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The Earth's atmosphere is composed of an enormous variety of chemical species associated with trace gases and aerosol particles whose composition and chemistry have critical impacts on the Earth's climate, air quality, and human health. Mass spectrometry analysis as a powerful and popular analytical technique has been widely developed and applied in atmospheric chemistry for decades. Mass spectrometry allows for effective detection, identification, and quantification of a broad range of organic and inorganic chemical species with high sensitivity and resolution. In this review, we summarize recently developed mass spectrometry techniques, methods, and applications in atmospheric chemistry research in the past several years on molecular‐level. Specifically, new developments of ion‐molecule reactors, various soft ionization methods, and unique coupling with separation techniques are highlighted. The new mass spectrometry applications in laboratory studies and field measurements focused on improving the detection limits for traditional and emerging volatile organic compounds, characterizing multiphase highly oxygenated molecules, and monitoring particle bulk and surface compositions. [ABSTRACT FROM AUTHOR]

To quantify the volatility of organic aerosols (OA), a comprehensive campaign was conducted in the Chinese megacity. Volatility distributions of OA and particle‐phase organic nitrate (pON) were estimated based on five methods: (a) empirical method and (b) kinetic model based on the measurement of a thermodenuder (TD) coupled with an aerosol mass spectrometer; (c) Formula‐based SIMPOL model‐driven method; (d) Element‐based estimations using molecular formula measurements of OA; and (e) gas/particle partitioning. Our results demonstrate that the ambient OA volatility distribution shows good agreement between the two heating methods and the formula‐based method when assuming ambient OA was mainly composed of organic nitrate (pON), organic sulfate and acid groups using the SIMPOL model. However, the element‐based method tends to overestimate the volatility of OA compared to the above three methods, suggesting large uncertainties in the parameterizations or in the representativeness of the molecular measurements that need further refinement. The volatility of ambient OA is generally lower than that of the laboratory‐derived secondary OA, emphasizing the impact of aging. A large fraction at the higher and lower volatility ranges (approximately log C* ≤ −9 and ≥2 μg m−3) was found for pON, implying the importance of both extremely low volatile and semi‐volatile species. Overall, this study evaluates different methods for volatility estimation and gives new insight into the volatility of OA and pON in urban areas. Plain Language Summary: Volatility, which controls the gas/particle partitioning of organic compounds, is one of most the important physiochemistry properties of organic aerosols (OA). Multiple methods have been used to estimate OA volatility, whereas the accuracy of each method is still unclear. The purpose of this study is to verify the volatility of ambient OA and its key component (i.e., particulate organic nitrate, pON) in urban areas by comparing the estimated results using different methods. With the help of state‐of‐art mass spectrometers, the estimation methods, including two heating methods, one formula‐based method, one element‐based method, and one gas/particle partitioning method, were achieved. In general, we found the heating methods show good agreement with the formula‐based method with a reasonable assumption of functional groups contained in OA and pON. In general, we observed a large faction of extremely low volatile compounds exist in OA (30%–40%), and both extremely low volatile and semi‐volatile species exist in pON, suggesting the complex evolution of atmospheric particles. The results provide a better understanding of the volatility of OA and pON in urban areas and benefit accurate volatility estimation that facilitates the model simulations of OA. Key Points: The volatility of ambient organic aerosols (OA) and organic nitrate (pON) estimated from five methods were systematically comparedThe OA volatility from SIMPOL‐driven model under organic sulfate, pON and acid assumption are consistent with those from heating methodThe volatility distribution of pON indicates both extremely low volatility compounds as oligomers and semi‐volatile species exist in pON [ABSTRACT FROM AUTHOR]

• The chemical composition of PM 2.5 in a country in the East Mediterranean - Middle East region is investigated in the hot season, including organic markers. • Long-range transport was an important contributor to V, Ni, and sulfate in the region with a characteristic ratio based on the air mass origin. • Main local sources determined through the chemical speciation including organics are road transport, resuspension of dust and diesel private generators. • A health risk assessment of airborne metals was performed and the carcinogenic risk for all the metals exceeded by 14 and 42 times the acceptable risk level in the US (10−6). The chemical composition of PM 2.5 at two sites in Lebanon, a country in the East Mediterranean - Middle East region, is investigated in the spring and summer seasons. The average PM 2.5 concentrations were of (29 ± 16) µg/m3 for Beirut urban site and (32 ± 14) µg/m3 for Beirut suburban site. This study showed that the geographic location of the East Mediterranean region, such as its proximity to the Mediterranean Sea and the dust storm intrusion are a significant contributor to the high PM levels from natural sources, which cannot be mitigated, rendering the PM 2.5 WHO annual Air Quality guideline unattainable due to high natural background, which also applies to the entire Middle East region. Turkey and Eastern Europe are the dominant origin of air masses throughout our sampling days, suggesting the long-range transport as an important potential contributor to the high observed concentrations of V, Ni, and sulfate in this region most probably in other East Mediterranean countries than Lebanon too. Main local sources determined through the chemical speciation including organics are road transport, resuspension of dust and diesel private generators. A health risk assessment of airborne metals was performed and the carcinogenic risk for all the metals exceeded by 42 (adults) and 14 (children) times the acceptable risk level (10−6) at both sites. Vanadium was the predominant carcinogenic metal, emphasizing the need to replace energy production with cleaner energy on a regional level and highlighting the severe impact of air pollution on the health of inhabitants in this region's main cities. [ABSTRACT FROM AUTHOR]

The widespread presence of organic aerosols (OA) in the atmosphere and their dominant role in climate forcing are increasingly recognized. Measurements from the high‐altitude region provide insights into the natural processes and long‐range transport of aerosols. We studied water‐soluble organic compounds in PM1.1 during January‐March 2020 and February‐April 2021 at Ponmudi (8.8°N and 77.1°E), a tropical hill station (960 m a.s.l.) located on the Western Ghats of India. The 5‐day backward trajectories of air masses presented that continental and marine sources impacted the site during the campaign, and thus we classified samples as mixed and marine air masses. Their molecular fingerprints revealed the prevalence of oxalic acid (C2), followed by terephthalic acid in mixed air mass and malonic (C3) or succinic (C4) acid in maritime air mass aerosol samples. This feature and the phthalic to azelaic acid ratio, as well as the C3 to C4 and fumaric to maleic acid ratios, evidenced that water‐soluble OA were of anthropogenic origin and less photochemically aged in mixed air mass samples, whereas they derived from biogenic sources and more photochemical aging in marine air mass samples. However, we found their comparable contributions in water‐soluble organic carbon under mixed and marine air masses. Linear correlations between C2 relative abundance and its ratios with the precursor compounds implied that the oxidation of precursors to oxalic acid occurs during atmospheric transport. The results revealed that the input of anthropogenic and biogenic precursors followed by atmospheric processing controlled the burden of water‐soluble OA across the Western Ghats. Plain Language Summary: Dicarboxylic acids (DCAs), oxocarboxylic acids and dicarbonyls are ubiquitous water‐soluble components of organic aerosol (OA) that can serve as cloud condensation nuclei and affect the climate of the Earth. We reveal for the first time the molecular fingerprints and sources as well as formation processes of water‐soluble OA in PM1.1 at a tropical hill station in Western Ghats of India. Significant differences in the molecular fingerprints and atmospheric processes of water‐soluble OA were found due to the influence of different air masses. DCAs and related compounds in mixed air mass aerosols originated from anthropogenic sources and produced in the atmosphere by photooxidation during long‐range transport whereas they were of biogenic origin followed by intense photochemical aging of biogenic volatile organic compounds such as isoprene and unsaturated fatty acids during atmospheric transport in marine air mass aerosols. The results revealed that DCAs substantially contribute to water‐soluble OA not only in mixed air mass aerosols but also in marine air mass aerosols at the tropical hill station in the Western Ghats. These findings have implications for assessing climate‐forcing feedback of secondary OA over the Western Ghats that is driven by anthropogenic and biogenic sources followed by photochemical processes. Key Points: Mixed and marine air masses drive the molecular fingerprints of atmospheric water‐soluble organic compounds over the Western GhatsAerosols of mixed air masses comprised dicarboxylic acids (DCAs) of anthropogenic origin and less photochemically processedDCAs were produced from biogenic sources followed by intense photochemical aging in marine air mass aerosols [ABSTRACT FROM AUTHOR]

