Mapping pollution exposure and chemistry during an extreme air quality event (the 2018 Kilauea eruption) using a low-cost sensor network.

Extreme air quality episodes represent a major threat to human health worldwide but are highly dynamic and exceedingly challenging to monitor. The 2018 Kilauea Lower East Rift Zone eruption (May to August 2018) blanketed much of Hawai'i Island in "vog" (volcanic smog), a mixture of primary volcanic sulfur dioxide (SO2) gas and secondary particulate matter (PM). This episode was captured by several monitoring platforms, including a low-cost sensor (LCS) network consisting of 30 nodes designed and deployed specifically to monitor PM and SO2 during the event. Downwind of the eruption, network stations measured peak hourly PM2.5 and SO2 concentrations that exceeded 75 µg m-3 and 1,200 parts per billion (ppb), respectively. The LCS network's high spatial density enabled highly granular estimates of human exposure to both pollutants during the eruption, which was not possible using preexisting air quality measurements. Because of overlaps in population distribution and plume dynamics, a much larger proportion of the island's population was exposed to elevated levels of fine PM than to SO2 Additionally, the spatially distributed network was able to resolve the volcanic plume's chemical evolution downwind of the eruption. Measurements find a mean SO2 conversion time of ∼36 h, demonstrating the ability of distributed LCS networks to observe reaction kinetics and quantify chemical transformations of air pollutants in a real-world setting. This work also highlights the utility of LCS networks for emergency response during extreme episodes to complement existing air quality monitoring approaches.

Indoor Air Quality Implications of Germicidal 222 nm Light.

One strategy for mitigating the indoor transmission of airborne pathogens, including the SARS-CoV-2 virus, is irradiation by germicidal UV light (GUV). A particularly promising approach is 222 nm light from KrCl excimer lamps (GUV222); this inactivates airborne pathogens and is thought to be relatively safe for human skin and eye exposure. However, the impact of GUV222 on the composition of indoor air has received little experimental study. Here, we conduct laboratory experiments in a 150 L Teflon chamber to examine the formation of secondary species by GUV222. We show that GUV222 generates ozone (O3) and hydroxyl radicals (OH), both of which can react with volatile organic compounds to form oxidized volatile organic compounds and secondary organic aerosol particles. Results are consistent with a box model based on the known photochemistry. We use this model to simulate GUV222 irradiation under more realistic indoor air scenarios and demonstrate that under some conditions, GUV222 irradiation can lead to levels of O3, OH, and secondary organic products that are substantially elevated relative to normal indoor conditions. The results suggest that GUV222 should be used at low intensities and in concert with ventilation, decreasing levels of airborne pathogens while mitigating the formation of air pollutants.

Influence of the NO/NO2 Ratio on Oxidation Product Distributions under High-NO Conditions.

Organic oxidation reactions in the atmosphere can be challenging to parse due to the large number of branching points within each molecule's reaction mechanism. This complexity can complicate the attribution of observed effects to a particular chemical pathway. In this study, we simplify the chemistry of atmospherically relevant systems, and particularly the role of NOx, by generating individual alkoxy radicals via alkyl nitrite photolysis (to limit the number of accessible reaction pathways) and measuring their product distributions under different NO/NO2 ratios. Known concentrations of NO in the classically "high-NO" range are maintained in the chamber, thereby constraining first-generation RO2 (peroxy radicals) to react nearly exclusively with NO. Products are measured in both the gas phase (with a proton-transfer reaction mass spectrometer) and the particle phase (with an aerosol mass spectrometer). We observe substantial differences in measured products under varying NO/NO2 ratios (from ∼0.1 to >1); along with modeling simulations using the Master Chemical Mechanism (MCM), these results suggest indirect effects of NOx chemistry beyond the commonly cited RO2 + NO reaction. Specifically, lower-NO/NO2 ratios foster higher concentrations of secondary OH, higher concentrations of peroxyacyl nitrates (PAN, an atmospheric reservoir species), and a more highly oxidized product distribution that results in more secondary organic aerosol (SOA). The impact of NOx concentration beyond simple RO2 branching must be considered when planning laboratory oxidation experiments and applying their results to atmospheric conditions.

