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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 (O3), and nitrogen dioxide (NO2) on ROS formation, interconversion, and reactivity, and discuss different chemical metrics for oxidative stress, such as cumulative production of ROS and hydrogen peroxide (H2O2) to hydroxyl radical (OH) conversion. All three air pollutants produce ROS that accumulate in the ELF as H2O2, which serves as reservoir for radical species. At low PM2.5 concentrations (10 μg m-3), however, Fenton chemistry overwhelms the ROS buffering effect and leads to a tipping point in H2O2 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.

Wechselwirkungen von Kohlenstoff‐Nanopartikeln mit Gasen sind von zentraler Bedeutung in vielen Umwelt‐ und Technik‐Prozessen, jedoch sind die zugrundeliegenden Reaktionskinetiken und ‐mechanismen nicht ausreichend gut verstanden. Hier untersuchen wir die Oxidation und Gasifizierung von Kohlenstoff‐Nanopartikeln durch NO2 und O2 unter Verbrennungsabgasbedingungen. Mit Hilfe eines umfassenden experimentellen Datensatzes und einem kinetischen Mehrschichtmodell (KM‐GAP‐CARBON), werden die Aufnahme und Freisetzung von Gasmolekülen sowie die zeitliche Entwicklung der Partikelgröße und Oberflächenzusammensetzung verfolgt. Die experimentellen Ergebnisse werden durch einen Modellmechanismus beschrieben, der verschiedene Arten von Kohlenstoffatomen (rand‐ und basalflächenartig) und die Bildung eines reaktiven Sauerstoff‐Intermediats (aktivierter CO‐Komplex) als geschwindigkeitsbestimmenden Schritt umfasst. Ein Übergang zwischen unterschiedlichen chemischen Regimen, welche bei niedrigeren Temperaturen durch die Reaktivität von NO2 und bei höheren Temperaturen durch die Reaktivität von O2 bestimmt sind, spiegelt sich in einem Anstieg der beobachtbaren Aktivierungsenergie von ~60 kJ/mol auf ~130 kJ/mol wider. Wir leiten Energieprofile für drei alternative Reaktionspfade ab, die die uni‐ oder bimolekulare Zersetzung von reaktiven Sauerstoff‐Intermediaten beinhalten. [ABSTRACT FROM AUTHOR]

Carbon nanoparticle interactions with gases are central to many environmental and technical processes, but the underlying reaction kinetics and mechanisms are not well understood. Here, we investigate the oxidation and gasification of carbon nanoparticles by NO2 and O2 under combustion exhaust conditions. We build on a comprehensive experimental data set and use a kinetic multilayer model (KM‐GAP‐CARBON) to trace the uptake and release of gas molecules alongside the temporal evolution of particle size and surface composition. The experimental results are captured by a model mechanism that involves different types of carbon atoms (edge/plane‐like) and the formation of a reactive oxygen intermediate (activated CO complex) as the rate‐limiting step. A transition between distinct chemical regimes driven by NO2 at lower temperatures and O2 at higher temperatures is reflected by an increase in the observable activation energy from ∼ ${ \sim }$ 60 kJ/mol to ∼ ${ \sim }$ 130 kJ/mol. We derive energy profiles for three alternative reaction pathways that involve uni‐ or bimolecular decomposition of reactive oxygen intermediates. [ABSTRACT FROM AUTHOR]

Terbuthylazine (TBA) is a widely used herbicide, and its heterogeneous reaction with OH radicals is important for assessing its potential to undergo atmospheric long-range transport and to affect the environment and public health. The apparent reaction rate coefficients obtained in different experimental investigations, however, vary by orders of magnitude depending on the applied experimental techniques and conditions. In this study, we used a kinetic multilayer model of aerosol chemistry with reversible surface adsorption and bulk diffusion (KM-SUB) in combination with a Monte Carlo genetic algorithm to simulate the measured decay rates of TBA. Two experimental data sets available from different studies can be described with a consistent set of kinetic parameters resolving the interplay of chemical reaction, mass transport, and shielding effects. Our study suggests that mass transport and shielding effects can substantially extend the atmospheric lifetime of reactive pesticides from a few days to weeks, with strong implications for long-range transport and potential health effects of these substances.

