Elucidating the photodissociation fingerprint and quantifying the determination of organic hydroperoxides in gas-phase autoxidation.

Hydroperoxides are formed in the atmospheric oxidation of volatile organic compounds, in the combustion autoxidation of fuel, in the cold environment of the interstellar medium, and also in some catalytic reactions. They play crucial roles in the formation and aging of secondary organic aerosols and in fuel autoignition. However, the concentration of organic hydroperoxides is seldom measured, and typical estimates have large uncertainties. In this work, we developed a mild and environmental-friendly method for the synthesis of alkyl hydroperoxides (ROOH) with various structures, and we systematically measured the absolute photoionization cross-sections (PICSs) of the ROOHs using synchrotron vacuum ultraviolet-photoionization mass spectrometry (SVUV-PIMS). A chemical titration method was combined with an SVUV-PIMS measurement to obtain the PICS of 4-hydroperoxy-2-pentanone, a typical molecule for combustion and atmospheric autoxidation ketohydroperoxides (KHPs). We found that organic hydroperoxide cations are largely dissociated by loss of OOH. This fingerprint was used for the identification and accurate quantification of the organic peroxides, and it can therefore be used to improve models for autoxidation chemistry. The synthesis method and photoionization dataset for organic hydroperoxides are useful for studying the chemistry of hydroperoxides and the reaction kinetics of the hydroperoxy radicals and for developing and evaluating kinetic models for the atmospheric autoxidation and combustion autoxidation of the organic compounds.

Sunlight can convert atmospheric aerosols into a glassy solid state and modify their environmental impacts.

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

Model Simulations and Predictions of Hydroxymethanesulfonate (HMS) in the Beijing-Tianjin-Hebei Region, China: Roles of Aqueous Aerosols and Atmospheric Acidity.

Hydroxymethanesulfonate (HMS) has been found to be an abundant organosulfur aerosol compound in the Beijing-Tianjin-Hebei (BTH) region with a measured maximum daily mean concentration of up to 10 µg per cubic meter in winter. However, the production medium of HMS in aerosols is controversial, and it is unknown whether chemical transport models are able to capture the variations of HMS during individual haze events. In this work, we modify the parametrization of HMS chemistry in the nested-grid GEOS-Chem chemical transport model, whose simulations provide a good account of the field measurements during winter haze episodes. We find the contribution of the aqueous aerosol pathway to total HMS is about 36% in winter in Beijing, due primarily to the enhancement effect of the ionic strength on the rate constants of the reaction between dissolved formaldehyde and sulfite. Our simulations suggest that the HMS-to-inorganic sulfate ratio will increase from the baseline of 7% to 13% in the near future, given the ambitious clean air and climate mitigation policies for the BTH region. The more rapid reductions in emissions of SO2 and NOx compared to NH3 alter the atmospheric acidity, which is a critical factor leading to the rising importance of HMS in particulate sulfur species.

Secondary Organic Aerosol Formation from the Photooxidation of Aromatic Ketone Intermediate Volatile Organic Compounds.

Oxygenated aromatics are substantial secondary organic aerosol (SOA) precursors, such as benzyl alcohol and phenolic compounds. Aromatic ketone intermediate volatile organic compounds (IVOCs), as a subclass of oxygenated aromatics, were found in anthropogenic source emissions and may contribute to SOA formation. However, the SOA yields and formation pathways of aromatic ketone IVOCs remain unknown. In this study, the photooxidations of aromatic ketone IVOCs in the absence and presence of NOx were studied in an oxidation flow reactor, and the particle- and gas-phase oxidation products were measured. The maximum SOA yields of benzophenone and 1,2-diphenylethanone are 0.24 and 0.33-0.35, respectively, relatively high among oxygenated aromatics. The SOA yields in the presence of NOx are 2-3 times higher than those in the absence of NOx in the late stage of oxidation. As the photooxidation proceeds, H/C of SOA slightly increases with O/C, and a greater amount of more-oxidized ring-retaining products exists in the particle phase in the presence of NOx. Based on gas-phase products and possible reaction pathways, functionalization of benzoic acid via the phenolic pathway is favored in the presence of NOx. Thus, our study highlights the significant SOA formation from aromatic ketone IVOCs, especially in the presence of NOx during long-time photooxidation.