Laboratory Investigation of Renoxification from the Photolysis of Inorganic Particulate Nitrate.

Nitrogen oxides (NOx) play a key role in regulating the oxidizing capacity of the atmosphere through controlling the abundance of O3, OH, and other important gas and particle species. Some recent studies have suggested that particulate nitrate, which is conventionally considered as the ultimate oxidation product of NOx, can undergo "renoxification" via photolysis, recycling NOx and HONO back to the gas phase. However, there are large discrepancies in estimates of the importance of this channel, with reported renoxification rate constants spanning three orders of magnitude. In addition, previous laboratory studies derived the rate constant using bulk particle samples collected on substrates instead of suspended particles. In this work, we study renoxification of suspended submicron particulate sodium and ammonium nitrate through controlled laboratory photolysis experiments using an environmental chamber. We find that, under atmospherically relevant wavelengths and relative humidities, particulate inorganic nitrate releases NOx and HONO less than 10 times as rapidly as gaseous nitric acid, putting our measurements on the low end of recently reported renoxification rate constants. To the extent that our laboratory conditions are representative of the real atmosphere, renoxification from the photolysis of inorganic particulate nitrate appears to play a limited role in contributing to the NOx and OH budgets in remote environments. These results are based on simplified model systems; future studies should investigate renoxification of more complex aerosol mixtures that represent a broader spectrum of aerosol properties to better constrain the photolysis of ambient aerosols.

Chemistry of Functionalized Reactive Organic Intermediates in the Earth's Atmosphere: Impact, Challenges, and Progress.

The gas-phase oxidation of organic compounds is an important chemical process in the Earth's atmosphere. It governs oxidant levels and controls the production of key secondary pollutants, and hence has major implications for air quality and climate. Organic oxidation is largely controlled by the chemistry of a few reactive intermediates, namely, alkyl (R) radicals, alkoxy (RO) radicals, peroxy (RO2) radicals, and carbonyl oxides (R1R2COO), which may undergo a number of unimolecular and bimolecular reactions. Our understanding of these intermediates, and the reaction pathways available to them, is based largely on studies of unfunctionalized intermediates, formed in the first steps of hydrocarbon oxidation. However, it has become increasingly clear that intermediates with functional groups, which are generally formed later in the oxidation process, can exhibit fundamentally different reactivity than unfunctionalized ones. In this Perspective, we explore the unique chemistry available to functionalized organic intermediates in the Earth's atmosphere. After a brief review of the canonical chemistry available to unfunctionalized intermediates, we discuss how the addition of functional groups can introduce new reactions, either by changing the energetics or kinetics of a given reaction or by opening up new chemical pathways. We then provide examples of atmospheric reaction classes that are available only to functionalized intermediates. Some of these, such as unimolecular H-shift reactions of RO2 radicals, have been elucidated only relatively recently, and can have important impacts on atmospheric chemistry (e.g., on radical cycling or organic aerosol formation); it seems likely that other, as-yet undiscovered reactions of (multi)functional intermediates may also exist. We discuss the challenges associated with the study of the chemistry of such intermediates and review novel experimental and theoretical approaches that have recently provided (or hold promise for providing) new insights into their atmospheric chemistry. The continued use and development of such techniques and the close collaboration between experimentalists and theoreticians are necessary for a complete, detailed understanding of the chemistry of functionalized intermediates and their impact on major atmospheric chemical processes.

Chemistry of Simple Organic Peroxy Radicals under Atmospheric through Combustion Conditions: Role of Temperature, Pressure, and NOx Level.

