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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.

The limited characterization and detection capacity of unknown compounds hinder our understanding of the molecular composition of toxic compounds in PM 2.5 . The present study applied Fourier transform ion cyclotron resonance mass spectrometry coupled with negative and positive electrospray ionization sources (ESI - /ESI + FT-ICR-MS) to probe the molecular characteristics and dynamic formation processes of the effective proinflammatory components in organic aerosols (OAs) of PM 2.5 in Guangzhou for one year. We detected abundant proinflammatory molecules in OAs, mainly classified as CHON compounds (compounds composed of C, H, O, and N atoms) in elemental and nitroaromatic compounds (NACs) in structures. From the perspective of the formation process, we discovered that these proinflammatory molecules, especially toxic NACs, were largely driven by secondary nitrate formation and biomass burning (in emission source), as well as SO 2 (in atmospheric evolution). In addition, our results indicated that the secondary processes had replaced the primary emission as the main contributing source of the toxic proinflammatory compounds in OAs. This study highlights the importance of community measures to control the production of nitroaromatic compounds derived from secondary nitrate formation and biomass burning in urban areas.

Atmospheric aerosol deposition (wet and dry) is an important source of macro and micronutrients (N, P, C, Si, and Fe) to the oceans. Most of the mass flux of air particles is made of fine mineral particles emitted from arid or semi-arid areas (e.g., deserts) and transported over long distances until deposition to the oceans. However, this atmospheric deposition is affected by anthropogenic activities, which heavily impacts the content and composition of aerosol constituents, contributing to the presence of potentially toxic elements (e.g., Cu). Under this scenario, the deposition of natural and anthropogenic aerosols will impact the biogeochemical cycles of nutrients and toxic elements in the ocean, also affecting (positively or negatively) primary productivity and, ultimately, the marine biota. Given the importance of atmospheric aerosol deposition to the oceans, this paper reviews the existing knowledge on the impacts of aerosol deposition on the biogeochemistry of the upper ocean, and the different responses of marine biota to natural and anthropogenic aerosol input.

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.

Experimental results of the second series of experiments on the penetration of monodisperse polymeric particles, inhaled at low dose by mice, to different organs using direct way of particle registration, based on the ultra‐sensitive accelerator mass spectrometer (AMS), are presented. Polystyrene (PS) beads, composed of radiocarbon‐labeled styrene, were produced for testing them as model organic aerosols. Mice inhaled 14C‐PS aerosol of 3·105 ultrafine particles per 1 cm3 for 30 minutes every day during 5 days. Long‐term investigation showed that PS ultrafine particles have been effectively accumulated in lungs with the maximum content in the fifth day of postexposure, and have also appeared in liver on the fifth day of exposure and in the brain on the 30th day of experiments. No particles have been detected in kidneys, spleen, and excrements. Thirty‐five millions of particles remained in the lungs after half a year of postexposure showing extremely slow removal of such particles from the organ. [ABSTRACT FROM AUTHOR]

The cell-free dithiothreitol (DTT) assay is widely used and the DTT consumption rate is interpreted to assess the oxidative potential (OP). Most researchers use an experimental procedure developed by Cho et al. (2005) while some adopt a procedure by Li et al. (2009). The key difference between the two procedures is the initial DTT concentration, 100 μM used in the former and 20 μM in the latter, raising an unaddressed issue of comparability. We examine in this work this issue using metal-free humic-like substance (HULIS) samples isolated from ambient aerosol and two metals (i.e. copper and manganese). We found that higher initial DTT concentrations led to higher DTT consumption rates for both HULIS and metals. For HULIS, the increase in DTT consumption rate was proportional to the initial DTT concentration (i.e., roughly by 5-fold), allowing correction of the concentration effect and direct comparison of results from the two protocols. However, the proportionality did not hold for the metals or metal-organic mixtures. The increase was much lower than the proportionality of 5 and metal concentration-dependent, specifically, 1.2–1.3 for Cu and from negligible to 2.0 for Mn. For six water extracts of ambient aerosol samples, in which HULIS and metals co-exist, the proportionality ranged from 1.3 to 2.2. This deviation from a linear dependence on initial DTT concentration, plausibly due to metal-DTT binding, impedes assessing and comparing OP of metals and metal-organic mixtures using different implementations of the DTT assay. Considering the different antioxidants concentrations in real human lung fluid, this work raises caution about using the DTT assay to assess metal-containing mixtures, such as ambient aerosol samples. Image 1 • Oxidative potential of redox active organics is proportional to initial DTT concentration. • The proportionality does not hold for Cu and Mn with the DTT assay. • A 5-fold increase in DTT produced <2-fold rise in measured OP for Cu and Mn. • Deviation from linear dependence impedes the utility of the DTT assay for metals. • Caution is needed in quantifying OP of metal-organics mixtures by the DTT assay. Oxidative potential by metals measured with the dithiothreitol (DTT) assay significantly deviates from being proportional to the DTT concentration, raising concerns for the suitability of the DTT assay for aerosol samples. [ABSTRACT FROM AUTHOR]