Abstract. Organic compounds present at or near the surface of aqueous droplets can be efficiently oxidized by gas-phase OH radicals, which alter the molecular distribution of the reaction products within the droplet. A change in aerosol composition affects the hygroscopicity and leads to a concomitant response in the equilibrium amount of particle-phase water. The variation in the aerosol water content affects the aerosol size and physicochemical properties, which in turn governs the oxidation kinetics and chemistry. To attain better knowledge of the compositional evolution of aqueous organic droplets during oxidation, this work investigates the heterogeneous OH-radical-initiated oxidation of aqueous methylsuccinic acid (C5H8O4) droplets, a model compound for small branched dicarboxylic acids found in atmospheric aerosols, at a high relative humidity of 85 % through experimental and modeling approaches. Aerosol mass spectra measured by a soft atmospheric pressure ionization source (Direct Analysis in Real Time, DART) coupled with a high-resolution mass spectrometer reveal two major products: a five carbon atom (C5) hydroxyl functionalization product (C5H8O5) and a C4 fragmentation product (C4H6O3). These two products likely originate from the formation and subsequent reactions (intermolecular hydrogen abstraction and carbon–carbon bond scission) of tertiary alkoxy radicals resulting from the OH abstraction occurring at the methyl-substituted carbon site. Based on the identification of the reaction products, a kinetic model of oxidation (a two-product model) coupled with the Aerosol Inorganic–Organic Mixtures Functional groups Activity Coefficients (AIOMFAC) model is built to simulate the size and compositional changes of aqueous methylsuccinic acid droplets during oxidation. Model results show that at the maximum OH exposure, the droplets become slightly more hygroscopic after oxidation, as the mass fraction of water is predicted to increase from 0.362 to 0.424; however, the diameter of the droplets decreases by 6.1 %. This can be attributed to the formation of volatile fragmentation products that partition to the gas phase, leading to a net loss of organic species and associated particle-phase water, and thus a smaller droplet size. Overall, fragmentation and volatilization processes play a larger role than the functionalization process in determining the evolution of aerosol water content and droplet size at high-oxidation stages.

The allergenic potential of airborne proteins may be enhanced via post-translational modification induced by air pollutants like ozone (O3) and nitrogen dioxide (NO2). The molecular mechanisms and kinetics of the chemical modifications that enhance the allergenicity of proteins, however, are still not fully understood. Here, protein tyrosine nitration and oligomerization upon simultaneous exposure of O3 and NO2 were studied in coated-wall flow-tube and bulk solution experiments under varying atmospherically relevant conditions (5-200 ppb O3, 5-200 ppb NO2, 45-96% RH), using bovine serum albumin as a model protein. Generally, more tyrosine residues were found to react via the nitration pathway than via the oligomerization pathway. Depending on reaction conditions, oligomer mass fractions and nitration degrees were in the ranges of 2.5-25% and 0.5-7%, respectively. The experimental results were well reproduced by the kinetic multilayer model of aerosol surface and bulk chemistry (KM-SUB). The extent of nitration and oligomerization strongly depends on relative humidity (RH) due to moisture-induced phase transition of proteins, highlighting the importance of cloud processing conditions for accelerated protein chemistry. Dimeric and nitrated species were major products in the liquid phase, while protein oligomerization was observed to a greater extent for the solid and semi-solid phase states of proteins. Our results show that the rate of both processes was sensitive towards ambient ozone concentration, but rather insensitive towards different NO2 levels. An increase of tropospheric ozone concentrations in the Anthropocene may thus promote pro-allergic protein modifications and contribute to the observed increase of allergies over the past decades.

Mineral dust and secondary organic aerosols (SOA) account for a major fraction of atmospheric particulate matter, affecting climate, air quality and public health. How mineral dust interacts with SOA to influence cloud chemistry and public health, however, is not well understood. Here, we investigated the formation of reactive oxygen species (ROS), which are key species of atmospheric and physiological chemistry, in aqueous mixtures of SOA and mineral dust by applying electron paramagnetic resonance (EPR) spectrometry in combination with a spin-trapping technique, liquid chromatography-tandem mass spectrometry (LC-MS/MS), and a kinetic model. We found that substantial amounts of ROS including OH, superoxide as well as carbon- and oxygen-centred organic radicals can be formed in aqueous mixtures of isoprene, α-pinene, naphthalene SOA and various kinds of mineral dust (ripidolite, montmorillonite, kaolinite, palygorskite, and Saharan dust). The molar yields of total radicals were ∼0.02-0.5% at 295 K, which showed higher values at 310 K, upon 254 nm UV exposure, and under low pH (