Obscured Contribution of Oxygenated Intermediate-Volatility Organic Compounds to Secondary Organic Aerosol Formation from Gasoline Vehicle Emissions.

Secondary organic aerosol (SOA) formation from gasoline vehicles spanning a wide range of emission types was investigated using an oxidation flow reactor (OFR) by conducting chassis dynamometer tests. Aided by advanced mass spectrometric techniques, SOA precursors, including volatile organic compounds (VOCs) and intermediate/semivolatile organic compounds (I/SVOCs), were comprehensively characterized. The reconstructed SOA produced from the speciated VOCs and I/SVOCs can explain 69% of the SOA measured downstream of an OFR upon 0.5-3 days' OH exposure. While VOCs can only explain 10% of total SOA production, the contribution from I/SVOCs is 59%, with oxygenated I/SVOCs (O-I/SVOCs) taking up 20% of that contribution. O-I/SVOCs (e.g., benzylic or aliphatic aldehydes and ketones), as an obscured source, account for 16% of total nonmethane organic gas (NMOG) emission. More importantly, with the improvement in emission standards, the NMOG is effectively mitigated by 35% from China 4 to China 6, which is predominantly attributed to the decrease of VOCs. Real-time measurements of different NMOG components as well as SOA production further reveal that the current emission control measures, such as advances in engine and three-way catalytic converter (TWC) techniques, are effective in reducing the "light" SOA precursors (i.e., single-ring aromatics) but not for the I/SVOC emissions. Our results also highlight greater effects of O-I/SVOCs to SOA formation than previously observed and the urgent need for further investigation into their origins, i.e., incomplete combustion, lubricating oil, etc., which requires improvements in real-time molecular-level characterization of I/SVOC molecules and in turn will benefit the future design of control measures.

Tethered balloon system and High-Resolution Mass Spectrometry Reveal Increased Organonitrates Aloft Compared to the Ground Level.

Atmospheric particles play critical roles in climate. However, significant knowledge gaps remain regarding the vertically resolved organic molecular-level composition of atmospheric particles due to aloft sampling challenges. To address this, we use a tethered balloon system at the Southern Great Plains Observatory and high-resolution mass spectrometry to, respectively, collect and characterize organic molecular formulas (MF) in the ground level and aloft (up to 750 m) samples. We show that organic MF uniquely detected aloft were dominated by organonitrates (139 MF; 54% of all uniquely detected aloft MF). Organonitrates that were uniquely detected aloft featured elevated O/C ratios (0.73 ± 0.23) compared to aloft organonitrates that were commonly observed at the ground level (0.63 ± 0.22). Unique aloft organic molecular composition was positively associated with increased cloud coverage, increased aloft relative humidity (∼40% increase compared to ground level), and decreased vertical wind variance. Furthermore, 29% of extremely low volatility organic compounds in the aloft sample were truly unique to the aloft sample compared to the ground level, emphasizing potential oligomer formation at higher altitudes. Overall, this study highlights the importance of considering vertically resolved organic molecular composition (particularly for organonitrates) and hypothesizes that aqueous phase transformations and vertical wind variance may be key variables affecting the molecular composition of aloft organic aerosol.

Secondary Organic Aerosol Generated from Biomass Burning Emitted Phenolic Compounds: Oxidative Potential, Reactive Oxygen Species, and Cytotoxicity.

