 × 10-6 and partition coefficients (K) from 1 × 107 to 9 × 104. Trends in γ did not quantitatively follow trends in K, suggesting that the intermolecular forces involved in gas-surface interactions are not the same as those in the bulk, which is supported by theoretical calculations. Kinetic modeling showed that nitrates diffused throughout the organic films over several minutes, and that the bulk diffusion coefficients evolved as uptake/desorption occurred. A plasticizing effect occurred upon incorporation of the organic nitrates, whereas desorption caused decreases in diffusion coefficients in the upper layers, suggesting a crusting effect. Accurate predictions of particle growth in the atmosphere will require knowledge of uptake coefficients, which are likely to be several orders of magnitude less than one, and of the intermolecular interactions of gases with particle surfaces as well as with the particle bulk.

Ozone reacts with skin lipids such as squalene, generating an array of organic compounds, some of which can act as respiratory or skin irritants. Thus, it is important to quantify and predict the formation of these products under different conditions in indoor environments. We developed the kinetic multilayer model that explicitly resolves mass transport and chemical reactions at the skin and in the gas phase (KM-SUB-Skin). It can reproduce the concentrations of ozone and organic compounds in previous measurements and new experiments. This enabled the spatial and temporal concentration profiles in the skin oil and underlying skin layers to be resolved. Upon exposure to ~30 ppb ozone, the concentrations of squalene ozonolysis products in the gas phase and in the skin reach up to several ppb and on the order of ~10 mmol m-3 . Depending on various factors including the number of people, room size, and air exchange rates, concentrations of ozone can decrease substantially due to reactions with skin lipids. Ozone and dicarbonyls quickly react away in the upper layers of the skin, preventing them from penetrating deeply into the skin and hence reaching the blood.

We report the first measurements of HO2 uptake coefficients, γ, for secondary organic aerosol (SOA) particles and for the well-studied model compound sucrose which we doped with copper(II). Above 65% relative humidity (RH), γ for copper(II)-doped sucrose aerosol particles equalled the surface mass accommodation coefficient α = 0.22±0.06, but it decreased to γ = 0.012±0.007 upon decreasing the RH to 17 %. The trend of γ with RH can be explained by an increase in aerosol viscosity and the contribution of a surface reaction, as demonstrated using the kinetic multilayer model of aerosol surface and bulk chemistry (KM-SUB). At high RH the total uptake was driven by reaction in the near-surface bulk and limited by mass accommodation, whilst at low RH it was limited by surface reaction. SOA from two different precursors, α-pinene and 1,3,5-trimethylbenzene (TMB), was investigated, yielding low uptake coefficients of γ < 0.001 and γ = 0.004±0.002, respectively. It is postulated that the larger values measured for TMB-derived SOA compared to α-pinene-derived SOA are either due to differing viscosity, a different liquid water content of the aerosol particles, or an HO2 + RO2 reaction occurring within the aerosol particles.

Multiphase interactions and chemical reactions at indoor surfaces are of particular importance due to their impact on air quality in indoor environments with high surface to volume ratios. Kinetic multilayer models are a powerful tool to simulate various gas-surface interactions including partitioning, diffusion and multiphase chemistry of indoor compounds by treating mass transport and chemical reactions in a number of model layers in the gas and condensed phases with a flux-based approach. We have developed a series of kinetic multilayer models that have been applied to describe multiphase chemistry and interactions indoors. They include the K2-SURF model treating the reversible adsorption of volatile organic compounds on surfaces, the KM-BL model treating diffusion through an indoor surface boundary layer, the KM-FILM model treating organic film formation by multi-layer adsorption and film growth by absorption of indoor compounds, and the KM-SUB-Skin-Clothing model treating reactions of ozone with skin lipids in skin and clothing. We also developed the effective mass accommodation coefficient that can treat surface partitioning by effectively taking into account kinetic limitations of bulk diffusion. In this study we provide detailed instructions and code annotations of these models for the model user. Example sensitivity simulations that investigate the impact of input parameters are presented to help with familiarization to the codes. The user can adapt the codes as required to model experimental and indoor field campaign measurements, can use the codes to gain insights into important reactions and processes, and can extrapolate to new conditions that may not be accessible by measurements.

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.

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 (γ O3 ) 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 γ O3 by a factor of 3.0, and exposure to 134 ppb of α-terpineol for 1 h increased γ O3 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 γ O3 on RH and the presence of α-terpineol, indicating the reacto-diffusive depth for O 3 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.

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., (© The Author(s) 2024. Published by Oxford University Press on behalf of the Johns Hopkins Bloomberg School of Public Health. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.)

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.