Anthropogenic and biogenic gas emissions contribute to the formation of secondary organic aerosol (SOA). When present, soot particles from fossil fuel combustion can acquire a coating of SOA. We investigate SOA-soot biogenic-anthropogenic interactions and their impact on ice nucleation in relation to the particles' organic phase state. SOA particles were generated from the OH oxidation of naphthalene, α-pinene, longifolene, or isoprene, with or without the presence of sulfate or soot particles. Corresponding particle glass transition (Tg) and full deliquescence relative humidity (FDRH) were estimated using a numerical diffusion model. Longifolene SOA particles are solid-like and all biogenic SOA sulfate mixtures exhibit a core-shell configuration (i.e. a sulfate-rich core coated with SOA). Biogenic SOA with or without sulfate formed ice at conditions expected for homogeneous ice nucleation, in agreement with respective Tg and FDRH. α-pinene SOA coated soot particles nucleated ice above the homogeneous freezing temperature with soot acting as ice nuclei (IN). At lower temperatures the α-pinene SOA coating can be semisolid, inducing ice nucleation. Naphthalene SOA coated soot particles acted as ice nuclei above and below the homogeneous freezing limit, which can be explained by the presence of a highly viscous SOA phase. Our results suggest that biogenic SOA does not play a significant role in mixed-phase cloud formation and the presence of sulfate renders this even less likely. However, anthropogenic SOA may have an enhancing effect on cloud glaciation under mixed-phase and cirrus cloud conditions compared to biogenic SOA that dominate during pre-industrial times or in pristine areas.

Secondary organic aerosols (SOA) are a large source of uncertainty in our current understanding of climate change and air pollution. The phase state of SOA is important for quantifying their effects on climate and air quality, but its global distribution is poorly characterized. We developed a method to estimate glass transition temperatures based on the molar mass and molecular O:C ratio of SOA components, and we used the global chemistry climate model EMAC with the organic aerosol module ORACLE to predict the phase state of atmospheric SOA. For the planetary boundary layer, global simulations indicate that SOA are mostly liquid in tropical and polar air with high relative humidity, semi-solid in the mid-latitudes and solid over dry lands. We find that in the middle and upper troposphere SOA should be mostly in a glassy solid phase state. Thus, slow diffusion of water, oxidants and organic molecules could kinetically limit gas-particle interactions of SOA in the free and upper troposphere, promote ice nucleation and facilitate long-range transport of reactive and toxic organic pollutants embedded in SOA.

Cooking activities are responsible for substantial emissions of both particulate matter (PM) and volatile organic compounds (VOCs), two key indoor air pollutants, which can lead to numerous adverse health effects, including premature mortality. Chicken breast was prepared following tightly constrained cooking procedures with contrasting cooking methods in a well‐controlled research kitchen to investigate the PM and VOC emissions by simultaneous measurements with reference instruments (an optical aerosol spectrometer measuring light scattering of single particles for continuous PM monitoring and a proton‐transfer‐reaction time‐of‐flight mass spectrometer [PTR‐ToF‐MS] for VOCs). Peak concentrations of PM2.5 ranked in the order (median [μg m−3]) pan‐frying (92.9), stir‐frying (26.7), deep‐frying (7.7), boiling (0.7), and air‐frying (0.6). Peak concentrations of VOCs ranked in the order (median [ppb]) pan‐frying (260), deep‐frying (230), stir‐frying (110), boiling (30), and air‐frying (20). Key VOCs from different frying methods were identified in a detailed principal component analysis (PCA), including aldehydes, ketones, furans, aromatic hydrocarbons, alkenes, pyrazines, and alkanes. The cooking temperature was found to be the key factor that positively correlated with both PM and VOC emission strength, while the oil weight was negatively correlated with the PM levels. We also determined PM emission rates (varying over a wide range, e.g., for PM2.5 from 0.1 to 2931 μg min−1) and PM exposures (ranging, e.g., for PM2.5 from approximately 2 to more than 1000 μg m−3 min). In addition, by using EPR spectroscopy, we measured environmentally persistent free radicals (EPFRs) that formed from heating and cooking processes at levels of approximately 109 spins μg−1 of PM mass. These EPFR concentrations were shown to be unaffected by ozone exposure. [ABSTRACT FROM AUTHOR]