Abstract A high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) was deployed during wintertime (5 February to 15 March 2016) at a suburban site in Douai, northern France, in order to investigate the characteristics and sources of the organic matter (OM). The campaign average concentration of non-refractory submicron particulate matter (NR-PM 1) was 11.1 ± 9.3 μg m−3, and composed of 38% OM, 36% nitrate, 16% ammonium and 9% sulfate. The average values for the OM:OC, O:C and H:C ratios were 1.60 ± 0.15, 0.32 ± 0.11 and 1.55 ± 0.14, respectively, indicating a moderate level of aerosol oxidation. The positive matrix factorization (PMF) source apportionment method was applied to the high-resolution organic aerosol (OA) mass spectra, resulting in four factors: a hydrocarbon-like (HOA) factor; one associated with oxidized biomass burning (oBBOA); and two oxygenated factors (OOA) denoted as less oxidized (LO-OOA) and more oxidized (MO-OOA), with average contributions to OA of 20%, 28%, 17% and 35%, respectively. The oBBOA factor was found to be mainly local as shown by non-parametric wind regression (NWR) analysis, and to correlate well with relative humidity (RH), suggesting fast aqueous processing of locally emitted primary biomass burning emissions. During most part of the campaign, the sampling site was affected by different air masses. However, during the last period of the campaign (5–16 March 2016) the site was heavily impacted by air masses from Eastern Europe which were rich in secondary inorganic and organic aerosols. The H:C versus O:C (Van Krevelen, VK) diagram highlighted that the aerosol followed an oxidation process throughout the whole campaign, with an average slope of −1.05. The impact of continental air masses towards the end of the campaign confined the aerosol towards a narrower space in the VK diagram, suggesting a homogenization of the different aerosol sources due to OA ageing during transport. Several nocturnal NPF (new particle formation)-like events were observed and associated to the fast processing of BBOA emissions and the formation of ammonium nitrate. Graphical abstract Image 1 Highlights • Organic matter at a suburban site in winter investigated at high time resolution. • Aerosols were moderately oxidized with four sources of organic aerosol identified. • Oxidized biomass burning organic aerosols (BBOA) mostly local represented 28% of OA. • Several nocturnal NPF (new particle formation)-like events were observed. • It suggests a fast processing of BBOA and the possible role of ammonium nitrate. [ABSTRACT FROM AUTHOR]