Abstract The widespread presence of organic aerosols (OA) in the atmosphere and their dominant role in climate forcing are increasingly recognized. Measurements from the high‐altitude region provide insights into the natural processes and long‐range transport of aerosols. We studied water‐soluble organic compounds in PM1.1 during January‐March 2020 and February‐April 2021 at Ponmudi (8.8°N and 77.1°E), a tropical hill station (960 m a.s.l.) located on the Western Ghats of India. The 5‐day backward trajectories of air masses presented that continental and marine sources impacted the site during the campaign, and thus we classified samples as mixed and marine air masses. Their molecular fingerprints revealed the prevalence of oxalic acid (C2), followed by terephthalic acid in mixed air mass and malonic (C3) or succinic (C4) acid in maritime air mass aerosol samples. This feature and the phthalic to azelaic acid ratio, as well as the C3 to C4 and fumaric to maleic acid ratios, evidenced that water‐soluble OA were of anthropogenic origin and less photochemically aged in mixed air mass samples, whereas they derived from biogenic sources and more photochemical aging in marine air mass samples. However, we found their comparable contributions in water‐soluble organic carbon under mixed and marine air masses. Linear correlations between C2 relative abundance and its ratios with the precursor compounds implied that the oxidation of precursors to oxalic acid occurs during atmospheric transport. The results revealed that the input of anthropogenic and biogenic precursors followed by atmospheric processing controlled the burden of water‐soluble OA across the Western Ghats.

Complex organic aerosols in the upper atmosphere of Saturn's moon Titan reach the troposphere and surface, where a methane (CH4)‐based hydrological cycle occur. Previous studies have assumed no interactions between organic aerosols and liquid CH4, although the dissolution of low‐molecular‐weight photochemical products in liquid CH4 has been considered. Here we report experimental results of soaking a laboratory analog (so‐called tholin) of Titan's organic aerosols in liquid CH4 at 93–98 K for several hours and then evaporating the liquid, simulating wet–dry cycling on Titan. After wet–dry cycling, residual tholin particles form aggregates through cementation. Solid evaporitic deposits formed by evaporation of interacted liquid contain nitrogen‐bearing aromatics, suggesting selective dissolution of aromatics. Our results suggest that organic aerosols or high‐molecular‐weight compounds adsorbed on them partly dissolve in liquid CH4 on Titan, even during short‐term wetting events, promoting the growth of aerosols to dune particles via aggregation and providing aromatics to evaporites. Plain Language Summary: Saturn's largest moon, Titan has a dense atmosphere composed of nitrogen and methane. Active organic chemistry induced by sunlight occurs in the atmosphere to form complex organic aerosols. These organic aerosols eventually settle on the surface, where rivers, lakes, and seas of liquid methane are present. Upon seasonal changes in precipitation and evaporation, wet–dry cycling of liquid methane is believed to occur on Titan, similar to Earth's water cycles. Can organic aerosols settled on the surface be dissolved into liquid methane? If so, what components of aerosol can be dissolved, and how could this affect Titan's geology? Here we perform laboratory experiments to address these questions. Unlike predictions by previous studies, we find that organic aerosols or aromatics adsorbed on them would partly dissolve into liquid methane efficiently. These processes could play key roles in the formation of unique landforms, such as dunes and evaporites, on Titan. Key Points: We experimentally simulate interactions between laboratory analogs (tholin) of Titan's aerosols and liquid methane at low temperaturesComplex aromatics are dissolved from tholin, forming evaporites after drying; while, residual tholin form aggregatesWet–dry cycling of aerosols on Titan may provide aromatics to evaporites and could explain size growth of aerosols to dune particles [ABSTRACT FROM AUTHOR]

By quantifying the absorption of black carbon (BC), brown carbon (BrC) and the lensing effect, we found that BrC dominates the total absorption at 450 nm, and the largest absorption contribution proportion of BrC could reach 78.3% during heavy pollution. The average absorption enhancement (Eabs) at 530 nm was only 1.38, indicating that BC is not coated well here. The average value of the absorption Ångstrom exponent (AAE) between 450 nm and 530 nm was 5.3, suggesting a high concentration of BrC in Wangdu. CHN+ was the greatest contributor to the light absorption of molecules detected in MSOC with a proportion of 12.2–22.4%, in which the polycyclic aromatic nitrogen heterocycles (PANHs) were the dominant compounds. The C6H5NO3 and its homologous series accounted for 3.0–11.3%, and the C15H9N and its homologous series, including one C16H11N and three C17H13N compounds, accounted for 5.1–12.3%. The absorption of these PANHs is comparable to that of nitro–aromatics, which should attract more attention to the impact of climate radiative forcing. [ABSTRACT FROM AUTHOR]

Brown carbon is a type of strong light-absorbing carbonaceous aerosol associated with radiative forcing. Nevertheless, the difficulty in correlating the chemical composition of brown carbon with its light absorption properties impairs the proper elucidation of its role in radiative forcing. Here, we have used a time-dependent density functional theory (TD-DFT)-based procedure to revisit the “real-world” absorption spectra of polycyclic aromatic hydrocarbons (PAHs) over the city of Porto, in Portugal, while correcting the spectra for their quantity in PM10 particulate matter. Our aim is to, by comparing these new results with those obtained previously regarding PM2.5 data, evaluate the role of different groupings of particulate matter in the light absorption of brown carbon. The results indicate that irrespective of the absorption spectra corresponding to their PM10 or PM2.5 data, the studied PAHs should contribute to radiative forcing by light absorption at UVA and (sub)visible wavelengths. However, the identity of the individual PAH species that contribute the most for the considered wavelengths can be quite different. Thus, different groupings of particulate matter appear to provide distinct contributions to light absorption and radiative forcing over the same location, even when considering the same class of molecular compounds.

Observed surface organic aerosols (OA) concentrations slightly increased in the western US (WUS) but significantly decreased in the eastern US (EUS) in summer, and continuously decreased in winter over the US region. To understand the driving factors for the long‐term surface OA trend, we apply a revised version of the Community Atmosphere Model version 6 with comprehensive tropospheric and stratospheric chemistry representation, considering the heterogeneous formation of isoprene‐epoxydiol‐derived secondary organic aerosols (SOAIE) and fast photolysis rate of monoterpene‐derived secondary organic aerosols (MTSOA) to diagnose the OA evolution in 1988–2019. Compared to older versions, the revised model better reproduces the climatology, seasonal cycle, and long‐term trend of surface OA as evaluated against the Interagency Monitoring of Protected Visual Environments measurements. We find the decrease in EUS summertime OA is likely attributed to the interplay between SOAIE and MTSOA. With anthropogenic emissions reduction, primary organic aerosols (POA) declined, SOAIE decreased along with sulfate, while MTSOA increased along with biogenic emissions driven by a warming climate. POA from wildfires with a significant trend of 2.9% yr−1 and considerable interannual variation of 62.8% drive the statistically insignificant but increasing WUS summertime OA, while anthropogenic POA dominates the decreasing wintertime OA in the US. Through sensitivity experiments, we find MTSOA show linear responses to the increasing monoterpenes emissions and negligible responses to NOx emissions reduction due to the mutual offsets between MTSOA components from different oxidation pathways. This study reveals the increasingly important role of MTSOA in summertime OA under a warming climate. Plain Language Summary: As the major components of fine particles, organic aerosols (OA) increased in the western United States and decreased in the eastern United States in the summer, and kept decreasing in the winter in the past decades. The driving factors for the long‐term trend of OA and their components remain unclear and are investigated by conducting a series of long‐term simulations. We find the isoprene‐epoxydiol‐derived secondary organic aerosols decrease with sulfate emission controls, which is partly offset by the increasing monoterpene‐derived secondary organic aerosols (MTSOA) under global warming and the statistically insignificant increase of primary organic aerosols driven by wildfires in summer. In winter, anthropogenic emissions dominate the declining surface OA. We also find MTSOA are more sensitive to increasing biogenic emissions than anthropogenic emissions reduction. Our results reveal the important role of MTSOA in total summertime OA under a warming climate. Key Points: Monoterpene‐derived and isoprene‐epoxydiol‐derived secondary organic aerosols (SOA) contribute to the descending surface summertime organic aerosols (OA) in the eastern USPrimary organic aerosols (POA) from wildfires drive the statistically insignificant but increasing trend of surface summertime OA in the western USMonoterpene‐derived SOA linearly respond to increasing monoterpenes emissions but negligibly respond to NOx emissions reduction [ABSTRACT FROM AUTHOR]