Abstract. Discontinuities in apparent hygroscopicity below and above water saturation have been observed for organic and mixed organic–inorganic aerosol particles in both laboratory studies and in the ambient atmosphere. However, uncertainty remains regarding the factors that contribute to observations of low hygroscopic growth below water saturation but enhanced cloud condensation nuclei (CCN) activity for a given aerosol population. Utilizing laboratory surrogates for oligomers in atmospheric aerosols, we explore the extent to which such discontinuities are influenced by organic component molecular mass and viscosity, non-ideal thermodynamic interactions between aerosol components, and the combination of these factors. Measurements of hygroscopic growth under subsaturated conditions and the CCN activity of aerosols comprised of polyethylene glycol (PEG) with average molecular masses ranging from 200 to 10 000 g mol−1 and mixtures of PEG with ammonium sulfate (AS) were conducted. Experimental results are compared to calculations of hygroscopic growth at thermodynamic equilibrium conducted with the Aerosol Inorganic Organic Mixtures Functional groups Activity Coefficients (AIOMFAC) model, and the potential influence of kinetic limitations on observed water uptake was further explored through estimations of water diffusivity in the PEG oligomers. Particle-phase behavior, including the prevalence of liquid–liquid phase separation (LLPS), was also modeled with AIOMFAC. Under subsaturated relative humidity (RH) conditions, we observed little variability in hygroscopic growth across PEG systems with different molecular masses; however, an increase in CCN activity with increasing PEG molecular mass was observed. This effect is most pronounced for PEG–AS mixtures, and, in fact, an enhancement in CCN activity was observed for the PEG10000–AS mixture as compared to pure AS, as evidenced by a 15 % reduction in critical activation diameter at a supersaturation of 0.8 %. We also observed a marked increase in apparent hygroscopicity for mixtures of higher molecular mass PEG and AS under supersaturated conditions as compared to subsaturated hygroscopic growth. AIOMFAC-based predictions and estimations of water diffusivity in PEG suggest that such discontinuities in apparent hygroscopicity above and below water saturation can be attributed, at least in part, to differences in the sensitivity of water uptake behavior to surface tension effects. There is no evidence that kinetic limitations to water uptake due to the presence of viscous aerosol components influenced hygroscopic growth. For the systems that display an enhancement in apparent hygroscopicity above water saturation, LLPS is predicted to persist to high RH. This indicates a miscibility gap and is likely to influence bulk-to-surface partitioning of PEG at high RH, impacting droplet surface tension and CCN activity. This work provides insight into the factors likely to be contributing to discontinuities in aerosol water-uptake behavior below and above water saturation that have been observed previously in the ambient atmosphere.

Air pollution can cause oxidative stress and adverse health effects such as asthma and other respiratory diseases, but the underlying chemical processes are not well characterized. Here we present chemical exposure-response relations between ambient concentrations of air pollutants and the production rates and concentrations of reactive oxygen species (ROS) in the epithelial lining fluid (ELF) of the human respiratory tract. In highly polluted environments, fine particulate matter (PM2.5) containing redox-active transition metals, quinones, and secondary organic aerosols can increase ROS concentrations in the ELF to levels characteristic for respiratory diseases. Ambient ozone readily saturates the ELF and can enhance oxidative stress by depleting antioxidants and surfactants. Chemical exposure-response relations provide a quantitative basis for assessing the relative importance of specific air pollutants in different regions of the world, showing that aerosol-induced epithelial ROS levels in polluted megacity air can be several orders of magnitude higher than in pristine rainforest air.