This study reports for the first-time the ambient concentrations of HULIS mass (HULIS-OM, Humic-like substances) and HULIS-C (carbon) in PM10 (particulate matter with aerodynamic diameter ≤ 10 μm) from the Indo-Gangetic Plain (IGP at Kanpur, wintertime). HULIS extraction followed by purification and isolation protocol with methanol: acetonitrile (1:1 v/v) on HLB (Hydrophilic-Lipophilic Balanced) cartridge has been established. Quantification of HULIS-C was achieved on a total organic carbon (TOC) analyser whereas HULIS-OM was determined gravimetrically. Consistently high recovery (> 90%) of HULIS-C based on analysis of Humic standard (sodium salt of Humic acid) suggested suitability of our established analytical protocol involving solvent extraction, purification and accurate quantification of HULIS. HULIS-OM varied from 17.3-38 μg m−3 during daytime and from 19.8-40.6 μg m−3 during night in this study. During daytime the HULIS-OM constituted 20-30% mass fraction of OMTotal and 10-15% of PM10 mass. However, a relatively low contribution of HULIS-OM has been observed during the night. This observation has been attributed to higher concentrations of OM and PM10 in night owing to nighttime chemical reactivity and condensation of organics in conjunction with shallower planetary boundary layer height. Strong correlation of HULIS-C with K+BB (R2 > 0.80) and significant day-night variability of HULIS-C/WSOC ratio in conjunction with air-mass back trajectories (showing transport of pollutants from upwind IGP) suggest biomass burning emission and secondary transformations as important sources of HULIS over IGP. High-loading of atmospheric PM10 (as high as 440 μg m−3) with significant contribution of water-soluble organic aerosols (WSOC/OC: ~ 0.40-0.80) during wintertime highlights their plausible potential role in fog and haze formation and their impact on regional-scale atmospheric radiative forcing over the IGP. [ABSTRACT FROM AUTHOR]

The characteristics of non-refractory submicron aerosols (NR-PM 1), focusing on organic aerosols, are examined over a tropical coastal location, Thumba, in southern peninsular India. The measurements were carried out using an aerosol chemical speciation monitor during 2017–2021. The results indicated organic aerosols as the major component (67–85%) in the NR-PM 1 mass loading during all seasons. Positive matrix factorization (PMF) analysis on the OA mass spectra yielded two factors resolving Hydrocarbon-like organic aerosols (HOA) and Oxygenated organic aerosols (OOA), with the major contribution to OA coming from OOA (mass fraction >50%) during all the seasons. Examination of the diurnal variations revealed the daytime enhancement in OOA and sulfate mass fractions, indicating photochemical production overwhelming the dilution at the surface due to local atmospheric boundary layer expansion. The OOA mass concentration showed a good correlation (R > 0.5) with odd oxygen (O 3 +NO 2) and with an increase in oxygen-to-carbon ratio (ΔO:C = 0.11 to 0.35 with Δodd oxygen = 60 μg m−3 for different seasons) (i.e., increased oxidation degree of OA) signifying the dominance of photochemistry and subsequent enhanced atmospheric oxidative capacity in OOA formation. Interestingly, the aerosol liquid water content (ALWC) doubled during the nighttime (>40 μg m−3) compared to the daytime (<20 μg m−3) in different seasons, indicating the combined impact of varying submicron aerosol composition and ambient relative humidity. Since highly humid (relative humidity >85%) conditions prevail over this tropical coastal station, especially during the nighttime, the role of aqueous-phase formation of OA is also examined. It was found that less oxidized/less-hygroscopic OA were prevalent during the nighttime, resulting in lower aqueous-phase OA processing. During all the seasons, the hygroscopicity of organics (к organics) reached as high as > 0.22 and was mainly driven by photochemical processing rather than aqueous-phase chemistry. These results highlight the importance of the OA formation pathways in affecting their hygroscopic properties over the tropical atmosphere. • Organics are the dominant NR-PM 1 species in all seasons. • Oxygenated species dominated (>50%) the overall OA. • Photochemical reactions dominated OOA production. • The hygroscopicity of organics is mainly driven by photochemical processing. [ABSTRACT FROM AUTHOR]