Phenolic compounds are largely emitted from biomass burning (BB) and have a significant potential to form SOA (Phc-SOA). However, the toxicological properties of Phc-SOA remain unclear. In this study, phenol and guaiacol were chosen as two representative phenolic gases in BB plumes, and the toxicological properties of water-soluble components of their SOA generated under different photochemical ages and NOx levels were investigated. Phenolic compounds contribute greatly to the oxidative potential (OP) of biomass-burning SOA. OH-adducts of guaiacol (e.g., 2-methoxyhydroquinone) were identified as components of guaiacol SOA (GSOA) with high OP. The addition of nitro groups to 2,5-dimethyl-1,4-benzoquinone, a surrogate quinone compound in Phc-SOA, increased its OP. The toxicity of both phenol SOA (PSOA) and GSOA in vitro in human alveolar epithelial cells decreased with aging in terms of both cell death and cellular reactive oxygen species (ROS), possibly due to more ring-opening products with relatively low toxicity. The influence of NOx was consistent between cell death and cellular ROS for GSOA but not for PSOA, indicating that cellular ROS production does not necessarily represent all processes contributing to cell death caused by PSOA. Combining different acellular and cellular assays can provide a comprehensive understanding of aerosol toxicological properties.

Organic Emissions of Volatile Chemical Products in Canada: Emission Inventories, Indoor-to-Outdoor Transfer, and Regional Impacts.

The contribution of volatile chemical products (VCPs) to ambient air pollution has increased following decades of regulating combustion sources. There is a research gap concerning the impact of indoor physicochemical phenomena on VCP emissions. In this work, a bottom-up speciated VCP emission inventory with indoor-outdoor resolution was developed for Canada, an industrialized country with low air pollution levels, whose major cities are among the largest urban areas in North America. VCPs were estimated to account for about 290 kilotons of gaseous organic emissions for a typical year in the 2010s, with more than 60% of emissions occurring indoors. Coatings and cleaners were the most emissive VCP categories. Oxygenated species and saturated aliphatics dominated the chemical profiles of most emissions. Less than 5% of VCP emissions were impacted by indoor physicochemical phenomena. VCP emissions were predicted to account for 0.8-3.2 s-1 of OH reactivity and 0.22-0.52 µg/m3 of secondary organic aerosol formation potential in major urban areas in Canada. Our predictions aligned with previous measurements concerning indoor and outdoor organic pollutant levels, underscoring the important air quality impacts of VCPs relative to other sources. Our results provide helpful insights for future research regarding VCP emissions, especially from indoor spaces.

Formation and Transport of Secondary Contaminants Associated with Germicidal Ultraviolet Light Systems in an Occupied Classroom.

Germicidal ultraviolet light (GUV) systems are designed to control airborne pathogen transmission in buildings. However, it is important to acknowledge that certain conditions and system configurations may lead GUV systems to produce air contaminants including oxidants and secondary organic aerosols (SOA). In this study, we modeled the formation and dispersion of oxidants and secondary contaminants generated by the operation of GUV systems employing ultraviolet C 254 and 222 nm. Using a three-dimensional computational fluid dynamics model, we examined the breathing zone concentrations of chemical species in an occupied classroom. Our findings indicate that operating GUV 222 leads to an approximate increase of 10 ppb in O3 concentration and 5.2 µg·m-3 in SOA concentration compared to a condition without GUV operation, while GUV 254 increases the SOA concentration by about 1.2 µg·m-3, with a minimal impact on the O3 concentration. Furthermore, increasing the UV fluence rate of GUV 222 from 1 to 5 µW·cm-2 results in up to 80% increase in the oxidants and SOA concentrations. For GUV 254, elevating the UV fluence rate from 30 to 50 µW·cm-2 or doubling the radiating volume results in up to 50% increase in the SOA concentration. Note that indoor airflow patterns, particularly buoyancy-driven airflow (or displacement ventilation), lead to 15-45% lower SOA concentrations in the breathing zone compared to well-mixed airflow. The results also reveal that when the ventilation rate is below 2 h-1, operating GUV 254 has a smaller impact on human exposure to secondary contaminants than GUV 222. However, GUV 254 may generate more contaminants than GUV 222 when operating at high indoor O3 levels (>15 ppb). These results suggest that the design of GUV systems should consider indoor O3 levels and room ventilation conditions.