Organic peroxy radicals (RO2) are key intermediates in the oxidation of organic compounds in both combustion systems and the atmosphere. While many studies have focused on reactions of RO2 in specific applications, spanning a relatively limited range of reaction conditions, the generalized behavior of RO2 radicals across the full range of reaction conditions (temperatures, pressures, and NO levels) has, to our knowledge, never been explored. In this work, two simple model systems, n-propyl peroxy radical and γ-isobutanol peroxy radical, are used to evaluate RO2 fate using pressure-dependent kinetics. The fate of these radicals was modeled based on literature data over 250-1250 K, 0.01-100 bar, and 1 ppt to 100 ppm of NO, which spans the typical range of atmospheric and combustion conditions. Covering this entire range provides a broad overview of the reactivity of these species under both atmospheric and combustion conditions, as well as under conditions intermediate to the two. A particular focus is on the importance of reactions that were traditionally considered to occur in only one of the two sets of conditions: RO2 unimolecular isomerization reactions (long known to occur in combustion systems but only recently appreciated in atmospheric systems) and RO2 bimolecular reactions of RO2 with NO (thought to occur mainly in atmospheric systems and rarely considered in combustion chemistry).

Screening for New Pathways in Atmospheric Oxidation Chemistry with Automated Mechanism Generation.

In the Earth's atmosphere, reactive organic carbon undergoes oxidation via a highly complex, multigeneration process, with implications for air quality and climate. Decades of experimental and theoretical studies, primarily on the reactions of hydrocarbons, have led to a canonical understanding of how gas-phase oxidation of organic compounds takes place. Recent research has brought to light a number of examples where the presence of certain functional groups opens up reaction pathways for key radical intermediates, including alkyl radicals, alkoxy radicals, and peroxy radicals, that are substantially different from traditional oxidation mechanisms. These discoveries highlight the need for methods that systematically explore the chemistry of complex, functionalized molecules without being prohibitively expensive. In this work, automated reaction network generation is used as a screening tool for new pathways in atmospheric oxidation chemistry. The reaction mechanism generator (RMG) is used to generate reaction networks for the OH-initiated oxidation of 200 mono- and bifunctionally substituted n-pentanes. The resulting networks are then filtered to highlight the reactions of key radical intermediates that are fast enough to compete with traditional atmospheric removal processes as well as "uncanonical" processes which differ from traditionally accepted oxidation mechanisms. Several recently reported, uncanonical atmospheric mechanisms appear in the RMG dataset. These "proof of concept" results provide confidence in this approach as a tool in the search for overlooked atmospheric oxidation chemistry. Several previously unreported reaction types are also encountered in the dataset. The most potentially atmospherically important of these is a radical-carbonyl ring-closure reaction that produces a highly functionalized cyclic alkoxy radical. This pathway is proposed as a promising target for further study via experiments and more detailed theoretical calculations. The approach presented herein represents a new way to efficiently explore atmospheric chemical space and unearth overlooked reaction steps in atmospheric oxidation.

Oxygenated Aromatic Compounds are Important Precursors of Secondary Organic Aerosol in Biomass-Burning Emissions.

Biomass burning is the largest combustion-related source of volatile organic compounds (VOCs) to the atmosphere. We describe the development of a state-of-the-science model to simulate the photochemical formation of secondary organic aerosol (SOA) from biomass-burning emissions observed in dry (RH <20%) environmental chamber experiments. The modeling is supported by (i) new oxidation chamber measurements, (ii) detailed concurrent measurements of SOA precursors in biomass-burning emissions, and (iii) development of SOA parameters for heterocyclic and oxygenated aromatic compounds based on historical chamber experiments. We find that oxygenated aromatic compounds, including phenols and methoxyphenols, account for slightly less than 60% of the SOA formed and help our model explain the variability in the organic aerosol mass (R2 = 0.68) and O/C (R2 = 0.69) enhancement ratios observed across 11 chamber experiments. Despite abundant emissions, heterocyclic compounds that included furans contribute to ∼20% of the total SOA. The use of pyrolysis-temperature-based or averaged emission profiles to represent SOA precursors, rather than those specific to each fire, provide similar results to within 20%. Our findings demonstrate the necessity of accounting for oxygenated aromatics from biomass-burning emissions and their SOA formation in chemical mechanisms.