Matrix-induced signal suppression or enhancements are known phenomena in electrospray ionization mass spectrometry. Very few studies report on method development for organic aerosols analyses with the evaluation of the matrix effects. The matrix effects lead to errors in the quantification of the analytes and affect the detection capability, precision, and accuracy of an analysis method. The present study reports on the matrix effects in the analysis of organic chemical compounds present in atmospheric aerosol particles collected on quartz filters. A total number of 19 analytes, including different classes of organic compounds, such as monoaromatic phenols and derivatives (e.g., catechol, 4-methylcatechol, 3-methoxycatechol, 4-nitrocatechol, 4-nitrophenol, 2,4-dinitrophenol, 2,6-dimethyl-4-nitrophenol), carboxylic acids (terebic acid, adipic acid, pimelic acid, phthalic acid, vanillic acid), and sulfonic acids (e.g., camphor-10-sulfonic acid), was investigated by high-performance liquid chromatography coupled to electrospray ionization time-of-flight mass spectrometry (HPLC/ESI-ToF-MS). The HPLC and ESI set-up parameters used in this study were previously optimized for the investigated compounds. Different volumes of a standard mixture were added to sample extracts, with final solutions concentrations in the 50–1500 μg L−1 range. For the investigated concentration range, the observed matrix effect was independent of the standard concentration level. For quartz filter extracts, the average matrix effect determined on a concentration-based method was 109.5 ± 6.1%. Both signal suppression and enhancement effects were observed for different compounds. For other analytes, the influence of the matrix effect is variable, suggesting that the use of an internal standard is not sufficient for the matrix effects correction. Competition between analyte ions and matrix components in the gas-phase ionization processes occurring in electrospray might explain signal suppression while generated coeluted isobaric compounds might induce signal enhancement.

The impact of aerosols on human health and climate is well-recognized, yet many studies have only focused on total PM 2.5 or changes from anthropogenic activities. This study quantifies the health and climate effects of organic aerosols (OA) from anthropogenic, biomass burning, and biogenic sources. Using two atmospheric chemistry models, CAM-chem and GEOS-Chem, our findings reveal that anthropogenic primary OA (POA) has the highest efficiency for health effects but the lowest for direct radiative effects due to spatial and temporal variations associated with population and surface albedo. The treatment of POA as nonvolatile or semivolatile also influences these efficiencies through different chemical processes. Biogenic OA shows moderate efficiency for health effects and the highest for direct radiative effects but has the lowest efficiency for indirect effects due to the reduced high cloud, caused by stabilized temperature profiles from aerosol-radiation interactions in biogenic OA-rich regions. Biomass burning OA is important for cloud radiative effect changes in remote atmospheres due to its ability to be transported further than other OAs. This study highlights the importance of not only OA characteristics such as toxicity and refractive index but also atmospheric processes such as transport and chemistry in determining health and climate impact efficiencies.

Organic aerosols (OAs) account typically for 20–90% of fine particles (PM 2.5 ) in the lower troposphere. They contribute to a wide range of environmental problems, from local issues (e.g., urban haze) to global problems (e.g., climate change). Huge efforts have been dedicated to studying the composition, abundance, spatial and temporal distribution and sources of organic aerosols in China. This review aims to summarize recent studies on characteristics and sources of OAs and assesses the current state of understanding of the organic aerosol pollution in China. The OA constitutes ∼20–45% of the PM 2.5 with an annual mean value of 5.2–44.5 μg/m 3 at sites across China, which is about five times higher than that reported in North America and Europe. There are thousands of different organic compounds in atmospheric aerosols, but only about 5–10% of them have been identified and quantified. OAs show pronounced spatial variations with much higher concentrations in Northern than Southern China. Seasonally, the highest OA concentrations are observed in the winter, whereas the lowest are in the summer. This is due to higher emission rates from anthropogenic sources (e.g., biomass and coal combustion) and poorer dispersion conditions in the winter. Approximately 60–80% of total OA is apportioned by receptor modeling (such as Chemical Mass Balance, CMB) and tracer-yield method, based on the source profiles of primary organic aerosols (POA) and secondary OA (SOA) derived from local emission sources. A number of OA sources are identified, including motor vehicles, industrial emissions, biomass combustion, food cooking, and coal combustion for POA and anthropogenic and biogenic emissions for SOA. Industrial emissions and motor vehicular exhaust are the dominant sources of organic aerosols in the industrialized areas of Northern China, as well as the Pearl River Delta and Eastern China, whereas in other urban areas, residential coal combustion and motor vehicular exhaust are the dominant sources in winter and summer respectively. [ABSTRACT FROM AUTHOR]