Introduction: Oxidative stress mediated by reactive oxygen species (ROS) is a key process for adverse aerosol health effects. Secondary organic aerosols (SOA) account for a major fraction of particulate matter with aerodynamic diameter ≤2.5 µm (PM 2.5 ). PM 2.5 inhalation and deposition into the respiratory tract causes the formation of ROS by chemical reactions and phagocytosis of macrophages in the epithelial lining fluid (ELF), but their relative contributions are not well quantified and their link to oxidative stress remains uncertain. The specific aims of this project were (1) elucidating the chemical mechanism and quantifying the formation kinetics of ROS in the ELF by SOA; (2) quantifying the relative importance of ROS formation by chemical reactions and macrophages in the ELF., Methods: SOA particles were generated using reaction chambers from oxidation of various precursors including isoprene, terpenes, and aromatic compounds with or without nitrogen oxides (NO x ). We collected size-segregated PM at two highway sites in Anaheim, CA, and Long Beach, CA, and at an urban site in Irvine, CA, during two wildfire events. The collected particles were extracted into water or surrogate ELF that contained lung antioxidants. ROS generation was quantified using electron paramagnetic resonance (EPR) spectroscopy with a spin-trapping technique. PM oxidative potential (OP) was also quantified using the dithiothreitol assay. In addition, kinetic modeling was applied for analysis and interpretation of experimental data. Finally, we quantified cellular superoxide release by RAW264.7 macrophage cells upon exposure to quinones and isoprene SOA using a chemiluminescence assay as calibrated with an EPR spin-probing technique. We also applied cellular imaging techniques to study the cellular mechanism of superoxide release and oxidative damage on cell membranes., Results: Superoxide radicals (·O 2 - ) were formed from aqueous reactions of biogenic SOA generated by hydroxy radical (·OH) photooxidation of isoprene, β-pinene, α-terpineol, and d-limonene. The temporal evolution of ·OH and ·O 2 - formation was elucidated by kinetic modeling with a cascade of aqueous reactions, including the decomposition of organic hydroperoxides (ROOH), ·OH oxidation of primary or secondary alcohols, and unimolecular decomposition of α-hydroxyperoxyl radicals. Relative yields of various types of ROS reflected the relative abundance of ROOH and alcohols contained in SOA, which generated under high NO x conditions, exhibited lower ROS yields. ROS formation by SOA was also affected by pH. Isoprene SOA had higher ·OH and organic radical yields at neutral than at acidic pH. At low pH ·O 2 - was the dominant species generated by all types of SOA. At neutral pH, α-terpineol SOA exhibited a substantial yield of carbon-centered organic radicals (R·), while no radical formation was observed by aromatic SOA., Organic radicals in the ELF were formed by mixtures of Fe 2+ and SOA generated from photooxidation of isoprene, α-terpineol, and toluene. The molar yields of organic radicals by SOA were 5-10 times higher in ELF than in water. Fe 2+ enhanced organic radical yields by a factor of 20-80. Ascorbate mediated redox cycling of iron ions and sustained organic peroxide decomposition, as supported by kinetic modeling reproducing time- and concentration-dependence of organic radical formation, as well as by additional experiments observing the formation of Fe 2+ and ascorbate radicals in mixtures of ascorbate and Fe 3+ . ·OH and superoxide were found to be efficiently scavenged by antioxidants., Wildfire PM mainly generated ·OH and R· with minor contributions from superoxide and oxygen-centered organic radicals (RO·). PM OP was high in wildfire PM, exhibiting very weak correlation with radical forms of ROS. These results were in stark contrast with PM collected at highway and urban sites, which generated much higher amounts of radicals dominated by ·OH radicals that correlated well with OP. By combining field measurements of size-segregated chemical composition, a human respiratory tract model, and kinetic modeling, we quantified production rates and concentrations of different types of ROS in different regions of the ELF by considering particle-size-dependent respiratory deposition. While hydrogen peroxide (H 2 O 2 ) and ·O 2 - production were governed by Fe and Cu ions, ·OH radicals were mainly generated by organic compounds and Fenton-like reactions of metal ions. We obtained mixed results for correlations between PM OP and ROS formation, providing rationale and limitations of the use of oxidative potential as an indicator for PM toxicity in epidemiological and toxicological studies., Quinones and isoprene SOA activated nicotinamide adenine dinucleotide phosphate (NADPH) oxidase in macrophages, releasing massive amounts of superoxide via respiratory burst and overwhelming the superoxide formation by aqueous chemical reactions in the ELF. The threshold dose for macrophage activation was much smaller for quinones compared with isoprene SOA. The released ROS caused lipid peroxidation to increase cell membrane fluidity, inducing oxidative damage and stress. Further increases of doses led to the activation of antioxidant response elements, reducing the net cellular superoxide production. At very high doses and long exposure times, chemical production became comparably important or dominant if the escalation of oxidative stress led to cell death., Conclusions: The mechanistic understandings and quantitative information on ROS generation by SOA particles provided a basis for further elucidation of adverse aerosol health effects and oxidative stress by PM 2.5 . For a comprehensive assessment of PM toxicity and health effects via oxidative stress, it is important to consider both chemical reactions and cellular processes for the formation of ROS in the ELF. Chemical composition of PM strongly influences ROS formation; further investigations are required to study ROS formation from various PM sources. Such research will provide critical information to environmental agencies and policymakers for the development of air quality policy and regulation., (© 2023 Health Effects Institute. All rights reserved.)