Pressure-dependent kinetics of peroxy radicals formed in isobutanol combustion.

Bio-derived isobutanol has been approved as a gasoline additive in the US, but our understanding of its combustion chemistry still has significant uncertainties. Detailed quantum calculations could improve model accuracy leading to better estimation of isobutanol's combustion properties and its environmental impacts. This work examines 47 molecules and 38 reactions involved in the first oxygen addition to isobutanol's three alkyl radicals located α, ß, and γ to the hydroxide. Quantum calculations are mostly done at CCSD(T)-F12/cc-pVTZ-F12//B3LYP/CBSB7, with 1-D hindered rotor corrections obtained at B3LYP/6-31G(d). The resulting potential energy surfaces are the most comprehensive isobutanol peroxy networks published to date. Canonical transition state theory and a 1-D microcanonical master equation are used to derive high-pressure-limit and pressure-dependent rate coefficients, respectively. At all conditions studied, the recombination of γ-isobutanol radical with O2 forms HO2 + isobutanal. The recombination of ß-isobutanol radical with O2 forms a stabilized hydroperoxy alkyl radical below 400 K, water + an alkoxy radical at higher temperatures, and HO2 + an alkene above 1200 K. The recombination of ß-isobutanol radical with O2 results in a mixture of products between 700-1100 K, forming acetone + formaldehyde + OH at lower temperatures and forming HO2 + alkenes at higher temperatures. The barrier heights, high-pressure-limit rates, and pressure-dependent kinetics generally agree with the results from previous quantum chemistry calculations. Six reaction rates in this work deviate by over three orders of magnitude from kinetics in detailed models of isobutanol combustion, suggesting the rates calculated here can help improve modeling of isobutanol combustion and its environmental fate.

Infrared Ion Spectroscopy of Environmental Organic Mixtures: Probing the Composition of α-Pinene Secondary Organic Aerosol.

Characterizing the chemical composition of organic aerosols can elucidate aging mechanisms as well as the chemical and physical properties of the aerosol. However, the high chemical complexity and often low atmospheric abundance present a difficult analytical challenge. Milligrams or more of material may be needed for speciated spectroscopic analysis. In contrast, mass spectrometry provides a very sensitive platform but limited structural information. Here, we combine the strengths of mass spectrometry and infrared (IR) action spectroscopy to generate characteristic IR spectra of individual, mass-isolated ion populations. Soft ionization combined with in situ infrared ion spectroscopy, using the tunable free-electron laser FELIX, provides detailed information on molecular structures and functional groups. We apply this technique, along with quantum mechanical modeling, to characterize organic molecules in secondary organic aerosol (SOA) formed from the ozonolysis of α-pinene. Spectral overlap with a standard is used to identify cis-pinonic acid. We also demonstrate the characterization of isomers for multiple SOA products using both quantum mechanical computations and analyses of fragment ion spectra. These results demonstrate the detailed structural information on isolated ions obtained by combining mass spectrometry with fingerprint IR spectroscopy.

The Essential Role for Laboratory Studies in Atmospheric Chemistry.

Laboratory studies of atmospheric chemistry characterize the nature of atmospherically relevant processes down to the molecular level, providing fundamental information used to assess how human activities drive environmental phenomena such as climate change, urban air pollution, ecosystem health, indoor air quality, and stratospheric ozone depletion. Laboratory studies have a central role in addressing the incomplete fundamental knowledge of atmospheric chemistry. This article highlights the evolving science needs for this community and emphasizes how our knowledge is far from complete, hindering our ability to predict the future state of our atmosphere and to respond to emerging global environmental change issues. Laboratory studies provide rich opportunities to expand our understanding of the atmosphere via collaborative research with the modeling and field measurement communities, and with neighboring disciplines.

Effects of Condensed-Phase Oxidants on Secondary Organic Aerosol Formation.