Fifteen hydrolyzed amino acids (THAA) were quantified in urban aerosols (TSP samples) collected during April 2012 to May 2013 in Beijing, China using high-performance liquid chromatography (HPLC) after their derivatization with o -phthalaldehyde (OPA), to investigate their molecular distributions and seasonal variation. Total concentrations of amino acids ranged from 1.73–25.7 nmol m − 3 with a peak in spring (13.7 nmol m − 3 ), followed by winter (11.5 nmol m − 3 ), fall (9.51 nmol m − 3 ) and summer (7.45 nmol m − 3 ). Glycine (Gly), alanine (Ala) and valine (Val) are found to be the most abundant species, which account for 46% of the total THAA. Compared with those recorded in previous studies, the atmospheric levels of amino acids in Beijing were higher than those from other regions. Enhanced amounts of methionine, tyrosine, histidine, aspartic acid and glutamic acid were found during the rainfall events. The factor analysis further suggests that amino acids in urban Beijing originated from multiple sources including biological emission, biomass burning, as well as anthropogenic activities. [ABSTRACT FROM AUTHOR]

Real time chemical characterization of non-refractory submicron aerosols (NR-PM 1 ) was carried out during post monsoon (September–October) via Aerosol Mass Spectrometer (AMS) at a polluted urban location of Kanpur, India. Organic aerosol (OA) was found to be the dominant species with 58% contribution to total NR-PM 1 mass, followed by sulfate (16%). Overall, OA was highly oxidized (average O/C = 0.66) with the dominance of oxidized OAs (60% of total OA) as revealed by source apportionment. Oxidized nature of OA was also supported by very high OC/EC ratios (average = 8.2) obtained from simultaneous offline filter sampling. High and low OA loading periods have very dramatic effects on OA composition and oxidation. OA O/C ratios during lower OA loading periods were on average 30% higher than the same from high loading periods with significant changes in types and relative contribution from oxidized OAs (OOA). Comparison of OA sources and chemistry among post monsoon and other seasons revealed significant differences. Characteristics of primary OAs remain very similar, but features of OOAs showed substantial changes from one season to another. Winter had lowest OOA contribution to total OA but similar overall O/C ratios as other seasons. This reveals that processing of primary OAs, local atmospheric chemistry, and regional contributions can significantly alter OA characteristics from one season to another. This study provides interesting insights into the seasonal variations of OA sources and evolution in a very polluted and complex environment. [ABSTRACT FROM AUTHOR]

Atmospheric aerosol optical, physical, and chemical properties play a fundamental role in the Earth's climate system. A better understanding of the processes involved in their formation, evolution, and interaction with radiation and the water cycle is critical. We report the analysis of atmospheric molecules/particles collected with a new sampling system that flew under regular weather balloons for the first time. The flight took place on January 18, 2022 from Reims (France). The samples were subsequently analyzed by high-resolution mass spectrometry (Orbitrap) to specifically infer hundreds of organic components present in 4 different layers from the troposphere to the stratosphere (up to 20 km). Additional measurements of O 3 , CO, and aerosol concentrations a few hours before this flight took place to contextualize the sampling. After separating common species found on each filter that might be common to atmospheric layers or residuals for contaminations, we found that each sample yields significant differences in the number and size of organic species detected that should reflect the unique composition of atmospheric layers. While tropospheric samples yield significantly oxidized and saturated components, with carbon numbers below 30 that might be explained by complex organics chemistry from local and distant source emissions, the upper tropospheric and stratospheric samples were associated with increased carbon numbers (C > 30), with a significantly reduced unsaturation number for the stratosphere, that might be induced by strong UV radiations. The multimodal distributions of carbon numbers in chemical formulas observed between 15 and 20 km suggest that oligomerization and growth of organic molecules may take place in aged air masses of tropical origin that are known to carry organic compounds even several km above the tropopause where their lifetime significantly increases. In addition, the presence of organics may also reflect the extended influence of wildfires smoke injected during the spring and summer in the NH hemisphere before the in situ observations and their long-lifetime in the upper troposphere and stratosphere. Photographic credit: Marc Fourmentin - Laboratoire de PhysicoChimie de l'Atmosphère. [Display omitted] • Unique launching infrastructure in Europe (Reims/France) to operate state-of-the art atmospheric instruments • New balloon-borne sampling device to characterize the chemical composition of organics (troposphere to stratosphere) • Offline analysis reveals the growth of organics aerosol in the stratosphere • Organics aerosol could derive from oligomerization processes along transport from the tropics and/or influenced by wildfires [ABSTRACT FROM AUTHOR]