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., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Background: Although many studies have linked prenatal exposure to PM 2.5 to adverse birth outcomes, little is known about the effects of exposure to specific constituents of PM 2.5 or mechanisms that contribute to these outcomes., Objectives: Our objective was to investigate effects of oxidative potential and PM 2.5 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 PM 2.5 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 ( OP OH ), and dithiothreitol (DTT) loss ( OP DTT ). Using logistic regression, we estimated odds ratios (OR) and 95% confidence intervals (CI) for PTB and TLBW with speciated PM 2.5 exposures and PM 2.5 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 PM 2.5 mass. Associations for PM 2.5 mass, black carbon, metal components, and oxidative potential (especially ROS and OP OH ) with adverse birth outcomes were stronger in Hispanic, Black, and mixed-race or Native American women., Discussion: Our results indicate that exposure to PM 2.5 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 PM 2.5 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.

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 ( α eff ) was introduced for efficient and effective treatments of gas-particle partitioning. In this study, we extended this approach to a film geometry with α eff 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 α eff 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 ( D b ∼<10 -15 cm 2 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 D b > ∼10 -17 -10 -19 cm 2 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.

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 HO 2 • 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.

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 (PM 2.5 ) 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 (O x , a redox-weighted average of nitrogen dioxide and ozone) and cardiovascular deaths. Analyses were performed across strata of two measures of PM 2.5 oxidative potential and reactive oxygen species concentrations (ROS) adjusting for relevant confounding factors., Results: PM 2.5 mass concentration showed little within-city variability, but PM 2.5 oxidative potential and ROS were more variable. Spatial variations in outdoor O x 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 O x on cardiovascular mortality was stronger above the median of each measure of PM 2.5 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 PM 2.5 oxidative potential may modify long-term cardiovascular health impacts of O x . Regions with elevated O x and PM 2.5 oxidative potential may be priority areas for interventions to decrease the population health impacts of outdoor air pollution., Competing Interests: The authors declare that they have no conflicts of interest with regard to the content of this report., (Copyright © 2023 The Authors. Published by Wolters Kluwer Health, Inc. on behalf of The Environmental Epidemiology. All rights reserved.)

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 2 , there is also evidence of volatile organoiodide compound emissions in the presence of organics without biological activity occuring [M. Martino, G. P. Mills, J. Woeltjen and P. S. Liss, A new source of volatile organoiodine compounds in surface seawater, Geophys. Res. Lett. , 2009, 36 , L01609, L. Tinel, T. J. Adams, L. D. J. Hollis, A. J. M. Bridger, R. J. Chance, M. W. Ward, S. M. Ball and L. J. Carpenter, Influence of the Sea Surface Microlayer on Oceanic Iodine Emissions, Environ. Sci. Technol. , 2020, 54 , 13228-13237]. In this study, we evaluate our fundamental understanding of the ozonolysis of iodide which leads to gas-phase iodine emissions. To do this, we compare experimental measurements of ozone-driven gas-phase I 2 formation in a flow tube to predictions made with the kinetic multilayer model for surface and bulk chemistry (KM-SUB). The KM-SUB model uses literature rate coefficients used in current atmospheric chemistry models to predict I 2(g) formation in pH-buffered solutions of marine composition containing chloride, bromide, and iodide compared to solutions containing only iodide. Experimentally, I 2(g) formation was found to be suppressed in solutions containing seawater levels of chloride compared to solutions containing only iodide, but the model does not predict this effect using literature rate constants. However, the model is able to predict this trend upon adjustment of two specific reaction rate constants. To more closely represent true oceanic conditions, we add an organic component to the proxy seawater solutions using material generated from Thalassiosira pseudonana phytoplankton cultures. Whereas the rate of ozone deposition is unaffected, the formation rate of I 2(g) is strongly suppressed in the presence of biological organic material, indicative of a sink or reduction of reactive iodine formed during the oxidation process.

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 -1 ), 44% of indoor ROS on PM is of indoor origin. An indoor source of ozone, such as an electrostatic air cleaner, also increases OPX present in indoor PM. The results of the simulations support the hypothesis that ozone-induced formation of OPX on indoor surfaces, and subsequent partitioning to aerosols, is sufficient to explain field observations. Therefore, indoor sourced ROS could contribute meaningfully to total inhaled PM-ROS.