We present a new volatility basis set (VBS) representation of aromatic secondary organic aerosol (SOA) for atmospheric chemistry models by fitting a statistical oxidation model with aerosol microphysics (SOM‐TOMAS) to results from laboratory chamber experiments. The resulting SOM‐VBS scheme also including previous work on SOA formation from semi‐ and intermediate volatile organic compounds (S/IVOCs) is implemented in the GEOS‐Chem chemical transport model and applied to simulation of observations from the Korea‐United States Air Quality Study (KORUS‐AQ) field campaign over South Korea in May–June 2016. Our SOM‐VBS scheme can simulate the KORUS‐AQ organic aerosol (OA) observations from aircraft and surface sites better than the default schemes used in GEOS‐Chem including for vertical profiles, diurnal cycle, and partitioning between hydrocarbon‐like OA and oxidized OA. Our results confirm the important contributions of oxidized primary OA and aromatic SOA found in previous analyses of the KORUS‐AQ data and further show a large contribution from S/IVOCs. Model source attribution of OA in surface air over South Korea indicates one third from domestic anthropogenic emissions, with a large contribution from toluene and xylenes, one third from external anthropogenic emissions, and one third from natural emissions. Plain Language Summary: We have created a new way of understanding how air pollution is formed. We did this by looking at how certain chemicals change when they are exposed to oxygen in the air. We used a computer model of lab experiments to see how these chemicals would react in the atmosphere. The new method is called SOM‐VBS. We used this method to study a type of air pollution called secondary organic aerosol that comes from the reaction of oxygen in the air with emissions from both natural and human activities. We found that the new method was able to explain the observations from a field campaign in South Korea better than previous methods. This new understanding can help us figure out where the pollution is coming from. We also found that one third of the pollution comes from human activities in South Korea, one third comes from human activities outside of South Korea, and one third comes from natural sources like plants and wildfires. Key Points: We present an updated representation of aromatic organic aerosol (OA) formation incorporating advances in interpreting chamber experimentsOur model's improved scheme is better able to simulate OA observed during the Korea‐United States Air Quality Study field campaignSurface OA in South Korea has on average one third each domestic anthropogenic, external anthropogenic, and natural origins [ABSTRACT FROM AUTHOR]

Abstract Complex organic aerosols in the upper atmosphere of Saturn's moon Titan reach the troposphere and surface, where a methane (CH4)‐based hydrological cycle occur. Previous studies have assumed no interactions between organic aerosols and liquid CH4, although the dissolution of low‐molecular‐weight photochemical products in liquid CH4 has been considered. Here we report experimental results of soaking a laboratory analog (so‐called tholin) of Titan's organic aerosols in liquid CH4 at 93–98 K for several hours and then evaporating the liquid, simulating wet–dry cycling on Titan. After wet–dry cycling, residual tholin particles form aggregates through cementation. Solid evaporitic deposits formed by evaporation of interacted liquid contain nitrogen‐bearing aromatics, suggesting selective dissolution of aromatics. Our results suggest that organic aerosols or high‐molecular‐weight compounds adsorbed on them partly dissolve in liquid CH4 on Titan, even during short‐term wetting events, promoting the growth of aerosols to dune particles via aggregation and providing aromatics to evaporites.

A hygroscopic tandem differential mobility analyser (H-TDMA) was used to observe the size-resolved hygroscopic characteristics of submicron particles in January and April 2018 in urban Beijing. The probability distribution of the hygroscopic growth factor (HGF-PDF) in winter and spring usually showed a bimodal pattern, with more hygroscopic mode (MH) being more dominant. The seasonal variation in particle hygroscopicity was related to the origin of air mass, which received polluted southerly air masses in spring and clean northwesterly air masses in winter. Particles showed stronger hygroscopic behaviour during heavy pollution episodes (HPEs) with elevated concentrations of secondary aerosols, especially higher mass fraction of nitrate, which were indicated using the PM 2.5 (particulate matter with diameter below 2.5 µm) mass concentration normalised by CO mass concentration. The hygroscopic parameter (κ) values were calculated using H-TDMA (κ htdma) and chemical composition (κ chem). The closure study showed that κ chem was overestimated in winter afternoon when compared with κ htdma , because the organic particle hygroscopic parameter (κ org) was overestimated in the calculations. It was influenced by the presence of a high concentration of hydrocarbon-like organic aerosol (HOA) with a weak water uptake ability. A positive relationship was observed between κ org and the ratio of oxygenated organic aerosol (OOA) and HOA, thereby indicating that the strong oxidation state enhanced the hygroscopicity of the particles. This study revealed the effect of local emission sources and secondary aerosol formation processes on particle hygroscopicity, which is of great significance for understanding the pollution formation mechanism in the North China Plain. [Display omitted] [ABSTRACT FROM AUTHOR]

Organosulfates in atmospheric PM2.5 were investigated at two urban sites in Hefei and Shijiazhuang of southern and northern China during the summer and winter seasons of 2019–2020. Organic molecular composition was characterized using ultrahigh‐performance liquid chromatography coupled with Orbitrap mass spectrometry in negative electrospray ionization mode. There were overall 2,516–6,190 and 2,417–3,474 organic molecular formulas assigned on individual days in Hefei and Shijiazhuang, respectively, among which approximately 25%–41% were sulfur‐containing CHOS and CHONS compounds. The number of total organosulfates (including nitrooxy‐organosulfates) accounted for on average 84% and 79% of sulfur‐containing compounds during summer and winter in Shijiazhuang, which were much higher than those of 36% and 57% in Hefei. The higher fractions of organosulfates in the northern city of Shijiazhuang might be closely associated with the higher prevalence of SO2 and particulate sulfate. More than 96% in the peak areas of total organosulfates were present in aliphatic molecular structures instead of aromatics in both cities, suggesting the substantial contributions from biogenic precursors and anthropogenic long‐chain alkanes. The positive correlations (r: 0.33–0.96) of inorganic sulfate with the peak area abundance of organosulfates derived from isoprene and monoterpenes revealed the significant role of sulfate particles in the production of organosulfates. Particle acidity also correlated positively with these species during the winter in Hefei and summer in Shijiazhuang, yet negatively during other periods, indicating that additional reaction pathways would compete with acid‐catalyzed chemistry under atmospheric conditions limited by particle acidity or hydrocarbon precursors. Plain Language Summary: Organosulfates are a class of organic compounds containing one or more sulfate ester functional groups (R‐O‐SO3−) in the molecular structures. They are ubiquitously present in ambient atmosphere and are important constituents of atmospheric organic aerosols. However, the properties and formation pathways of organosulfates remain poorly understood and warrant a comprehensive investigation worldwide. In this study, the molecular characteristics of atmospheric organosulfates were investigated in two urban areas (Hefei and Shijiazhuang) of southern and northern China. We have found that the organosulfates constituted a majority of sulfur‐containing organic molecules in the northern city of Shijiazhuang, due to the higher prevalence of SO2 and particulate sulfate, compared with those in the southern city of Hefei. Organosulfates were mostly present in aliphatic structures, suggesting the substantial contribution from biogenic precursors and anthropogenic long‐chain alkanes. The organic precursors, particle acidity, and ambient relative humidity have been found to be important factors affecting the formation of organosulfates. This study provides a parallel comparison of the characteristics of organosulfates between two contrasting environments, which advances our knowledge regarding the properties and sources of organosulfates and will be helpful for an accurate assessment of aerosol impacts on climate and environment. Key Points: Organosulfates constituted a majority of sulfur‐containing organic molecules in northern city Shijiazhuang due to the higher sulfur dioxide and sulfateOrganosulfates were mostly present in aliphatic molecular structures produced by biogenic precursors and anthropogenic long‐chain alkanesParticle acidity can promote organosulfates formation under ambient conditions when organic precursors and acidic particles were abundant [ABSTRACT FROM AUTHOR]