The chemical kinetics of organic nitrate production during new particle formation and growth of secondary organic aerosols (SOA) were investigated using the short-lived radioactive tracer (13)N in flow-reactor studies of α-pinene oxidation with ozone. Direct and quantitative measurements of the nitrogen content indicate that organic nitrates accounted for ∼40% of SOA mass during initial particle formation, decreasing to ∼15% upon particle growth to the accumulation-mode size range (>100 nm). Experiments with OH scavengers and kinetic model results suggest that organic peroxy radicals formed by α-pinene reacting with secondary OH from ozonolysis are key intermediates in the organic nitrate formation process. The direct reaction of α-pinene with NO3 was found to be less important for particle-phase organic nitrate formation. The nitrogen content of SOA particles decreased slightly upon increase of relative humidity up to 80%. The experiments show a tight correlation between organic nitrate content and SOA particle-number concentrations, implying that the condensing organic nitrates are among the extremely low volatility organic compounds (ELVOC) that may play an important role in the nucleation and growth of atmospheric nanoparticles.

Heterogeneous and multiphase reactions of ozone are important pathways for chemical ageing of atmospheric organic aerosols. To demonstrate and quantify how moisture-induced phase changes can affect the gas uptake and chemical transformation of organic matter, we apply a kinetic multi-layer model to a comprehensive experimental data set of ozone uptake by shikimic acid. The bulk diffusion coefficients were determined to be 10(-12) cm(2) s(-1) for ozone and 10(-20) cm(2) s(-1) for shikimic acid under dry conditions, increasing by several orders of magnitude with increasing relative humidity (RH) due to phase changes from amorphous solid over semisolid to liquid. Consequently, the reactive uptake of ozone progresses through different kinetic regimes characterised by specific limiting processes and parameters. At high RH, ozone uptake is driven by reaction throughout the particle bulk; at low RH it is restricted to reaction near the particle surface and kinetically limited by slow diffusion and replenishment of unreacted organic molecules. Our results suggest that the chemical reaction mechanism involves long-lived reactive oxygen intermediates, likely primary ozonides or O atoms, which may provide a pathway for self-reaction and catalytic destruction of ozone at the surface. Slow diffusion and ozone destruction can effectively shield reactive organic molecules in the particle bulk from degradation. We discuss the potential non-orthogonality of kinetic parameters, and show how this problem can be solved by using comprehensive experimental data sets to constrain the kinetic model, providing mechanistic insights into the coupling of transport, phase changes, and chemical reactions of multiple species in complex systems.

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.

Ageing of particulate organic matter affects the composition and properties of atmospheric aerosol particles. Driven by temperature and humidity, the organic fraction can vary its physical state between liquid and amorphous solid, or rarely even crystalline. These transitions can influence the reaction kinetics due to limitations of mass transport in such (semi-) solid states, which in turn may influence the chemical ageing of particles containing such compounds. We have used coated wall flow tube experiments to investigate the reaction kinetics of the ozonolysis of shikimic acid, which serves as a proxy for oxygenated, water-soluble organic matter and can form a glass at room temperature. Particular attention was paid to how the presence of water influences the reaction, since it acts a plasticiser and thereby induces changes in the physical state. We analysed the results by means of a traditional resistor model, which assumes steady-state conditions. The ozonolysis rate of shikimic acid is strongly increased in the presence of water, a fact we attribute to the increased transport of O3 and shikimic acid through the condensed phase at lower viscosities. The analysis using the resistor model suggests that the system undergoes both surface and bulk reaction. The second-order rate coefficient of the bulk reaction is 3.7 (+1.5/-3.2) × 10(3) L mol(-1) s(-1). At low humidity and long timescales, the resistor model fails to describe the measurements appropriately. The persistent O3 uptake at very low humidity suggests contribution of a self-reaction of O3 on the surface.

Air pollution is a potential driver for the increasing prevalence of allergic disease, and post-translational modification by air pollutants can enhance the allergenic potential of proteins. Here, the kinetics and mechanism of protein oligomerization upon ozone (O3) exposure were studied in coated-wall flow tube experiments at environmentally relevant O3 concentrations, relative humidities and protein phase states (amorphous solid, semisolid, and liquid). We observed the formation of protein dimers, trimers, and higher oligomers, and attribute the cross-linking to the formation of covalent intermolecular dityrosine species. The oligomerization proceeds fast on the surface of protein films. In the bulk material, reaction rates are limited by diffusion depending on phase state and humidity. From the experimental data, we derive a chemical mechanism and rate equations for a kinetic multilayer model of surface and bulk reaction enabling the prediction of oligomer formation. Increasing levels of tropospheric O3 in the Anthropocene may promote the formation of protein oligomers with enhanced allergenicity and may thus contribute to the increasing prevalence of allergies.