Oxidative stress mediated by reactive oxygen species (ROS) is a key process for adverse aerosol health effects. Secondary organic aerosols (SOA) account for a major fraction of fine particulate matter, and their inhalation and deposition into the respiratory tract causes the formation of ROS by chemical and cellular processes, but their relative contributions are hardly quantified and their link to oxidative stress remains uncertain. Here, we quantified cellular and chemical superoxide generation by 9,10-phenanthrenequinone (PQN) and isoprene SOA using a chemiluminescence assay combined with electron paramagnetic resonance spectroscopy as well as kinetic modeling. We also applied cellular imaging techniques to study the cellular mechanism of superoxide release and oxidative damage on cell membranes. We show that PQN and isoprene SOA activate NADPH oxidase in macrophages to release massive amounts of superoxide, overwhelming the superoxide formation by aqueous chemical reactions in the epithelial lining fluid. The activation dose for PQN is 2 orders of magnitude lower than that of isoprene SOA, suggesting that quinones are more toxic. While higher exposures trigger cellular antioxidant response elements, the released ROS induce oxidative damage to the cell membrane through lipid peroxidation. Such mechanistic and quantitative understandings provide a basis for further elucidation of adverse health effects and oxidative stress by fine particulate matter.

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 -1 (∼0.68 mg h -1 ), which increased the in-cabin O 3 concentrations of a Mitsubishi Mirage to ∼10 ppb with the fan off and ∼6 ppb in the recirculation mode. In the fresh air mode, in-cabin O 3 concentrations were dominated by outdoor-to-indoor transport. Ionizer B and C produced O 3 at a rate of less than 0.008 ppb s -1 (<0.14 mg h -1 ); however, during retesting, ionizer C was shown to emit large amounts of ozone for short amounts of time while being tested up close. The same testing was completed on vehicles with built-in ionizers; these produced <0.01 ppb s -1 (<0.32 mg h -1 in the Buick Enclave and <0.25 mg h -1 in the Hyundai Genesis), and in-cabin O 3 concentrations were again dominated by outdoor-to-indoor transport with fresh air ventilation. While ionizers are currently regulated, the negative impact they have on in cabin air quality is important to continue monitoring.

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.

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.

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 O 2 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 cm 3 molecule -1 s -1 for 2-methyl-1-nitroprop-1-ene and (6.8 ± 0.8) × 10 -19 cm 3 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 cm 3 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 cm 2 molecule -1 s -1 and in the bulk 1× 10 -16 cm 3 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.

Commonly found in atmospheric aerosols, cooking oils, and human sebum, unsaturated lipids rapidly decay upon exposure to ozone, following the Criegee mechanism. Here, the gas-surface ozonolysis of three oleic acid-based compounds was studied in a reactor and indoors. Under dry conditions, quantitative product analyses by 1 H NMR indicate up to 79% molar yield of stable secondary ozonides (SOZs) in oxidized triolein and methyl oleate coatings. Elevated relative humidity (RH) significantly suppresses the SOZ yields, enhancing the formation of condensed-phase aldehydes and volatile C9 products. Along with kinetic parameters informed by molecular dynamics simulations, these results were used as constraints in a kinetic multilayer model (KM-GAP) simulating triolein ozonolysis. Covering a wide range of coating thicknesses and ozone levels, the model predicts a much faster decay near the gas-lipid interface compared to the bulk. Although the dependence of RH on SOZ yields is well predicted, the model overestimates the production of H 2 O 2 and aldehydes. With negligible dependence on RH, the product composition for oxidized oleic acid is substantially affected by a competitive reaction between Criegee intermediates (CIs) and carboxylic acids. The resulting α-acyloxyalkyl hydroperoxides (α-AAHPs) have much higher molar yields (29-38%) than SOZs (12-16%). Overall, the ozone-lipid chemistry could affect the indoor environment through "crust" accumulation on surfaces and volatile organic compound (VOC) emission. In the atmosphere, the peroxide formation and changes in particle hygroscopicity may have effects on climate. The related health impacts are also discussed.

There is growing interest to move beyond fine particle mass concentrations (PM 2.5 ) when evaluating the population health impacts of outdoor air pollution. However, few exposure models are currently available to support such analyses. In this study, we conducted large-scale monitoring campaigns across Montreal and Toronto, Canada during summer 2018 and winter 2019 and developed models to predict spatial variations in (1) the ability of PM 2.5 to generate reactive oxygen species in the lung fluid (ROS), (2) PM 2.5 oxidative potential based on the depletion of ascorbate (OP AA ) and glutathione (OP GSH ) in a cell-free assay, and (3) anhysteretic magnetic remanence ( X ARM ) as an indicator of magnetite nanoparticles. We also examined how exposure to PM oxidative capacity metrics (ROS/OP) varied by socioeconomic status within each city. In Montreal, areas with higher material deprivation, indicating lower area-level average household income and employment, were exposed to PM 2.5 characterized by higher ROS and OP. This relationship was not observed in Toronto. The developed models will be used in epidemiologic studies to assess the health effects of exposure to PM 2.5 and iron-rich magnetic nanoparticles in Toronto and Montreal.