Brown carbon is a type of strong light-absorbing carbonaceous aerosol associated with radiative forcing. Nevertheless, the difficulty in correlating the chemical composition of brown carbon with its light absorption properties impairs the proper elucidation of its role in radiative forcing. Here, we have used a time-dependent density functional theory (TD-DFT)-based procedure to revisit the "real-world" absorption spectra of polycyclic aromatic hydrocarbons (PAHs) over the city of Porto, in Portugal, while correcting the spectra for their quantity in PM10 particulate matter. Our aim is to, by comparing these new results with those obtained previously regarding PM2.5 data, evaluate the role of different groupings of particulate matter in the light absorption of brown carbon. The results indicate that irrespective of the absorption spectra corresponding to their PM10 or PM2.5 data, the studied PAHs should contribute to radiative forcing by light absorption at UVA and (sub)visible wavelengths. However, the identity of the individual PAH species that contribute the most for the considered wavelengths can be quite different. Thus, different groupings of particulate matter appear to provide distinct contributions to light absorption and radiative forcing over the same location, even when considering the same class of molecular compounds. [ABSTRACT FROM AUTHOR]

Organic aerosols (OAs) are key components of atmospheric PM 2.5, which impose an important influence on citizens' health and atmospheric chemistry. However, the vertical distribution and evolutionary mechanisms of OAs have remained unclear, posing challenges for accurate model simulations. To compare the difference in molecular distribution and sources at different altitudes and explore the impact of vertical transport of mountain-valley breezes on OAs in mountainous regions, PM 2.5 samples were simultaneously collected at both the summit (SM: 1840 m a.s.l) and the foot Mt. Huang (FM: 480 m a.s.l.) in winter. All the 128 detected organic species presented higher concentrations at FM (237 ± 118 ng m−3) than at SM (89.3 ± 40.9 ng m−3), indicating that the influence of anthropogenic emissions on OAs became more significant as elevation decreased. Levoglucosan was the dominant single organic species and displayed robust correlations with most organic components at both sites, suggesting the notable effect of biomass burning on OAs in the alpine atmosphere. Molecular composition, characteristic ratios, and positive matrix factorization analysis suggested that OAs at SM were more aged and mostly derived from secondary oxidation and biomass burning from long-range transport. However, anthropogenic sources (e.g., biomass burning and fossil fuel combustion) contributed more to OAs at FM. Potential source contribution function results revealed that the northeastern part of Jiangxi Province and the nearby regions of the observation point are the potential source regions for OAs at FM, while long-range transport from northwestern Anhui Province and northern Jiangxi Province played a key role in OAs at SM. This study proved that OAs at FM could influence the mountaintop aerosols through the vertical transport of valley breeze in the day at Mt. Huang. These findings enhance our understanding of the vertical distribution of OAs and provide a scientific foundation for cross-regional atmospheric pollution control. [Display omitted] • The concentrations of all the 128 organic species decreased as elevation increased. • The effect of anthropogenic pollutants became more significant as elevation decreased. • The mountaintop organic aerosols (OAs) were more aged than those at the foot. • The mountaintop OAs in the day were strongly impacted by the valley wind in winter. [ABSTRACT FROM AUTHOR]

The presence of organic compounds on the particulate matter (PM) or aerosols can arise from the condensation of gaseous organic compounds on the existing aerosols, or from organic precursors to form secondary organic aerosols (SOA) through photochemistry. The objective of this study is to characterize organic constituents on aerosols relevant to their emission sources and the key compounds revealing the evolution of aerosols with the use of a novel analytical technique. A time-of-flight mass spectrometry (TOFMS) coupled with comprehensive two-dimensional gas chromatography (GC×GC) was developed using a flow type of modulator instead of a thermal type as a prelude to field applications without the need for cryogen. The methodology of GC×GC-TOFMS is discussed in this study in detail. Since the coarse PM (PM 10-2.5) may exhibit with a relatively high OC content compared to PM 2.5 , the GC×GC results have been obtained by analyzing PM 10 samples collected in parallel with OC/EC analysis of PM 2.5 samples at the Lulin Atmospheric Background Station (LABS, 23.47°N, 120.87°E, 2862 m ASL) as the high-mountain background site in East Asia. We found that the organic analytes were in a majority in the range of 12–30 carbon numbers falling in the category of semi-volatile organic compounds (SVOCs) with 43 compounds of alcohol, aldehyde, ketone, and ester varieties if excluding alkanes. Intriguingly, trace amounts of plasticizers and phosphorus flame retardants such as phthalates (PAEs) and triphenyl phosphate (TPP) were also found, likely originating from regions involved in open burning of household solid waste in Southeast Asia or e-waste recycling in southern China and along the long-range transport route. Compounds such as these are unique to the specific sources, demonstrating the wide spread of these hazardous compounds in the environment. [Display omitted] • A GC×GC-TOFMS method is developed for aerosols using flow type modulation. • The PM organic constituents at a high-mountain site in March 2015 were analyzed. • PAEs and TPP were detected presumably from transboundary sources. [ABSTRACT FROM AUTHOR]

Secondary particulate matter exerts adverse effects on air quality and human health. The production or reaction rate of secondary aerosols in polluted environments remains uncertain and is complicated by diverse emissions and meteorological conditions. By concurrently measuring the mass spectra of compounds in both particulate (using an aerosol mass spectrometer) and gas phases (using proton‐transfer‐reaction mass spectrometry) in suburban Beijing, we linked the secondary organic aerosol (OA) and volatile organic compounds (VOCs) to photochemical age (tage) and obtained their reaction or production rates. Factorization analysis of the mass spectra of OA and the 108 VOC species resolved three oxygenated OAs (OOA) and three secondary VOC factors at different oxidation levels. Primary organic aerosols and VOCs from traffic sources were determined to be important sources for secondary aerosol formation. At high pollution levels under the conditions of weaker solar radiation and higher relative humidity, moderately oxygenated OA (O/C = 0.61) and secondary inorganics were coproduced in combination with rapid consumption of all VOCs. At lower pollution levels, the intense solar radiation caused substantial and rapid production of OOA (O/C = 0.81) and intermediate VOCs (both in a high oxidation state) at a rate of 15.0% h−1 and 14.0% h−1, respectively. These results highlight the feedback effects between radiation and moisture in terms of altering the formation mechanism of secondary aerosols. In particular, highly oxygenated secondary airborne products under strong radiation should be considered in regard to their environmental impact. Plain Language Summary: In this study, the compositions of submicron aerosols and volatile organic compounds (VOCs) in suburban Beijing were concurrently characterized for their detailed mass spectra, and based on these spectra, the primary and secondary sources were apportioned to investigate their evolution and conversion. Our results demonstrate the contrasting phenomena of chemical evolution under the influence of solar radiation and moisture. Photo‐oxidation was observed to rapidly produce organic aerosol (OA) and secondary VOCs in a considerably high oxidation state, while higher relative humidity induced overall moderately oxygenated OA and secondary inorganic aerosols but resulted in more rapid consumption of all VOCs. Key Points: Mass spectra of organic compounds in both aerosols and gases were concurrently characterized in suburban BeijingThe production and consumption rates of organic aerosols (OAs) and gases were obtained under high radiation or moist conditionsHighly oxidized OAs and intermediate volatile gases are rapidly produced through photo oxidation under strong solar radiation [ABSTRACT FROM AUTHOR]

Brown carbon is a type of carbonaceous aerosol with strong light absorption in the ultraviolet and visible wavelengths that leads to radiative forcing. However, it is difficult to correlate the chemical composition of brown carbon with its atmospheric light absorption properties, which translates into significant uncertainty. Thus, a time-dependent density functional theory (TD-DFT) approach was used to model the real-world absorption properties of 14 polycyclic aromatic hydrocarbons (PAHs) over three regions of the Basque Country (Spain): Bilbao, Urretxu, and Azpeitia. The data were corrected for atmospheric concentration. The results show that the absorption spectra over each region are qualitatively identical, with the absorption intensities being significantly higher over Bilbao than over Azpeitia and Urretxu. Furthermore, it was found that the light absorption by PAHs should be more relevant for radiative forcing when it occurs at UVA and (sub)visible wavelengths. Finally, among the 14 studied PAHs, benzo[b]fluoranthene, pyrene, fluoranthene, benzo[a]pyrene, and benzo[k]fluoranthene and benzoperylene were identified as the molecules with larger contributions to radiative forcing.