A Near-Explicit Reaction Mechanism of Chlorine-Initiated Limonene: Implications for Health Risks Associated with the Concurrent Use of Cleaning Agents and Disinfectants.

Limonene, a key volatile chemical product (VCP) commonly found in personal care and cleaning agents, is emerging as a major indoor air pollutant. Recently, elevated levels of reactive chlorine species during bleach cleaning and disinfection have been reported to increase indoor oxidative capacity. However, incomplete knowledge of the indoor transformation of limonene, especially the missing chlorine chemistry, poses a barrier to evaluating the environmental implications associated with the concurrent use of cleaning agents and disinfectants. Here, we investigated the reaction mechanisms of chlorinated limonene peroxy radicals (Cl-lim-RO2•), key intermediates in determining the chlorine chemistry of limonene, and toxicity of transformation products (TPs) using quantum chemical calculations and toxicology modeling. The results indicate that Cl-lim-RO2• undergoes a concerted autoxidation process modulated by RO2• and alkoxy radicals (RO•), particularly emphasizing the importance of RO• isomerization. Following this generalized autoxidation mechanism, Cl-lim-RO2• can produce low-volatility precursors of secondary organic aerosols. Toxicological findings further indicate that the majority of TPs exhibit increased respiratory toxicity, mutagenicity, and eye/skin irritation compared to limonene, presenting an occupational hazard for indoor occupants. The proposed near-explicit reaction mechanism of chlorine-initiated limonene significantly enhances our current understanding of both RO2• and RO• chemistry while also highlighting the health risks associated with the concurrent use of cleaning agents and disinfectants.

Aqueous-Phase Photoreactions of Mixed Aromatic Carbonyl Photosensitizers Yield More Oxygenated, Oxidized, and less Light-Absorbing Secondary Organic Aerosol (SOA) than Single Systems.

Aromatic carbonyls have been mainly probed as photosensitizers for aqueous secondary organic aerosol (aqSOA) and light-absorbing organic aerosol (i.e., brown carbon or BrC) formation, but due to their organic nature, they can also undergo oxidation to form aqSOA and BrC. However, photochemical transformations of aromatic carbonyl photosensitizers, particularly in multicomponent systems, are understudied. This study explored aqSOA formation from the irradiation of aromatic carbonyl photosensitizers in mixed and single systems under cloud/fog conditions. Mixed systems consisting of phenolic carbonyls only (VL + ActSyr + SyrAld: vanillin [VL] + acetosyringone [ActSyr] + syringaldehyde [SyrAld]) and another composed of both nonphenolic and phenolic carbonyls (DMB + ActSyr + SyrAld: 3,4-dimethoxybenzaldehyde [DMB], a nonphenolic carbonyl, + ActSyr + SyrAld) were compared to single systems of VL (VL*) and DMB (DMB*), respectively. In mixed systems, the shorter lifetimes of VL and DMB indicate their diminished capacity to trigger the oxidation of other organic compounds (e.g., guaiacol [GUA], a noncarbonyl phenol). In contrast to the slow decay and minimal photoenhancement for DMB*, the rapid photodegradation and significant photoenhancement for VL* indicate efficient direct photosensitized oxidation (i.e., self-photosensitization). Relative to single systems, the increased oxidant availability promoted functionalization in VL + ActSyr + SyrAld and accelerated the conversion of early generation aqSOA in DMB + ActSyr + SyrAld. Moreover, the increased availability of oxidizable substrates countered by stronger oxidative capacity limited the contribution of mixed systems to aqSOA light absorption. This suggests a weaker radiative effect of BrC from mixed photosensitizer systems than BrC from single photosensitizer systems. Furthermore, more oxygenated and oxidized aqSOA was observed with increasing complexity of the reaction systems (e.g., VL* < VL + ActSyr + SyrAld < VL + ActSyr + SyrAld + GUA). This work offers new insights into aqSOA formation by emphasizing the dual role of organic photosensitizers as oxidant sources and oxidizable substrates.