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  cm 2 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., (© 2021 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.)

Air pollution is a major risk factor for human health. Chemical reactions in the epithelial lining fluid (ELF) of the human respiratory tract result in the formation of reactive oxygen species (ROS), which can lead to oxidative stress and adverse health effects. We use kinetic modeling to quantify the effects of fine particulate matter (PM2.5), ozone (O 3 ), and nitrogen dioxide (NO 2 ) on ROS formation, interconversion, and reactivity, and discuss different chemical metrics for oxidative stress, such as cumulative production of ROS and hydrogen peroxide (H 2 O 2 ) to hydroxyl radical (OH) conversion. All three air pollutants produce ROS that accumulate in the ELF as H 2 O 2 , which serves as reservoir for radical species. At low PM2.5 concentrations (<10 μg m -3 ), we find that less than 4% of all produced H 2 O 2 is converted into highly reactive OH, while the rest is intercepted by antioxidants and enzymes that serve as ROS buffering agents. At elevated PM2.5 concentrations (>10 μg m -3 ), however, Fenton chemistry overwhelms the ROS buffering effect and leads to a tipping point in H 2 O 2 fate, causing a strong nonlinear increase in OH production. This shift in ROS chemistry and the enhanced OH production provide a tentative mechanistic explanation for how the inhalation of PM2.5 induces oxidative stress and adverse health effects.

Respiratory deposition of secondary organic aerosols (SOA) and iron may lead to the generation of reactive oxygen species and free radicals in lung fluid to cause oxidative stress, but their underlying mechanism and formation kinetics are not well understood. Here we demonstrate substantial formation of organic radicals in surrogate lung fluid (SLF) by mixtures of Fe 2+ and SOA generated from photooxidation of isoprene, α-terpineol, and toluene. The molar yields of organic radicals by SOA are measured to be 0.03-0.5% in SLF, which are 5-10 times higher than in water. We observe that Fe 2+ enhances organic radical yields dramatically by a factor of 20-80, which can be attributed to Fe 2+ -facilitated decomposition of organic peroxides, in consistency with a positive correlation between peroxide contents and organic radical yields. Ascorbate mediates redox cycling of iron ions to sustain organic peroxide decomposition, as supported by kinetic modeling reproducing time- and concentration-dependence of organic radical formation as well as additional experiments observing the formation of Fe 2+ and ascorbate radicals in mixtures of ascorbate and Fe 3+ . • OH and superoxide are found to be scavenged by antioxidants efficiently. These findings have implications on the role of organic radicals in oxidative damage and lipid peroxidation.

Historically air constituents have been assumed to be well mixed in indoor environments, with single point measurements and box modeling representing a room or a house. Here we demonstrate that this fundamental assumption needs to be revisited through advanced model simulations and extensive measurements of bleach cleaning. We show that inorganic chlorinated products, such as hypochlorous acid and chloramines generated via multiphase reactions, exhibit spatial and vertical concentration gradients in a room, with short-lived ⋅OH radicals confined to sunlit zones, close to windows. Spatial and temporal scales of indoor constituents are modulated by rates of chemical reactions, surface interactions and building ventilation, providing critical insights for better assessments of human exposure to hazardous pollutants, as well as the transport of indoor chemicals outdoors., (© 2021. The Author(s).)

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 such as access to testing and control measures that may not be independent of air pollution concentrations. Moreover, studies have yet to focus on key mechanisms of air pollution toxicity such as oxidative stress. Objectives: To conduct a within-city analysis of spatial variations in COVID-19 incidence and the estimated generation of reactive oxygen species (ROS) in lung lining fluid attributable to fine particulate matter (particulate matter with an aerodynamic diameter ⩽2.5 μm [PM 2.5 ]). Methods: Sporadic and outbreak-related COVID-19 case counts, testing data, population data, and sociodemographic data for 140 neighborhoods were obtained from the City of Toronto. ROS estimates were based on a mathematical model of ROS generation in lung lining fluid in response to iron and copper in PM 2.5 . Spatial variations in long-term average ROS were predicted using a land-use regression model derived from measurements of iron and copper in PM 2.5 . Data were analyzed using negative binomial regression models adjusting for covariates identified using a directed acyclic graph and accounting for spatial autocorrelation. Measurements and Main Results: A significant positive association was observed between neighborhood-level ROS and COVID-19 incidence (incidence rate ratio = 1.07; 95% confidence interval, 1.01-1.15 per interquartile range ROS). Effect modification by neighborhood-level measures of racialized group membership and socioeconomic status was also identified. Conclusions: Examination of neighborhood characteristics associated with COVID-19 incidence can identify inequalities and generate hypotheses for future studies.