Air quality simulations were performed for the Greater Athens Area in very high spatial resolution using the modeling system WRF-CAMx. Sensitivity runs were performed using the SOAP and VBS schemes for organic gas–aerosol partitioning and oxidation. In January 2019, OA-VBS decreased compared to OA-SOAP because of POA reduction. In July 2019, the OA-VBS increased with respect to OA-SOAP as a result of the increase in SOA levels exceeding the decrease in POA ones. The comparison of the WRF-CAMx results against PM10, PM2.5, and OC surface measurements provides the first indications for improved CAMx performance with the VBS scheme.

Air pollution is an important environmental risk factor associated with increased morbidity and excess mortality. Fine particulate matter (PM2.5) is a complex mixture of both organic and inorganic compounds, depending on emissions sources and atmospheric chemistry. According to toxicological studies, there is strong evidence that anthropogenic carbonaceous aerosols, especially those emitted from combustion sources, are more hazardous to human health than other types of fine particles. In this study, we use WRF-Chem to simulate PM2.5 and the carbonaceous sub-components (black carbon and organics from anthropogenic sources) over Europe. The excess mortality attributed to long-term exposure to these particles is quantified using the MR-BRT (meta-Regression–Bayesian, regularized, trimmed) and the Global Exposure Mortality Model (GEMM) exposure–response functions to assess the public health outcomes. Differential toxicity of carbonaceous aerosols is assumed to account for their potentially more pronounced effect on excess mortality.

As a part of the Integrated Campaign for Aerosols, gases and Radiation Budget (ICARB-2018), shipborne measurements of aerosol properties were carried out to study the influence of South Asian outflow on cloud condensation nuclei (CCN) characteristics over the South East Arabian Sea (SEAS) and equatorial Indian Ocean (EIO) during winter, 2018. The poor association between CCN concentration and mass concentrations of the major aerosol species (organic matter, sulfate, and elemental carbon) is observed over SEAS, where airmass is mostly continental. In comparison, the CCN is well-correlated with aerosol mass concentrations over remote EIO. The dependence of CCN activation (at lower supersaturations) on the ultrafine particle fraction differs between SEAS and EIO depending on the mass concentration of organic aerosols. The coexistence of small and hydrophobic aerosols (organics) decreased the CCN activation ratio during ultrafine particle events. The hygroscopicity estimated using the chemical composition of aerosols is comparable to that estimated from CCN measurements over the Indian Ocean, except for the SEAS, where organic aerosols dominate. The effect of outflow aerosols on cloud droplet number concentration (CDNC) is simulated using a parcel model, which showed a good association (R ∼0.96) with CCN measurements over the EIO; however, the estimated CDNC did not follow the CCN variation over the SEAS region. This study highlights the importance of aerosol chemical composition, especially organics, in CCN activation and cloud droplet formation in the South Asian outflow over the Indian Ocean. • Hygroscopicity (κ) of continental aerosols over the Indian Ocean is examined. • Ultrafine particles and organics decrease the CCN activation of South Asian outflow. • CCN at 0.2% SS estimated from measured κ has positive bias over the Arabian Sea. • Estimated CDNC over near-coastal regions is mostly invariant with CCN concentration. [ABSTRACT FROM AUTHOR]

Organic aerosols (OA) represent a significant fraction of total submicron particulate matter (PM1) concentrations globally, including densely populated megacities such as Seoul. However, scientific understanding of the atmospheric formation and removal processes of OA, especially for secondary organic aerosols (SOA), is still highly uncertain. In this study, we examine the characteristics of SOA formation in Seoul during spring‐summer 2016 and fall‐winter 2017/2018, using airborne and ground observations along with a 3‐D global chemical transport model, GEOS‐Chem. We use four different SOA schemes in the model, including simplified and complex volatility‐based frameworks, and evaluate them by comparing the simulations with the observations to examine how our scientific understanding embedded in each SOA scheme affects the observed biases. Our analysis of the model performance of each scheme also provides the most suitable approach in simulating SOA in a typical urban environment. Comparisons of the simulated versus observed OA concentrations show that model biases range from −72% to +118%, with considerable variability among different schemes and seasons. We find that the inclusion of semi/intermediate volatile precursors, in addition to the traditional precursors, and chemical aging (functionalization) are important factors to simulate surface SOA concentrations in Seoul. However, a comparison of observed and simulated SOA/∆CO enhancement ratios suggests that most schemes underpredict SOA aging in upper levels in the boundary layer. We also find that the simplified SOA scheme can reproduce observed OA but often shows overestimation in surface air, indicating that uncertainties exist in bottom‐up emissions and precursor parameterization in Seoul. Plain Language Summary: We compare four different modeling approaches for simulating secondary organic aerosol (SOA) formation, accounting for a significant fraction of total fine particulate matter concentrations in Seoul, Korea. Using GEOS‐Chem, a chemical transport model, we find that current SOA schemes show large variabilities. Including an additional precursor species and further oxidation (i.e., chemical aging) of simulated SOA improves model performance. We also find that a simplified scheme with less computational cost can reproduce observed values but generally shows an overestimation in Seoul, indicating uncertainties in parameterization. Key Points: Model evaluation of simulated organic aerosols (OA) using different secondary organic aerosols (SOA) schemes in Seoul shows large variabilityThe inclusion of semi/intermediate volatile precursors and chemical aging are important factors in reducing model biasesThe simplified SOA scheme can reproduce observed OA, but uncertainties exist in precursor parameterization in Seoul [ABSTRACT FROM AUTHOR]

Brown carbon is a type of carbonaceous aerosol with strong light absorption in the ultraviolet and visible wavelengths that leads to radiative forcing. However, it is difficult to correlate the chemical composition of brown carbon with its atmospheric light absorption properties, which translates into significant uncertainty. Thus, a time-dependent density functional theory (TD-DFT) approach was used to model the real-world absorption properties of 14 polycyclic aromatic hydrocarbons (PAHs) over three regions of the Basque Country (Spain): Bilbao, Urretxu, and Azpeitia. The data were corrected for atmospheric concentration. The results show that the absorption spectra over each region are qualitatively identical, with the absorption intensities being significantly higher over Bilbao than over Azpeitia and Urretxu. Furthermore, it was found that the light absorption by PAHs should be more relevant for radiative forcing when it occurs at UVA and (sub)visible wavelengths. Finally, among the 14 studied PAHs, benzo[b]fluoranthene, pyrene, fluoranthene, benzo[a]pyrene, and benzo[k]fluoranthene and benzoperylene were identified as the molecules with larger contributions to radiative forcing. [ABSTRACT FROM AUTHOR]

Abstract Organic aerosols (OA) represent a significant fraction of total submicron particulate matter (PM1) concentrations globally, including densely populated megacities such as Seoul. However, scientific understanding of the atmospheric formation and removal processes of OA, especially for secondary organic aerosols (SOA), is still highly uncertain. In this study, we examine the characteristics of SOA formation in Seoul during spring‐summer 2016 and fall‐winter 2017/2018, using airborne and ground observations along with a 3‐D global chemical transport model, GEOS‐Chem. We use four different SOA schemes in the model, including simplified and complex volatility‐based frameworks, and evaluate them by comparing the simulations with the observations to examine how our scientific understanding embedded in each SOA scheme affects the observed biases. Our analysis of the model performance of each scheme also provides the most suitable approach in simulating SOA in a typical urban environment. Comparisons of the simulated versus observed OA concentrations show that model biases range from −72% to +118%, with considerable variability among different schemes and seasons. We find that the inclusion of semi/intermediate volatile precursors, in addition to the traditional precursors, and chemical aging (functionalization) are important factors to simulate surface SOA concentrations in Seoul. However, a comparison of observed and simulated SOA/∆CO enhancement ratios suggests that most schemes underpredict SOA aging in upper levels in the boundary layer. We also find that the simplified SOA scheme can reproduce observed OA but often shows overestimation in surface air, indicating that uncertainties exist in bottom‐up emissions and precursor parameterization in Seoul.