In this study we investigate the hypothesis that oxidants present within atmospheric particles can promote the formation of highly oxidized organic aerosol (OA) via oxidation reactions in the condensed phase. Secondary organic aerosol (SOA) was generated from the ozonolysis of α-pinene and isoprene in an environmental chamber, with seed particles systematically varied in order to assess the effects of condensed-phase oxidant levels on SOA loading and composition. The effects of particle phase (aqueous vs dry), condensed-phase oxidant source (none vs H2O2 vs Fenton chemistry), and irradiation (none vs UV) were all examined. For experiments conducted with aqueous particles but without any added oxidants, UV irradiation resulted in a small but measurable enhancement in the oxygen-to-carbon ratio (O/C). OA formed in the presence of aqueous oxidants was substantially more oxidized, with the highest oxidant concentrations leading to OA with an O/C as high as 1.4 for α-pinene and 2.0 for isoprene, strongly suggesting the formation of oxalate. High aqueous oxidant levels also resulted in increased loss of carbon from the condensed phase. This OA was more oxidized than in any other ozonolysis experiment reported to date, indicating that, when present, aqueous oxidants can have a dramatic effect on SOA formation. However, oxidant concentrations within atmospheric aqueous particles remain poorly constrained, making it difficult to assess the impacts of aqueous-phase oxidation on the loadings and oxidation state of atmospheric OA.

Load-Dependent Emission Factors and Chemical Characteristics of IVOCs from a Medium-Duty Diesel Engine.

A detailed understanding of the climate and air quality impacts of mobile-source emissions requires the characterization of intermediate-volatility organic compounds (IVOCs), relatively-low-vapor-pressure gas-phase species that may generate secondary organic aerosol with high yields. Due to challenges associated with IVOC detection and quantification, IVOC emissions remain poorly understood at present. Here, we describe measurements of the magnitude and composition of IVOC emissions from a medium-duty diesel engine. Measurements are made on an engine dynamometer and utilize a new mass-spectrometric instrument to characterize the load dependence of the emissions in near-real-time. Results from steady-state engine operation indicate that IVOC emissions are highly dependent on engine power, with highest emissions at engine idle and low-load operation (≤25% maximum rated power) with a chemical composition dominated by saturated hydrocarbon species. Results suggest that unburned fuel components are the dominant IVOCs emitted at low loads. As engine load increases, IVOC emissions decline rapidly and become increasingly characterized by unsaturated hydrocarbons and oxygenated organics, newly formed from incomplete combustion processes at elevated engine temperatures and pressures. Engine transients, including a cold-start ignition and engine acceleration, show IVOC emission profiles that are different in amount or composition compared to steady-state combustion, underscoring the utility of characterizing IVOC emissions with high time resolution across realistic engine operating conditions. We find possible evidence for IVOC losses on unheated dilution and sampling surfaces, which need to be carefully accounted for in IVOC emission studies.

Atmospheric evolution of sulfur emissions from KiÌ lauea: real-time measurements of oxidation, dilution, and neutralization within a volcanic plume.

The high atmospheric concentrations of toxic gases, particulate matter, and acids in the areas immediately surrounding volcanoes can have negative impacts on human and ecological health. To better understand the atmospheric fate of volcanogenic emissions in the near field (in the first few hours after emission), we have carried out real-time measurements of key chemical components of the volcanic plume from Ki̅lauea on the Island of Hawai'i. Measurements were made at two locations, one ∼ 3 km north-northeast of the vent and the other 31 km to the southwest, with sampling at each site spanning a range of meteorological conditions and volcanic influence. Instrumentation included a sulfur dioxide monitor and an Aerosol Chemical Speciation Monitor, allowing for a measurement of the partitioning between the two major sulfur species (gas-phase SO2 and particulate sulfate) every 5 min. During trade wind conditions, which sent the plume toward the southwest site, sulfur partitioning exhibited a clear diurnal pattern, indicating photochemical oxidation of SO2 to sulfate; this enabled the quantitative determination of plume age (5 h) and instantaneous SO2 oxidation rate (2.4 × 10(-6) s(-1) at solar noon). Under stagnant conditions near the crater, the extent of SO2 oxidation was substantially higher, suggesting faster oxidation. The particles within the plume were extremely acidic, with pH values (controlled largely by ambient relative humidity) as low as -0.8 and strong acidity (controlled largely by absolute sulfate levels) up to 2200 nmol/m(3). The high variability of sulfur partitioning and particle composition underscores the chemically dynamic nature of volcanic plumes, which may have important implications for human and ecological health.