Tropical aerosols of PM2.5 and PM10 were collected at a rural site in Morogoro, Tanzania (East Africa), and analysed for stable carbon isotopic composition (δ13C) of dicarboxylic acids (C2–C9), glyoxylic acid (ωC2) and glyoxal (Gly) using gas chromatography/isotope ratio mass spectrometer. PM2.5 samples showed that δ13C of oxalic (C2) acid are largest (mean, −18.3±1.7‰) followed by malonic (C3, −19.6±1.0‰) and succinic (C4, −21.8±2.2‰) acids, whereas those in PM10 are a little smaller: −19.9±3.1‰ (C2), −20.2±2.7‰ (C3) and −23.3±3.2‰ (C4). The δ13C of C2–C4 diacids showed a decreasing trend with an increase in carbon numbers. The higher δ13C values of oxalic acid can be explained by isotopic enrichment of 13C in the remaining C2 due to the atmospheric decomposition of oxalic acid or its precursors. δ13C of ωC2 and Gly that are precursors of oxalic acid also showed larger values (mean, −22.5‰ and −20.2‰, respectively) in PM2.5 than those (−26.7‰ and −23.7‰) in PM10. The δ13C values of ωC2 and Gly are smaller than those of C2 in both PM2.5 and PM10. On the other hand, azelaic acid (C9; mean, −28.5‰) is more depleted in 13C, which is consistent with the previous knowledge; that is, C9 is produced by the oxidation of unsaturated fatty acids emitted from terrestrial higher plants. A significant enrichment of 13C in oxalic acid together with its negative correlations with relative abundance of C2 in total diacids and ratios of water-soluble organic carbon and organic carbon further support that a photochemical degradation of oxalic acid occurs during long-range transport from source regions.

The main emission source in Central and Southern Chilean cities is biomass combustion from residential heating and cooking due to old combustion technologies that are still widely utilized. In order to improve our understanding of biomass burning pollution and how it ages in the atmosphere, emissions from a pellet and wood stoves were studied with the aid of a photochemical chamber. Firewood combustion is an inefficient process that produces higher chamber loading of primary emission (gases and particles) compared to pellets. When these emissions are exposed to UV irradiation secondary particles are formed. However, with both fuels the secondary particle concentration was negligible with regards to the primary initial particle concentration. Observations show that when the initial mass is the same, firewood combustion emissions are more rapidly oxidized compared to emissions from pellet combustion. Particle aging evolution inside the chamber was evaluated using fragment tracer signals, via the mass fractions f44 vs f43 and f44 vs f60 triangles plots. For the same UV irradiation time, it was found that primary particles emitted form from firewood combustion show a slower aging rate compared to those emitted from pellet combustion, but this is due to high primary loading from wood combustion. Particle aging observed inside the chamber was similar to that found it in ambient urban air of Santiago de Chile in spring of 2011, indicating that chamber measurements can be a good indicator for some atmospheric processes. Levoglucosan, a well-known tracer for biomass combustion was also studied. It was found that wood stoves yielded higher levels than pellet stoves. This is due to the higher fuel combustion efficiency in pellet stoves, which yield low levoglucosan levels, making it difficult to use it for evaluation of the impact of pellet emissions on pollution.