Abstract The Community Earth System Model version 2 (CESM2) includes three main atmospheric configurations: the Community Atmosphere Model version 6 (CAM6) with simplified chemistry and a simplified organic aerosol (OA) scheme, CAM6 with comprehensive tropospheric and stratospheric chemistry representation (CAM6‐chem), and the Whole Atmosphere Community Climate Model version 6 (WACCM6). Both, CAM6‐chem and WACCM6 include a more comprehensive secondary organic aerosols (SOA) approach using the Volatility Basis Set (VBS) scheme and prognostic stratospheric aerosols. This paper describes the different OA schemes available in the different atmospheric configurations of CESM2 and discusses differences in aerosol burden and resulting climate forcings. Derived OA burden and trends differ due to differences in OA formation using the different approaches. Regional differences in Aerosol Optical Depth with larger values using the comprehensive approach occur over SOA source regions. Stronger increasing SOA trends between 1960 and 2015 in WACCM6 compared to CAM6 are due to increasing biogenic emissions aligned with increasing surface temperatures. Using the comprehensive SOA approach further leads to improved comparisons to aircraft observations and SOA formation of ≈143 Tg/yr. We further use WACCM6 to identify source contributions of OA from biogenic, fossil fuel, and biomass burning emissions, to quantify SOA amounts and trends from these sources. Increasing SOA trends between 1960 and 2015 are the result of increasing biogenic emissions aligned with increasing surface temperatures. Biogenic emissions are at least two thirds of the total SOA burden. In addition, SOA source contributions from fossil fuel emissions become more important, with largest values over Southeast Asia. The estimated total anthropogenic forcing of OA in WACCM6 for 1995–2010 conditions is −0.43 W/m2, mostly from the aerosol direct effect.

The current understanding of water-soluble organic aerosol (OA) composition, sources, transformations, and effects is still limited to outdoor scenarios. However, the OA is also an important component of particulate matter indoors, whose complexity impairs a full structural and molecular identification. The current limited knowledge on indoor OA, and particularly on its water-soluble organic matter (WSOM) fraction is the basis of this feature paper. Inspired by studies on outdoor OA, this paper discusses and prioritizes issues related to indoor water-soluble OA and their effects on human health, providing a basis for future research in the field. The following three main topics are addressed: (1) what is known about the origin, mass contribution, and health effects of WSOM in outdoor air particles; (2) the current state-of-the-art on the WSOM in indoor air particles, the main challenges and opportunities for its chemical characterization and cytotoxicity evaluation; and (3) why the aerosol WSOM should be considered in future indoor air quality studies. While challenging, studies on the WSOM fraction in air particles are highly necessary to fully understand its origin, fate, toxicity, and long-term risks indoors. [ABSTRACT FROM AUTHOR]

Aerosols represent an important source of terrestrial organic carbon (OC) from the East Asian continent to the China marginal seas, thus their provenance and transport play important roles in the global carbon cycle. Fifty samples of total suspended particle were collected seasonally from the nearshore Huaniao Island (HNI) in East China Sea (ECS) from April 2018 to January 2019; and they were analyzed for total organic carbon (TOC) content and stable carbon isotope (δ13C), as well as terrestrial bio-markers including n-alkanes (C20-C33), n-alkanols (C20-C32) and n-fatty acids (n-FAs, C20-C30), to distinguish the seasonal variabilities of terrestrial OC sources and reveal the influence of the long-range air mass transport on these sources. The TOC-δ13C values (range from −27.3‰ to −24.3‰) and molecular distributions of terrestrial biomarkers both suggested that terrestrial OC contributions to aerosols had significant seasonal variations. The source indices of terrestrial biomarkers (e.g., Fossil% = 82.8% for n-alkanes) revealed that the fossil fuel OC contributions, including coal burning and vehicular emission, were higher in winter, mainly because of the long-range air mass transport from the north of the East Asian continent. The terrestrial plant OC contributions were higher in summer (e.g., Wax% = 32.4% for n-alkanes), likely due to local vegetation sources from HNI and East Asian continental air masses. Cluster analysis of air mass backward-trajectories clearly showed that transport pathway plays an important role in determining the organic constituents of aerosols in China marginal seas. A comparison of these terrestrial OC contributions from different air mass origins suggested that fossil fuel OC showed less variations among various air mass origins from northern China in winter, while terrestrial plant OC sources from northern and southern China in summer contributed more than that from the air masses transported through the ECS. These results provided a basis for future quantification of terrestrial OC from different origins in marine aerosols, by combining biomarker index and carbon isotopes. [ABSTRACT FROM AUTHOR]

In the troposphere, the heterogeneous lifetime of an organic molecule in an aerosol exposed to hydroxyl radicals (OH) is thought to be weeks, which is orders of magnitude slower than the analogous gas phase reactions (hours). Here, we report an unexpectedly large acceleration in the effective heterogeneous OH reaction rate in the presence of NO. This 10-50 fold acceleration originates from free radical chain reactions, propagated by alkoxy radicals that form inside the aerosol by the reaction of NO with peroxy radicals, which do not appear to produce chain terminating products (e.g., alkyl nitrates), unlike gas phase mechanisms. A kinetic model, constrained by experiments, suggests that in polluted regions heterogeneous oxidation plays a much more prominent role in the daily chemical evolution of organic aerosol than previously believed.

The air quality in the outflow from Fort Worth, TX was studied in June 2011 at a location surrounded by oil and gas development in the Barnett Shale. The objectives of this study were to understand the major sources of volatile organic compounds (VOCs) and organic aerosols and explore the potential influence each VOC source had on ozone and secondary organic aerosol formation. Measurements of VOCs were apportioned between six factors using Positive Matrix Factorization (PMF): Natural Gas (25 ± 2%; ±99% CL); Fugitive Emissions (15 ± 2%); Internal Combustion Engines (15 ± 2%); Biogenic Emissions (7 ± 1%); Industrial Emissions/Oxidation 1(8 ± 1%); and Oxidation 2 (18 ± 2%). Reactivity calculations suggest the Biogenic and Oxidation 2 factors were the most likely VOC sources to influence local ozone. However, enough OH reactivity was calculated for factors related to the oil and gas development that they could incrementally increase O3. Three organic aerosol (OA) types were identified with PMF applied to high-resolution time-of-flight aerosol mass spectrometry measurements: hydrocarbon-like OA (HOA; 11% of mass) and two classes of oxidized OA (semi- and less-volatile OOA, SV and LV; 45% and 44%, respectively). The HOA correlated with the Internal Combustion Engine VOC factor indicating that a large fraction of the HOA was emitted by gasoline and diesel motors. The SV-OOA correlated with the oxidized VOC factors during most of the study, whereas a correlation between LV-OOA and the oxidized VOC factors was only observed during part of the study. It is hypothesized that SV-OOA and the oxidized VOC factors correlated reasonably well because these factors likely were separated by at most only a few oxidation generations on the oxidation pathway of organic compounds.