Heterogeneous Oxidation of Atmospheric Organic Aerosol: Kinetics of Changes to the Amount and Oxidation State of Particle-Phase Organic Carbon.

Atmospheric oxidation reactions are known to affect the chemical composition of organic aerosol (OA) particles over timescales of several days, but the details of such oxidative aging reactions are poorly understood. In this study we examine the rates and products of a key class of aging reaction, the heterogeneous oxidation of particle-phase organic species by the gas-phase hydroxyl radical (OH). We compile and reanalyze a number of previous studies from our laboratories involving the oxidation of single-component organic particles. All kinetic and product data are described on a common basis, enabling a straightforward comparison among different chemical systems and experimental conditions. Oxidation chemistry is described in terms of changes to key ensemble properties of the OA, rather than to its detailed molecular composition, focusing on two quantities in particular, the amount and the oxidation state of the particle-phase carbon. Heterogeneous oxidation increases the oxidation state of particulate carbon, with the rate of increase determined by the detailed chemical mechanism. At the same time, the amount of particle-phase carbon decreases with oxidation, due to fragmentation (C-C scission) reactions that form small, volatile products that escape to the gas phase. In contrast to the oxidation state increase, the rate of carbon loss is nearly uniform among most systems studied. Extrapolation of these results to atmospheric conditions indicates that heterogeneous oxidation can have a substantial effect on the amount and composition of atmospheric OA over timescales of several days, a prediction that is broadly in line with available measurements of OA evolution over such long timescales. In particular, 3-13% of particle-phase carbon is lost to the gas phase after one week of heterogeneous oxidation. Our results indicate that oxidative aging represents an important sink for particulate organic carbon, and more generally that fragmentation reactions play a major role in the lifecycle of atmospheric OA.

Changes to the chemical composition of soot from heterogeneous oxidation reactions.

The atmospheric aging of soot particles, in which various atmospheric processes alter the particles' chemical and physical properties, is poorly understood and consequently is not well-represented in models. In this work, soot aging via heterogeneous oxidation by OH and ozone is investigated using an aerosol flow reactor coupled to a new high-resolution aerosol mass spectrometric technique that utilizes infrared vaporization and single-photon vacuum ultraviolet ionization. This analytical technique simultaneously measures the elemental and organic carbon components of soot, allowing for the composition of both fractions to be monitored. At oxidant exposures relevant to the particles' atmospheric lifetimes (the equivalent of several days of oxidation), the elemental carbon portion of the soot, which makes up the majority of the particle mass, undergoes no discernible changes in mass or composition. In contrast, the organic carbon (which in the case of methane flame soot is dominated by aliphatic species) is highly reactive, undergoing first the addition of oxygen-containing functional groups and ultimately the loss of organic carbon mass from fragmentation reactions that form volatile products. These changes occur on time scales comparable to those of other nonoxidative aging processes such as condensation, suggesting that further research into the combined effects of heterogeneous and condensational aging is needed to improve our ability to accurately predict the climate and health impacts of soot particles.

Chemical compositions of black carbon particle cores and coatings via soot particle aerosol mass spectrometry with photoionization and electron ionization.