Fostering a Holistic Understanding of the Full Volatility Spectrum of Organic Compounds from Benzene Series Precursors through Mechanistic Modeling.

A comprehensive understanding of the full volatility spectrum of organic oxidation products from the benzene series precursors is important to quantify the air quality and climate effects of secondary organic aerosol (SOA) and new particle formation (NPF). However, current models fail to capture the full volatility spectrum due to the absence of important reaction pathways. Here, we develop a novel unified model framework, the integrated two-dimensional volatility basis set (I2D-VBS), to simulate the full volatility spectrum of products from benzene series precursors by simultaneously representing first-generational oxidation, multigenerational aging, autoxidation, dimerization, nitrate formation, etc. The model successfully reproduces the volatility and O/C distributions of oxygenated organic molecules (OOMs) as well as the concentrations and the O/C of SOA over wide-ranging experimental conditions. In typical urban environments, autoxidation and multigenerational oxidation are the two main pathways for the formation of OOMs and SOA with similar contributions, but autoxidation contributes more to low-volatility products. NOx can reduce about two-thirds of OOMs and SOA, and most of the extremely low-volatility products compared to clean conditions, by suppressing dimerization and autoxidation. The I2D-VBS facilitates a holistic understanding of full volatility product formation, which helps fill the large gap in the predictions of organic NPF, particle growth, and SOA formation.

Aqueous production of secondary organic aerosol from fossil-fuel emissions in winter Beijing haze.

Secondary organic aerosol (SOA) produced by atmospheric oxidation of primary emitted precursors is a major contributor to fine particulate matter (PM2.5) air pollution worldwide. Observations during winter haze pollution episodes in urban China show that most of this SOA originates from fossil-fuel combustion but the chemical mechanisms involved are unclear. Here we report field observations in a Beijing winter haze event that reveal fast aqueous-phase conversion of fossil-fuel primary organic aerosol (POA) to SOA at high relative humidity. Analyses of aerosol mass spectra and elemental ratios indicate that ring-breaking oxidation of POA aromatic species, leading to functionalization as carbonyls and carboxylic acids, may serve as the dominant mechanism for this SOA formation. A POA origin for SOA could explain why SOA has been decreasing over the 2013-2018 period in response to POA emission controls even as emissions of volatile organic compounds (VOCs) have remained flat.

Chronic Exposure to Secondary Organic Aerosols Causes Lung Tissue Damage.

Recently, secondary organic aerosols (SOAs) emerged as a predominant component of fine particulate matter. However, the pathogenic mechanism(s) of SOAs are still poorly understood. Herein, we show that chronic exposure of mice to SOAs resulted in lung inflammation and tissue destruction. Histological analyses found lung airspace enlargement associated with massive inflammatory cell recruitment predominated by macrophages. Concomitant with such cell influx, our results found changes in the levels of a series of inflammatory mediators in response to SOA. Interestingly, we observed that the expression of the genes encoding for TNF-α and IL-6 increased significantly after one month of exposure to SOAs; mediators that have been largely documented to play a role in chronic pulmonary inflammatory pathologies. Cell culture studies confirmed these in vivo findings. Of importance as well, our study indicates increased matrix metalloproteinase proteolytic activity suggesting its contribution to lung tissue inflammation and degradation. Our work represents the first in vivo study, which reports that chronic exposure to SOAs leads to lung inflammation and tissue injury. Thus, we hope that these data will foster new studies to enhance our understanding of the underlying pathogenic mechanisms of SOAs and perhaps help in the design of therapeutic strategies against SOA-mediated lung injury.

Combined Smog Chamber/Oxidation Flow Reactor Study on Aging of Secondary Organic Aerosol from Photooxidation of Aromatic Hydrocarbons.