The North China Plain (NCP) is a region that experiences serious aerosol pollution. A number of studies have focused on aerosol pollution in urban areas in the NCP region; however, research on characterizing aerosols in rural NCP areas is comparatively limited. In this study, we deployed a TD-HR-AMS (thermodenuder high-resolution aerosol mass spectrometer) system at a rural site in the NCP region in summer 2013 to characterize the chemical compositions and volatility of submicron aerosols (PM1). The average PM1 mass concentration was 51.2 ± 48.0 µg m−3 and organic aerosol (OA) contributed most (35.4%) to PM1. Positive matrix factorization (PMF) analysis of OA measurements identified four OA factors, including hydrocarbon-like OA (HOA, accounting for 18.4%), biomass burning OA (BBOA, 29.4%), less-oxidized oxygenated OA (LO-OOA, 30.8%) and more-oxidized oxygenated OA (MO-OOA, 21.4%). The volatility sequence of the OA factors was HOA > BBOA > LO-OOA > MO-OOA, consistent with their oxygen-to-carbon (O:C) ratios. Additionally, the mean concentration of organonitrates (ON) was 1.48–3.39 µg m−3, contributing 8.1%–19% of OA based on cross validation of two estimation methods with the high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) measurement. Correlation analysis shows that ON were more correlated with BBOA and black carbon emitted from biomass burning but poorly correlated with LO-OOA. Also, volatility analysis for ON further confirmed that particulate ON formation might be closely associated with primary emissions in rural NCP areas. [ABSTRACT FROM AUTHOR]

Biomass burning (BB) significantly influences the chemical composition of organic aerosols (OA) in the East Asian outflow. Source apportionment of BB-derived OA is an influential factor for understanding their regional emissions, which is crucial for reducing uncertainties in their projected climate and health-effects. We analyzed here three different classes of atmospheric sugar compounds (anhydrosugars, primary sugars, and sugar alcohols) and two types of biogenic secondary organic aerosol (BSOA) tracers (isoprene- and monoterpene derived SOA products) in a year-long collected total suspended particulate matter (TSP) from an island-based receptor site in South Korea, the Gosan. We investigate seasonal variations in the source-emissions of BB-derived OA using mass concentrations of anhydrosugars and radiocarbon (14C-) isotopic composition of organic carbon (OC) and elemental carbon (EC) in ambient aerosols. Levoglucosan (Lev) is the most abundant anhydrosugar, followed by galactosan (Gal) and/or mannosan (Man). Strong correlations of Lev with Gal and Man as well as their high mass ratios such as Lev/Gal (6.7±2.2) and Lev/Man (15.0±6.7), indicate the contribution from hardwood burning emissions. The seasonal trends revealed that the biomass-burning impact is more pronounced in winter and fall, as evidenced from the high concentrations of anhydrosugars. Likewise, significant correlations were observed among three primary sugars (i.e., glucose, fructose, and sucrose), emphasizing the contribution from airborne pollen. The primary sugars showed higher concentrations in spring/summer than winter/fall. The fungal spore tracer compounds (i.e., arabitol, mannitol, and erythritol) correlated well with trehalose (i.e., a proxy for soil organic carbon), suggesting the origin from airborne fungal spores and soil microbes in the East Asian outflow. These sugar alcohols peaked in summer, followed by spring/fall and winter. Monoterpene-derived SOA tracers were most abundant compared to isoprene-SOA tracers. Both BSOA tracers were dominant in summer, followed by fall, spring, and winter. The source apportionment based on multiple linear regressions, diagnostic mass ratios, and positive matrix factorization analysis altogether revealed that biomass burning (41.9%) and biogenic SOA (21.1%) mostly dictates the OA loading in the ambient aerosols from East Asian outflow. We also found significant positive linear relationships of 14C-based nonfossil- and fossil-derived organic carbon fractions with Lev-C along with the comparable regression slopes, suggesting the importance of BB and coal combustion sources in the East Asian outflow. [ABSTRACT FROM AUTHOR]

Two approaches were applied for characterization of organic compounds in the atmospheric aerosols. These were chemical and statistical grouping analysis. We applied chemical group analysis as a new approach using the GC×GC data. Based on the principle of GC×GC, analytes in two dimensional data were divided into 6 chemical group depending on their volatility and polarity. Using this classification standards, all analytes were classified as one of 6 chemical groups, HP-VOC, LP-VOC, HP-SVOC, LP-SVOC, HP-NVOC and LP-NVOC. The relationship between the sum of the peak areas of each chemical group with other variables such as the concentrations of OC, EC, OCPOC, OC/EC and OCSOC were studied. However, no apparent relationship was observed. The principle component analysis (PCA) was carried out to find out the relationship among the analytes based on their sources. The OVOCs were dominant compounds in 3 out of 4 factors in summer. In winter, factor 1 was related to secondary organic aerosol and factor 3 was related to primary emission sources. The proposed approach looks promising in characterization of chemical groups but have limitations at current stage which are discussed.

Criegee intermediates, or carbonyl oxides, are formed during the ozonolysis of alkenes, which are typical anthropogenic air pollutants. They play an important role in a variety of chemical reactions occurring both in the near-surface layer and in the upper layers of the Earth's atmosphere. In the lower troposphere, Criegee intermediates have time to lose their internal vibrational energy due to collisions with nitrogen molecules and interact with other components of the atmosphere in their original form. The products of such reactions are, for example, sulfuric and nitric acids. In the stratosphere and mesosphere, Criegee intermediates decompose into chemically active fragments that participate in a variety of secondary reactions. In this study, we consider the processes of decomposition of the methylcarbonyloxide isomer anti-CH3CHOO in the upper atmosphere. It is shown that the main decay products are atomic oxygen, methane, CO, CO2, and OH radicals. The formation of more complex chemically active fragments is also possible. [ABSTRACT FROM AUTHOR]

Water-soluble organic aerosols (OA) are an important component of air particles and one of the key drivers that impact both climate and human health. Understanding the processes involving water-soluble OA depends on how well the chemical composition of this aerosol component is decoded. Yet, obtaining detailed information faces several challenges, including water-soluble OA collection, extraction, and chemical complexity. This review highlights the multidimensional non-targeted analytical strategies that have been developed and employed for providing new insights into the structural and molecular features of water-soluble organic components present in air particles. First, the most prominent high-resolution mass spectrometric methods for near real-time measurements of water-soluble OA and their limitations are discussed. Afterward, a special emphasis is given to the degree of compositional information provided by offline multidimensional analytical techniques, namely excitation–emission (EEM) fluorescence spectroscopy, high-resolution mass spectrometry and two-dimensional nuclear magnetic resonance (NMR) spectroscopy and their hyphenation with chromatographic systems. The major challenges ahead on the application of these multidimensional analytical strategies for OA research are also addressed so that they can be used advantageously in future studies. [ABSTRACT FROM AUTHOR]

The aerosol size distribution of organic compounds is one of the fundamental characteristics that regulates their atmospheric deposition and environmental fate. In this study, we characterized the organic components (mostly nonpolar organic compounds) in size‐resolved particles, with a focus on polycyclic aromatic hydrocarbons (PAHs), oxygenated PAHs (O‐PAHs), n‐alkanes, and polybrominated diphenyl ethers (PBDEs), in the urban Shanghai atmosphere during a 1‐year sampling period using gas chromatography (GC) coupled to tandem mass spectrometry (GC‐MS/MS) and two‐dimensional GC with a flame ionization detector (GC × GC‐FID). These compounds ranged from volatile organic compounds (VOCs) to extremely low volatility organic compounds (ELVOCs). We related their aerosol size distributions with their volatilities. On average, high positive correlations (p < 0.01) were observed between the size distribution characteristics (e.g., geometric mean diameter [GMD] and mass fraction in coarse particles) and volatility (logarithmic value of the saturation mass concentration, log C*) for the compounds that we examined. A higher ambient temperature tends to increase the slope of the regression line between size distribution and volatility (log C*). Further dry deposition modeling of size‐resolved particles showed a positive correlation (p < 0.01) between the bulk dry deposition velocity and GMD and between the bulk dry deposition velocity and volatility of the target compounds, indicating that low‐volatility organic compounds have a lower dry deposition velocity and are more likely to be transported to remote areas if they do not have a short half‐life in the atmosphere. Key Points: Geometric mean diameter (GMD) is positively correlated with volatility (log C*), and the Kelvin effect may play a role in size distributionFactors such as the ambient temperature influence the characteristics (i.e., slope) of the regression line between GMD and log C*Low‐volatility organic compounds have lower dry deposition velocities and are more likely to be transported to remote areas [ABSTRACT FROM AUTHOR]