Drivers and passengers are exposed to high concentrations of air pollutants while driving. While there are many studies to assess exposure to air pollutants penetrating into a vehicle cabin, little is known about how individual gas pollutants are behaving (e.g. accumulating, depositing, reacting etc.) in the cabin. This study investigated the characteristic behavior of CO, NO, NO2 and O3 in a vehicle cabin in the presence of a driver with static, pseudo dynamic and dynamic tests. We found in our experiments that CO and NO concentrations increased while O3 and NO2 concentrations decreased rapidly when cabin air was recirculated. A kinetic model, which contains 20 chemical reactions, could predict the static test results well. CO and NO accumulations in the cabin were due to exhalation from the driver and conversion of NO2 to NO upon deposition to surfaces may also play a role. Pseudo dynamic and dynamic test results showed similar results. During the fresh air mode CO, NO, and NO2 followed similar trends between the inside and outside of the cabin, while in cabin O3 concentrations were lower compared to outside concentrations due to reactions with the human and surface deposition. The Cabin Air Quality Index approached 0.8 and 0.4 for O3 during pseudo dynamic and dynamic tests, respectively. Accumulation of NO in the cabin was not obvious during the dynamic test due to a large variation of outside NO concentrations. We encourage auto manufacturers to develop control algorithms and devices to reduce a passenger's exposure to gaseous pollutants in vehicle cabins.

Reactive oxygen species (ROS) play a central role in aqueous-phase processing and health effects of atmospheric aerosols. Although hydroxyl radical ( • OH) and hydrogen peroxide (H 2 O 2 ) are regarded as major oxidants associated with secondary organic aerosols (SOA), the kinetics and reaction mechanisms of superoxide (O 2 •- ) formation are rarely quantified and poorly understood. Here, we demonstrate a dominant formation of O 2 •- with molar yields of 0.01-0.03% from aqueous reactions of biogenic SOA generated by • OH photooxidation of isoprene, β-pinene, α-terpineol, and d-limonene. The temporal evolution of • OH and O 2 •- formation is elucidated by kinetic modeling with a cascade of aqueous reactions including the decomposition of organic hydroperoxides, • OH oxidation of primary or secondary alcohols, and unimolecular decomposition of α-hydroxyperoxyl radicals. Relative yields of various types of ROS reflect a relative abundance of organic hydroperoxides and alcohols contained in SOA. These findings and mechanistic understanding have important implications on the atmospheric fate of SOA and particle-phase reactions of highly oxygenated organic molecules as well as oxidative stress upon respiratory deposition.

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 NO 2 with grime adsorbed on glass window. The uptake coefficients of NO 2 [γ(NO 2 )] 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 NO 2 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.

The reaction of ozone with iodide in the ocean is a major ozone dry deposition pathway, as well as an important source of reactive iodine to the marine troposphere. Few prior laboratory experiments have been conducted with environmentally relevant ozone mixing ratios and iodide concentrations, leading to uncertainties in the rate of the reaction under marine boundary layer conditions. As well, there remains disagreement in the literature assessment of the relative contributions of an interfacial reaction via ozone adsorbed to the ocean surface versus a bulk reaction with dissolved ozone. In this study, we measure the uptake coefficient of ozone over a buffered, pH 8 salt solution replicating the concentrations of iodide, bromide, and chloride in the ocean over an ozone mixing ratio of 60-500 ppb. Due to iodide depletion in the solution, the measured ozone uptake coefficient is dependent on the exposure time of the solution to ozone and its mixing ratio. A kinetic multilayer model confirms that iodide depletion is occurring not only within ozone's reactodiffusive depth, which is on the order of microns for environmental conditions, but also deeper into the solution as well. Best model-measurement agreement arises when some degree of nondiffusive mixing is occurring in the solution, transporting iodide from deeper in the solution to a thin, diffusively mixed upper layer. If such mixing occurs rapidly in the environment, iodide depletion is unlikely to reduce ozone dry deposition rates. Unrealistically high bulk-to-interface partitioning of iodide is required for the model to predict a substantial interfacial component to the reaction, indicating that the Langmuir-Hinshelwood mechanism is not dominant under environmental conditions.