Multiphase reactions of OH radicals are among the most important pathways of chemical aging of organic aerosols in the atmosphere. Reactive uptake of OH by organic compounds has been observed in a number of studies, but the kinetics of mass transport and chemical reaction are still not fully understood. Here we apply the kinetic multilayer model of gas-particle interactions (KM-GAP) to experimental data from OH exposure studies of levoglucosan and abietic acid, which serve as surrogates and molecular markers of biomass burning aerosol (BBA). The model accounts for gas-phase diffusion within a cylindrical coated-wall flow tube, reversible adsorption of OH, surface-bulk exchange, bulk diffusion, and chemical reactions at the surface and in the bulk of the condensed phase. The nonlinear dependence of OH uptake coefficients on reactant concentrations and time can be reproduced by KM-GAP. We find that the bulk diffusion coefficient of the organic molecules is approximately 10(-16) cm(2) s(-1), reflecting an amorphous semisolid state of the organic substrates. The OH uptake is governed by reaction at or near the surface and can be kinetically limited by surface-bulk exchange or bulk diffusion of the organic reactants. Estimates of the chemical half-life of levoglucosan in 200 nm particles in a biomass burning plume increase from 1 day at high relative humidity to 1 week under dry conditions. In BBA particles transported to the free troposphere, the chemical half-life of levoglucosan can exceed 1 month due to slow bulk diffusion in a glassy matrix at low temperature.

Adsorption and desorption of gases on liquid or solid substrates are involved in multiphase processes and heterogeneous chemical reactions. The desorption energy (Edes0), which depends on the intermolecular forces between adsorbate and substrate, determines the residence time of chemical species at interfaces. We show how Edes0 and temperature influence the net uptake or release of gas species, the rates of surface–bulk exchange and surface or bulk reactions, and the equilibration timescales of gas–particle partitioning. Using literature data, we derive a parameterization to estimate Edes0 for a wide range of chemical species based on the molecular mass, polarizability, and oxygen-to-carbon ratio of the desorbing species independent of substrate-specific properties, which is possible because of the dominant role of the desorbing species' properties. Correlations between Edes0 and the enthalpies of vaporization and solvation are rooted in molecular interactions. The relation between Edes0 and desorption kinetics reflects the key role of interfacial exchange in multiphase processes. For small molecules and semi-volatile organics (VOC, IVOC, SVOC), Edes0 values around 10–100 kJ mol -1 correspond to desorption lifetimes around nanoseconds to days at room temperature. Even higher values up to years are obtained at low temperatures and for low volatile organic compounds (LVOC, ELVOC/ULVOC) relevant for secondary organic aerosols (SOA). Implications are discussed for SOA formation, gas–particle partitioning, organic phase changes, and indoor surface chemistry. We expect these insights to advance the mechanistic and kinetic understanding of multiphase processes in atmospheric and environmental physical chemistry, aerosol science, materials science, and chemical engineering. [ABSTRACT FROM AUTHOR]