As part of the ChArMEx project (Chemistry-Aerosol Mediterranean Experiment, http://charmex.lsce.ipsl.fr), one year of continuous filter sampling was conducted from August 2012 to August 2013 at a rural (coastal) site in Algeria aiming to better document fine aerosol seasonal variability and chemical composition in the Southern part of the Mediterranean. Over 350 filters have been collected, weighted, and analyzed for the main ions and organic and elemental carbon. The obtained mass concentrations varied between 2.5 and 50.6 μg/m3 for PM2.5. The annual modulations of PM2.5 showed higher concentrations in the end summer 2012 and the early summer 2013 (28.50 μg/m3 in August 2012, 20.23 μg/m3 in September 2012, 20.19 μg/m3 in July 2013, and 17.88 μg/m3in August 2013). The particulate organic matter (POM) presented the greatest contribution (50%), followed by the secondary inorganic aerosols (SIA, 27%). The average organic carbon OC concentrations ranged from 1.66 to 6.05 μgC/m3. The average elemental carbon EC concentrations ranged from 0.92 to 3.49 μgC/m3 and contributed 7% of the PM2.5 mass to Bou-Ismail. The average value of the OC /EC ratio was close to 5.1 in Bou-Ismail, and was close to that found in Finokalia 4 (Greece 2004, 2006) but was lower than that of Montseny 11 (Spain 2002–2007) Western Mediterranean Basin (WMB). The concentrations of water-soluble organic carbon WSOC in the PM2.5 ranging from 0.66 to 3.70 μg/m3 recorded the minimum level in March 2013, and the maximum level in August 2012, with an average of 2.02 μg/m3. [ABSTRACT FROM AUTHOR]

A method using ultra‐high performance liquid chromatography coupled to a high resolution Orbitrap mass spectrometer was developed to identify and quantify imidazoles in aqueous extracts of aerosol particles. The aqueous particle extract was used without further enrichment or sample clean‐up. Five columns were tested for efficient separation of ten imidazoles and the Acquity HSS T3 column was chosen for further optimization. Low limits of detection (<25 nM) and good intraday and interday repeatability (<1.6 and <6%, respectively) were achieved. Investigation of matrix effects showed that external calibration is applicable when the loading of organic carbon in the sample is below 10 µg m−3. The developed method was applied to ten real samples, and six out of the ten test imidazoles were successfully quantified, while six further imidazoles were qualitatively identified, among them 4‐imidazolecarboxaldehyde and 4‐methyl‐5‐imidazolecarboxaldehyde. Advantages of the method are the minimal sample preparation, the short run time for each sample, and the low detection limits. These allow for a fast and reliable quantification of imidazoles even in a large number of aqueous particle extract samples. [ABSTRACT FROM AUTHOR]

The Community Earth System Model version 2 (CESM2) includes three main atmospheric configurations: the Community Atmosphere Model version 6 (CAM6) with simplified chemistry and a simplified organic aerosol (OA) scheme, CAM6 with comprehensive tropospheric and stratospheric chemistry representation (CAM6‐chem), and the Whole Atmosphere Community Climate Model version 6 (WACCM6). Both, CAM6‐chem and WACCM6 include a more comprehensive secondary organic aerosols (SOA) approach using the Volatility Basis Set (VBS) scheme and prognostic stratospheric aerosols. This paper describes the different OA schemes available in the different atmospheric configurations of CESM2 and discusses differences in aerosol burden and resulting climate forcings. Derived OA burden and trends differ due to differences in OA formation using the different approaches. Regional differences in Aerosol Optical Depth with larger values using the comprehensive approach occur over SOA source regions. Stronger increasing SOA trends between 1960 and 2015 in WACCM6 compared to CAM6 are due to increasing biogenic emissions aligned with increasing surface temperatures. Using the comprehensive SOA approach further leads to improved comparisons to aircraft observations and SOA formation of ≈143 Tg/yr. We further use WACCM6 to identify source contributions of OA from biogenic, fossil fuel, and biomass burning emissions, to quantify SOA amounts and trends from these sources. Increasing SOA trends between 1960 and 2015 are the result of increasing biogenic emissions aligned with increasing surface temperatures. Biogenic emissions are at least two thirds of the total SOA burden. In addition, SOA source contributions from fossil fuel emissions become more important, with largest values over Southeast Asia. The estimated total anthropogenic forcing of OA in WACCM6 for 1995–2010 conditions is −0.43 W/m2, mostly from the aerosol direct effect. Key Points: CESM2 (WACCM6) includes an updated secondary aerosol scheme using the volatility basis set approachThe new SOA parameterization results in regional changes in radiative forcings and aerosol optical depthPositive SOA trends between 1960 and 2015 are caused by both increasing biogenic and anthropogenic sources [ABSTRACT FROM AUTHOR]

Observations during the 2006 dry season of highly elevated concentrations of cyanides in the atmosphere above Mexico City (MC) and the surrounding plains demonstrate that biomass burning (BB) significantly impacted air quality in the region. We find that during the period of our measurements, fires contribute more than half of the organic aerosol mass and submicron aerosol scattering, and one third of the enhancement in benzene, reactive nitrogen, and carbon monoxide in the outflow from the plateau. The combination of biomass burning and anthropogenic emissions will affect ozone chemistry in the MC outflow.

Here we report a new method for measuring the heterogeneous chemistry of submicron organic aerosol particles using a continuous flow stirred tank reactor. This approach is designed to quantify the real time heterogeneous kinetics, using a relative rate method, under conditions of low oxidant concentration and long reaction times that more closely mimic the real atmosphere. A general analytical expression, which couples the aerosol chemistry with the flow dynamics in the chamber is developed and applied to the heterogeneous oxidation of squalane particles by hydroxyl radicals (OH) in the presence of O2. The particle phase reaction is monitored via photoionization aerosol mass spectrometry and yields a reactive uptake coefficient of 0.51+-0.10, using OH concentrations of 1-7x108 molec cdot cm-3 and reaction times of 1.5+-3 hours. This uptake coefficient is larger than that found for the reaction carried out under high OH concentrations (~;;1x1010 molec cdot cm-3) and short reaction times in a flow tube reactor. This difference suggests that oxidant concentration and reaction time are not interchangeable quantities in reactions of organic aerosols with radicals. In general, this approach provides a new way to examine how the chemical aging of organic particles measured at short reaction times and high oxidant concentrations in flow tubes might differ from the long reaction times and low oxidant levels found in the real atmosphere.

The current understanding of water-soluble organic aerosol (OA) composition, sources, transformations, and effects is still limited to outdoor scenarios. However, the OA is also an important component of particulate matter indoors, whose complexity impairs a full structural and molecular identification. The current limited knowledge on indoor OA, and particularly on its water-soluble organic matter (WSOM) fraction is the basis of this feature paper. Inspired by studies on outdoor OA, this paper discusses and prioritizes issues related to indoor water-soluble OA and their effects on human health, providing a basis for future research in the field. The following three main topics are addressed: (1) what is known about the origin, mass contribution, and health effects of WSOM in outdoor air particles; (2) the current state-of-the-art on the WSOM in indoor air particles, the main challenges and opportunities for its chemical characterization and cytotoxicity evaluation; and (3) why the aerosol WSOM should be considered in future indoor air quality studies. While challenging, studies on the WSOM fraction in air particles are highly necessary to fully understand its origin, fate, toxicity, and long-term risks indoors.