Ozone has adverse effects on human health. Skin oil on the human surface acts as an ozone sink indoors, producing oxidation products that can cause skin and respiratory irritations. Concentrations of ozone and oxidation products near human surfaces, including the breathing zone, can be modulated by indoor ventilation modes and human surface conditions. The objective of this study is to examine concentrations and spatial heterogeneity of ozone and ozonolysis products under representative ranges of indoor ventilation, clothing, and breathing conditions. Using computational fluid dynamics (CFD) simulation in conjunction with a chemical kinetic model, details of ozone reactions with the human surface and subsequent chemical reactions are examined. The results show that primary ozonolysis products are concentrated near the soiled clothing, while the secondary products are relatively well distributed throughout the room. Increasing indoor air mixing enhances the ozone deposition to the human surface, thereby resulting in higher emission rates of oxidation products in the room. Soiled clothing consumes more ozone than clean clothing and accordingly produces ~ 65% more primary products and ~15% more secondary products. The results also reveal that unsaturated hydrocarbons from the human breath, such as isoprene, contribute to only ~0.5% of ozone removal compared to ozone deposition to the human surface., (© 2020 John Wiley & Sons A/S . Published by John Wiley & Sons Ltd.)

Isoprene hydroxy hydroperoxides (ISOPOOH) formed by the photooxidation of isoprene under low-NO conditions play an important role in the formation and evolution of secondary organic aerosols, yet multiphase processes of ISOPOOH are poorly understood. By applying electron paramagnetic resonance spectroscopy, we observe that ISOPOOH undergoes aqueous-phase decomposition upon interacting with Fe(II) ions to form OH and organic radicals at room temperature. To reproduce the measured dependence of OH formation on the Fe concentrations by kinetic modeling, we postulate that Fe(II) ions react with ISOPOOH via Fenton-like reactions to form OH radicals with a rate constant of 7.3 × 10 -18 cm 3 s -1 . At low concentrations, oxalate forms monocomplexes with Fe(II) ions, which can promote OH formation by ISOPOOH. However, at high concentrations, oxalate scavenges OH radicals, thereby lowering aqueous OH concentrations. These findings provide new insight for the atmospheric fate of ISOPOOH and reactive oxygen species generation in the aqueous phase.

The neonicotinoid nitenpyram (NPM) is a multifunctional nitroenamine [(R 1 N)(R 2 N)C=CHNO 2 ] pesticide. As a nitroalkene, it is structurally similar to other emerging contaminants such as the pharmaceuticals ranitidine and nizatidine. Because ozone is a common atmospheric oxidant, such compounds may be oxidized on contact with air to form new products that have different toxicity compared to the parent compounds. Here we show that oxidation of thin solid films of NPM by gas-phase ozone produces unexpected products, the majority of which do not contain oxygen, despite the highly oxidizing reactant. A further surprising finding is the formation of gas-phase nitrous acid (HONO), a species known to be a major photolytic source of the highly reactive hydroxyl radical in air. The results of application of a kinetic multilayer model show that reaction was not restricted to the surface layers but, at sufficiently high ozone concentrations, occurred throughout the film. The rate constant derived for the O 3 -NPM reaction is 1 × 10 -18 cm 3 ⋅s -1 , and the diffusion coefficient of ozone in the thin film is 9 × 10 -10 cm 2 ⋅s -1 These findings highlight the unique chemistry of multifunctional nitroenamines and demonstrate that known chemical mechanisms for individual moieties in such compounds cannot be extrapolated from simple alkenes. This is critical for guiding assessments of the environmental fates and impacts of pesticides and pharmaceuticals, and for providing guidance in designing better future alternatives., Competing Interests: The authors declare no competing interest.

We performed classical molecular dynamics simulations to quantify and understand the nonreactive, dermal uptake of volatile organic compounds formed during the ozonolysis of human skin oils. Our results include surface accommodation coefficients, partitioning constants, bulk diffusivities, and desorption lifetimes. These parameters were used to improve and to constrain the kinetic multilayer model of the surface and bulk chemistry of skin (KM-SUB-Skin). By comparing common outputs (bulk accommodation coefficients), we cross-validate the two approaches and, thus, increase the level of trust in their predictions relevant to indoor air chemistry.

We report elevated levels of gaseous inorganic chlorinated and nitrogenated compounds in indoor air while cleaning with a commercial bleach solution during the House Observations of Microbial and Environmental Chemistry field campaign in summer 2018. Hypochlorous acid (HOCl), chlorine (Cl 2 ), and nitryl chloride (ClNO 2 ) reached part-per-billion by volume levels indoors during bleach cleaning-several orders of magnitude higher than typically measured in the outdoor atmosphere. Kinetic modeling revealed that multiphase chemistry plays a central role in controlling indoor chlorine and reactive nitrogen chemistry during these periods. Cl 2 production occurred via heterogeneous reactions of HOCl on indoor surfaces. ClNO 2 and chloramine (NH 2 Cl, NHCl 2 , NCl 3 ) production occurred in the applied bleach via aqueous reactions involving nitrite (NO 2 - ) and ammonia (NH 3 ), respectively. Aqueous-phase and surface chemistry resulted in elevated levels of gas-phase nitrogen dioxide (NO 2 ). We predict hydroxyl (OH) and chlorine (Cl) radical production during these periods (10 6 and 10 7 molecules cm -3 s -1 , respectively) driven by HOCl and Cl 2 photolysis. Ventilation and photolysis accounted for <50% and <0.1% total loss of bleach-related compounds from indoor air, respectively; we conclude that uptake to indoor surfaces is an important additional loss process. Indoor HOCl and nitrogen trichloride (NCl 3 ) mixing ratios during bleach cleaning reported herein are likely detrimental to human health.