Siloxanes are composed of silicon, oxygen, and alkyl groups and are emitted from consumer chemicals. Despite being entirely anthropogenic, siloxanes are being detected in remote regions and are ubiquitous in indoor and urban environments. Decamethylcyclopentasiloxane (D 5) is one of the most common cyclic congeners, and smog chamber and oxidation flow reactor (OFR) experiments have found D 5 + OH to form secondary organosiloxane aerosol (SOSiA). However, there is uncertainty about the reaction products and the reported SOSiA mass yields (YSOSiA) appear inconsistent. To quantify small volatile oxidation products (VOPs) and to consolidate the YSOSiA in the literature, we performed experiments using a potential aerosol mass OFR while varying D 5 concentration, humidity, and OH exposure (OH exp). We use a proton transfer reaction time-of-flight mass spectrometer to quantify D 5 , HCHO, and HCOOH and to detect other VOPs, which we tentatively identify as siloxanols and siloxanyl formates. We determine molar yields of HCHO and HCOOH between 52 %–211 % and 45 %–127 %, respectively. With particle size distributions measured with a scanning mobility particle sizer, we find YSOSiA to be < 10 % at OH exp < 1.3 × 10 11 s cm -3 and ∼ 20 % at OH exp , corresponding to that of the lifetime of D 5 at atmospheric OH concentrations. We also find that YSOSiA is dependent on both organic aerosol mass loading and OH exp. We use a kinetic box model of SOSiA formation and oxidative aging to explain the YSOSiA values found in this study and the literature. The model uses a volatility basis set (VBS) of the primary oxidation products as well as an aging rate coefficient in the gas phase, kage,gas , of 2.2×10-12 cm 3 s -1 and an effective aging rate coefficient in the particle phase, kage,particle , of 2.0 × 10 -12 cm 3 s -1. The combination of a primary VBS and OH-dependent oxidative aging predicts SOSiA formation much better than a standard-VBS parameterization that does not consider aging (root mean square error = 42.6 vs. 96.5). In the model, multi-generational aging of SOSiA products occurred predominantly in the particle phase. The need for an aging-dependent parameterization to accurately model SOSiA formation shows that concepts developed for secondary organic aerosol precursors, which can form low-volatile products at low OH exp , do not necessarily apply to D 5 + OH. The resulting yields of HCHO and HCOOH and the parameterization of YSOSiA may be used in larger-scale models to assess the implications of siloxanes for air quality. [ABSTRACT FROM AUTHOR]

Interfacial and multiphase chemical processes involving gases typically involve adsorption and desorption onto liquid or solid substrates. The desorption energy, which depends on the intermolecular forces between adsorbate and substrate, determines the residence time of chemical species at the interface. In this study, we demonstrate how variations in desorption energy and temperature influence the net uptake or release of gas species, which in turn affects the rates of surface and bulk reactions, surface-bulk exchange, and the equilibration time scales of gas-particle partitioning. We survey experimentally and theoretically derived desorption energies to develop a parameterization that enables the prediction of desorption energies based on the molecular weight, polarizability, and oxygen to carbon ratio of the desorbing chemical species independent of substrate-specific properties, which is possible because of the dominating role of the desorbing species' polarizability. The data and analyses compiled in this study provide new insights into the relationship between desorption energy and enthalpies of vaporization and solvation, reflecting the central role of desorption in the multiple steps of interfacial exchange and multiphase processes, including mass accommodation and heterogeneous chemical reactions. Practical implications are discussed for gas-particle partitioning, organic phase changes, secondary organic aerosol formation, and indoor surface chemistry. We conclude that future research in aerosol, atmospheric, and environmental physical chemistry, air quality, climate, and Earth system science as well as chemical engineering and materials science may benefit from further insight and constraints on the influence of desorption lifetimes and energies on multiphase processes and their temperature dependence. [ABSTRACT FROM AUTHOR]

Interfacial and multiphase chemical processes involving gases typically involve adsorption and desorption onto liquid or solid substrates. The desorption energy, which depends on the intermolecular forces between adsorbate and substrate, determines the residence time of chemical species at the interface. In this study, we demonstrate how variations in desorption energy and temperature influence the net uptake or release of gas species, which in turn affects the rates of surface and bulk reactions, surface-bulk exchange, and the equilibration time scales of gas-particle partitioning. We survey experimentally and theoretically derived desorption energies to develop a parameterization that enables the prediction of desorption energies based on the molecular weight, polarizability, and oxygen to carbon ratio of the desorbing chemical species independent of substrate-specific properties, which is possible because of the dominating role of the desorbing species' polarizability. The data and analyses compiled in this study provide new insights into the relationship between desorption energy and enthalpies of vaporization and solvation, reflecting the central role of desorption in the multiple steps of interfacial exchange and multiphase processes, including mass accommodation and heterogeneous chemical reactions. Practical implications are discussed for gas-particle partitioning, organic phase changes, secondary organic aerosol formation, and indoor surface chemistry. We conclude that future research in aerosol, atmospheric, and environmental physical chemistry, air quality, climate, and Earth system science as well as chemical engineering and materials science may benefit from further insight and constraints on the influence of desorption lifetimes and energies on multiphase processes and their temperature dependence. [ABSTRACT FROM AUTHOR]