Secondary organic aerosol (SOA) is a significant component of atmospheric fine particulate matter (PM2.5), and their physicochemical properties can be significantly changed in the aging process. In this study, we used a combination consisting of a smog chamber (SC) and oxidation flow reactor (OFR) to investigate the continuous aging process of gas-phase organic intermediates and SOA formed from the photooxidation of toluene, a typical aromatic hydrocarbon. Our results showed that as the OH exposure increased from 2.6 × 1011 to 6.3 × 1011 molecules cm-3 s (equivalent aging time of 2.01-4.85 days), the SOA mass concentration (2.9 ± 0.05-28.7 ± 0.6 µg cm-3) and corrected SOA yield (0.073-0.26) were significantly enhanced. As the aging process proceeds, organic acids and multiple oxygen-containing oxidation products are continuously produced from the photochemical aging process of gas-phase organic intermediates (mainly semi-volatile and intermediate volatility species, S/IVOCs). The multigeneration oxidation products then partition to the aerosol phase, while functionalization of SOA rather than fragmentation dominated in the photochemical aging process, resulting in much higher SOA yield after aging compared to that in the SC. Our study indicates that SOA yields as a function of OH exposure should be considered in air quality models to improve SOA simulation, and thus accurately assess the impact on SOA properties and regional air quality.

Molecular-Scale Investigation on the Formation of Brown Carbon Aerosol via Iron-Phenolic Compound Reactions in the Dark.

Brown carbon (BrC) is one of the most mysterious aerosol components responsible for global warming and air pollution. Iron (Fe)-induced catalytic oxidation of ubiquitous phenolic compounds has been considered as a potential pathway for BrC formation in the dark. However, the reaction mechanism and product composition are still poorly understood. Herein, 13 phenolic precursors were employed to react with Fe under environmentally relevant conditions. Using Fourier transform ion cyclotron resonance mass spectrometry, a total of 764 unique molecular formulas were identified, and over 85% of them can be found in atmospheric aerosols. In particular, products derived from precursors with catechol-, guaiacol-, and syringol-like-based structures can be distinguished by their optical and molecular characteristics, indicating the structure-dependent formation of BrC from phenolic precursors. Multiple pieces of evidence indicate that under acidic conditions, the contribution of either autoxidation or oxygen-induced free radical oxidation to BrC formation is extremely limited. Ligand-to-Fe charge transfer and subsequent phenoxy radical coupling reactions were the main mechanism for the formation of polymerization products with high molecular diversity, and the efficiency of BrC generation was linearly correlated with the ionization potential of phenolic precursors. The present study uncovered how chemically diverse BrC products were formed by the Fe-phenolic compound reactions at the molecular level and also provide a new paradigm for the study of the atmospheric aerosol formation mechanism.

Marine Submicron Aerosols from the Gulf of Mexico: Polluted and Acidic with Rapid Production of Sulfate and Organosulfates.

We measured submicron aerosols (PM1) at a beachfront site in Texas in Spring 2021 to characterize the "background" aerosol chemical composition advecting into Texas and the factors controlling this composition. Observations show that marine "background" aerosols from the Gulf of Mexico were highly processed and acidic; sulfate was the most abundant component (on average 57% of total PM1 mass), followed by organic material (26%). These chemical characteristics are similar to those observed at other marine locations globally. However, Gulf "background" aerosols were much more polluted; the average non-refractory (NR-) PM1 mass concentration was 3-70 times higher than that observed in other clean marine atmospheres. Anthropogenic shipping emissions over the Gulf of Mexico explain 78.3% of the total measured "background" sulfate in the Gulf air. We frequently observed haze pollution in the air mass from the Gulf, with significantly elevated concentrations of sulfate, organosulfates, and secondary organic aerosol associated with sulfuric acid. Analysis suggests that aqueous oxidation of shipping emissions over the Gulf of Mexico by peroxides in the particles might potentially be an important pathway for the rapid production of acidic sulfate and organosulfates during the haze episodes under acidic conditions.