Black carbon is an important constituent of atmospheric aerosol particle matter (PM) with significant effects on the global radiation budget and on human health. The soot particle aerosol mass spectrometer (SP-AMS) has been developed and deployed for real-time ambient measurements of refractory carbon particles. In the SP-AMS, black carbon or metallic particles are vaporized through absorption of 1064 nm light from a CW Nd:YAG laser. This scheme allows for continuous "soft" vaporization of both core and coating materials. The main focus of this work is to characterize the extent to which this vaporization scheme provides enhanced chemical composition information about aerosol particles. This information is difficult to extract from standard SP-AMS mass spectra because they are complicated by extensive fragmentation from the harsh 70 eV EI ionization scheme that is typically used in these instruments. Thus, in this work synchotron-generated vacuum ultraviolet (VUV) light in the 8-14 eV range is used to measure VUV-SP-AMS spectra with minimal fragmentation. VUV-SP-AMS spectra of commercially available carbon black, fullerene black, and laboratory generated flame soots were obtained. Small carbon cluster cations (C(+)-C5(+)) were found to dominate the VUV-SP-AMS spectra of all the samples, indicating that the corresponding neutral clusters are key products of the SP vaporization process. Intercomparisons of carbon cluster ratios observed in VUV-SP-AMS and SP-AMS spectra are used to confirm spectral features that could be used to distinguish between different types of refractory carbon particles. VUV-SP-AMS spectra of oxidized organic species adsorbed on absorbing cores are also examined and found to display less thermally induced decomposition and fragmentation than spectra obtained with thermal vaporization at 200 °C (the minimum temperature needed to quantitatively vaporize ambient oxidized organic aerosol with a continuously heated surface). The particle cores tested in these studies include black carbon, silver, gold, and platinum nanoparticles. These results demonstrate that SP vaporization is capable of providing enhanced organic chemical composition information for a wide range of organic coating materials and IR absorbing particle cores. The potential of using this technique to study organic species of interest in seeded laboratory chamber or flow reactor studies is discussed.

Volatility and aging of atmospheric organic aerosol.

Organic-aerosol phase partitioning (volatility) and oxidative aging are inextricably linked in the atmosphere because partitioning largely controls the rates and mechanisms of aging reactions as well as the actual amount of organic aerosol. Here we discuss those linkages, describing the basic theory of partitioning thermodynamics as well as the dynamics that may limit the approach to equilibrium under some conditions. We then discuss oxidative aging in three forms: homogeneous gas-phase oxidation, heterogeneous oxidation via uptake of gas-phase oxidants, and aqueous-phase oxidation. We present general scaling arguments to constrain the relative importance of these processes in the atmosphere, compared to each other and compared to the characteristic residence time of particles in the atmosphere.

Secondary organic aerosol formation from acyclic, monocyclic, and polycyclic alkanes.

A large number of organic species emitted into the atmosphere contain cycloalkyl groups. While cyclic species are believed to be important secondary organic aerosol (SOA) precursors, the specific role of cyclic moieties (particularly for species with multiple or fused rings) remains uncertain. Here we examine the yields and composition of SOA formed from the reaction of OH with a series of C10 (cyclo)alkanes, with 0-3 rings, in order to better understand the role of multiple cyclic moieties on aerosol formation pathways. A chamber oxidation technique using high, sustained OH radical concentrations was used to simulate long reaction times in the atmosphere. This aging technique leads to higher yields than in previously reported chamber experiments. Yields were highest for cyclic and polycyclic precursors, though yield exhibited little dependence on number of rings. However, the oxygen-to-carbon ratio of the SOA was highest for the polycyclic precursors. These trends are consistent with aerosol formation requiring two generations of oxidation and 3-4 oxygen-containing functional groups in order to condense. Cyclic, unbranched structures are protected from fragmentation during the first oxidation step, with C-C bond scission instead leading to ring opening, efficient functionalization, and high SOA yields. Fragmentation may occur during subsequent oxidation steps, limiting yields by forming volatile products. Polycyclic structures can undergo multiple ring opening reactions, but do not have markedly higher yields, likely due to enhanced fragmentation in the second oxidation step. By contrast, C-C bond scission for the linear and branched structures leads to fragmentation prior to condensation, resulting in low SOA yields. The results highlight the key roles of multigenerational chemistry and susceptibility to fragmentation in the formation and evolution of SOA.