Reactive oxygen species (ROS) play a central role in adverse health effects of atmospheric particulate matter (PM). Respiratory deposition can lead to the formation of ROS in the epithelial lining fluid due to redox reactions of PM components with lung antioxidants. As direct quantification of ROS is challenging, PM oxidative potential is more commonly measured using antioxidant surrogates including dithiothreitol and ascorbic acid, assuming that the decay of surrogates corresponds to ROS formation. However, this assumption has not yet been validated and the lack of ROS quantification in the respiratory tract causes major limitations in evaluating PM impacts on oxidative stress. By combining field measurements of size-segregated chemical composition, a human respiratory tract model, and kinetic modeling, we quantified production rates and concentrations of different types of ROS in different regions of the epithelial lining fluid by considering particle-size-dependent respiratory deposition. The extrathoracic region is found to have higher ROS concentrations compared to the bronchial and alveolar regions. Although H 2 O 2 and O 2 - production is governed by Fe and Cu ions, OH radicals are mainly generated by organic compounds and Fenton-like reactions of metal ions. In winter when affected by biomass burning, model comparisons suggest that humic-like substances (HULIS) contribute to ROS formation substantially. We found that PM oxidative potential is a good indicator of the chemical production of H 2 O 2 and O 2 - but does not represent OH generation. These results provide rationale and limitations of the use of oxidative potential as an indicator of PM toxicity in epidemiological and toxicological studies.

Ozone (O 3 ) chemistry is thought to dominate the oxidation of indoor surfaces. We consider the hypothesis that reactions taking place within indoor boundary layers result in greater than anticipated hydroxyl radical (OH) deposition rates. We develop models that account for boundary layer mass-transfer phenomena, O 3 -terpene chemistry and OH formation, removal, and deposition; we solve these analytically and by applying numerical methods. For an O 3 -limonene system, we find that OH flux to a surface with an O 3 reaction probability of 10 -8 is 4.3 × 10 -5 molec/(cm 2 s) which is about 10 times greater than predicted by a traditional boundary layer theory. At very low air exchange rates the OH surface flux can be as much as 10% of that for O 3 . This effect becomes less pronounced for more O 3 -reactive surfaces. Turbulence intensity does not strongly influence the OH concentration gradient except for surfaces with an O 3 reaction probability >10 -4 . Although the O 3 flux dominates OH flux under most conditions, OH flux can be responsible for as much as 10% of total oxidant uptake to otherwise low-reactivity surfaces. Further, OH chemistry differs from that for ozone; therefore, its deposition is important in understanding the chemical evolution of some indoor surfaces and surface films., (© 2019 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.)

We report on the development of a modelling consortium for chemistry in indoor environments that connects models over a range of spatial and temporal scales, from molecular to room scales and from sub-nanosecond to days, respectively. Our modeling approaches include molecular dynamics (MD) simulations, kinetic process modeling, gas-phase chemistry modeling, organic aerosol modeling, and computational fluid dynamics (CFD) simulations. These models are applied to investigate ozone reactions with skin and clothing, oxidation of volatile organic compounds and formation of secondary organic aerosols, and mass transport and partitioning of indoor species to surfaces. MD simulations provide molecular pictures of limonene adsorption on SiO2 and ozone interactions with the skin lipid squalene, providing kinetic parameters such as surface accommodation coefficient, desorption lifetime, and bulk diffusivity. These parameters then constrain kinetic process models, which resolve mass transport and chemical reactions in gas and condensed phases for analysis of experimental data. A detailed indoor chemical box model is applied to simulate α-pinene ozonolysis with improved representation of gas-particle partitioning. Application of 2D-volatility basis set reveals that OH-induced aging sometimes drives increases in indoor organic aerosol concentrations, due to organic mass functionalization and enhanced partitioning. CFD simulations show that concentrations of ozone and primary product change near the human surface rapidly, indicating non-uniform spatial distributions from the occupant surface to ambient air, while secondary ozone product is relatively well-mixed throughout the room. This development establishes a framework to integrate different modeling tools and experimental measurements, opening up an avenue for development of comprehensive and integrated models with representations of various chemistry in indoor environments.