Synergistic Effects of SO2 and NH3 Coexistence on SOA Formation from Gasoline Evaporative Emissions.

Vehicular evaporative emissions make an increasing contribution to anthropogenic sources of volatile organic compounds (VOCs), thus contributing to secondary organic aerosol (SOA) formation. However, few studies have been conducted on SOA formation from vehicle evaporative VOCs under complex pollution conditions with the coexistence of NOx, SO2, and NH3. In this study, the synergistic effects of SO2 and NH3 on SOA formation from gasoline evaporative VOCs with NOx were examined using a 30 m3 smog chamber with the aid of a series of mass spectrometers. Compared with the systems involving SO2 or NH3 alone, SO2 and NH3 coexistence had a greater promotion effect on SOA formation, which was larger than the cumulative effect of the two promotions alone. Meanwhile, contrasting effects of SO2 on the oxidation state (OSc) of SOA in the presence or absence of NH3 were observed, and SO2 could further increase the OSc with the coexistence of NH3. The latter was attributed to the synergistic effects of SO2 and NH3 coexistence on SOA formation, wherein N-S-O adducts can be formed from the reaction of SO2 with N-heterocycles generated in the presence of NH3. Our study contributes to the understanding of SOA formation from vehicle evaporative VOCs under highly complex pollution conditions and its atmospheric implications.

Chemical Signatures of Seasonally Unique Anthropogenic Influences on Organic Aerosol Composition in the Central Amazon.

Urbanization and fires perturb the quantities and composition of fine organic aerosol in the central Amazon, with ramifications for radiative forcing and public health. These disturbances include not only direct emissions of particulates and secondary organic aerosol (SOA) precursors but also changes in the pathways through which biogenic precursors form SOA. The composition of ambient organic aerosol is complex and incompletely characterized, encompassing millions of potential structures relatively few of which have been synthesized and characterized. Through analysis of submicron aerosol samples from the Green Ocean Amazon (GoAmazon2014/5) field campaign by two-dimensional gas chromatography coupled with machine learning, ∼1300 unique compounds were traced and characterized over two seasons. Fires and urban emissions produced chemically and interseasonally distinct impacts on product signatures, with only ∼50% of compounds observed in both seasons. Seasonally unique populations point to the importance of aqueous processing in Amazonian aerosol aging, but further mechanistic insights are impeded by limited product identity knowledge. Less than 10% of compounds were identifiable at an isomer-specific level. Overall, the findings (i) provide compositional characterization of anthropogenic influence on submicron organic aerosol in the Amazon, (ii) identify key season-to-season differences in chemical signatures, and (iii) highlight high-priority knowledge gaps in current speciated knowledge.

Nonequilibrium Behavior in Isoprene Secondary Organic Aerosol.

Recent studies have shown that instantaneous gas-particle equilibrium partitioning assumptions fail to predict SOA formation, even at high relative humidity (∼85%), and photochemical aging seems to be one driving factor. In this study, we probe the minimum aging time scale required to observe nonequilibrium partitioning of semivolatile organic compounds (SVOCs) between the gas and aerosol phase at ∼50% RH. Seed isoprene SOA is generated by photo-oxidation in the presence of effloresced ammonium sulfate seeds at <1 ppbv NOx, aged photochemically or in the dark for 0.3-6 h, and subsequently exposed to fresh isoprene SVOCs. Our results show that the equilibrium partitioning assumption is accurate for fresh isoprene SOA but breaks down after isoprene SOA has been aged for as short as 20 min even in the dark. Modeling results show that a semisolid SOA phase state is necessary to reproduce the observed particle size distribution evolution. The observed nonequilibrium partitioning behavior and inferred semisolid phase state are corroborated by offline mass spectrometric analysis on the bulk aerosol particles showing the formation of organosulfates and oligomers. The unexpected short time scale for the phase transition within isoprene SOA has important implications for the growth of atmospheric ultrafine particles to climate-relevant sizes.