Although atmospheric organic N compounds are considered to be important, especially in new particle formation and their contribution to brown carbon, these species are not that well understood. This can be partially attributed to their chemical complexity. Therefore, the aim of this study was to assess the characteristics of organic N compounds utilising comprehensive two-dimensional gas chromatography coupled with a time-of-flight mass spectrometer (GCxGC-TOFMS) in aerosol samples that were collected at a savanna-grassland background region and to determine the possible sources. 135 atmospheric organic N compounds were tentatively characterised and semi-quantified, which included amines, nitriles, amides, urea, pyridine derivatives, amino acids, nitro-and nitroso compounds, imines, cyanates and isocyanates, and azo compounds. Amines contributed to 51% of the semi-quantified concentrations, while nitriles, pyridine derivatives, and amides comprised 20%, 11%, and 8%, respectively, of the semi-quantified concentrations. Amines, nitriles, amides, and pyridine derivatives concentrations were higher during the dry season, which were attributed to meteorology and open biomass burning. Anthropogenic sources impacting air masses measured at Welgegund, as well as regional agricultural activities, were considered as the major sources of amines, while the regional influence of household combustion was most likely the main source of nitriles, amides, and pyridine derivatives. The other organic N species were most likely related to the influence of local and regional agricultural activities.

Particulate matter 2.5 (PM2.5) filter samples were collected in July and October 2014 and January and April 2015 in urban Shanghai and analyzed using ultrahigh-performance liquid chromatography coupled to Orbitrap mass spectrometry. The measured chromatogram-mass spectra were processed by a nontarget screening approach to identify significant signals. In total, 810-1,510 chemical formulas of organic compounds in the negative polarity (negative electrospray ionization (ESI−)) and 860-1,790 in the positive polarity (ESI+), respectively, were determined. The chemical characteristics of organic aerosols (OAs) in Shanghai varied among different months and between daytime and nighttime. In the January samples, organics were generally richer in terms of both number and abundance, whereas those in the July samples were far lower. More CHO− (compounds containing only carbon, hydrogen, and oxygen and detected in ESI−) and CHOS− (sulfur-containing organics) were found in the daytime samples, suggesting a photochemical source, whereas CHONS− (nitrogen- and sulfur-containing organics) were more abundant in the nighttime samples, due to nocturnal nitrate radical chemistry. A significant number of monocyclic and polycyclic aromatic compounds, and nitrogen- and sulfur-containing heterocyclic compounds, were detected in all samples, indicating that biomass burning and fossil fuel combustion made important contributions to the OAs in urban Shanghai. Additionally, precursor-product pair analysis indicates that the epoxide pathway is an important formation route for organosulfates observed in Shanghai. Moreover, a similar analysis suggests that 35-57% of nitrogen-containing compounds detected in ESI+ could be formed through reactions between ammonia and carbonyls. Our study presents a comprehensive overview of OAs in urban Shanghai, which helps to understand their characteristics and sources. [ABSTRACT FROM AUTHOR]

Polycyclic aromatic hydrocarbons (PAHs) have toxic impacts on humans and ecosystems. One of the most carcinogenic PAHs, benzo(a)pyrene (BaP), is efficiently bound to and transported with atmospheric particles. Laboratory measurements show that particle-bound BaP degrades in a few hours by heterogeneous reaction with ozone, yet field observations indicate BaP persists much longer in the atmosphere, and some previous chemical transport modeling studies have ignored heterogeneous oxidation of BaP to bring model predictions into better agreement with field observations. We attribute this unexplained discrepancy to the shielding of BaP from oxidation by coatings of viscous organic aerosol (OA). Accounting for this OA viscosity-dependent shielding, which varies with temperature and humidity, in a global climate/chemistrymodel brings model predictions into much better agreement with BaP measurements, and demonstrates stronger long-range transport, greater deposition fluxes, and substantially elevated lung cancer risk from PAHs. Model results indicate that the OA coating is more effective in shielding BaP in the middle/high latitudes compared with the tropics because of differences in OA properties (semisolid when cool/dry vs. liquid-like when warm/humid). Faster chemical degradation of BaP in the tropics leads to higher concentrations of BaP oxidation products over the tropics compared with higher latitudes. This study has profound implications demonstrating that OA strongly modulates the atmospheric persistence of PAHs and their cancer risks. [ABSTRACT FROM AUTHOR]

Chemical characterization of ambient non-refractory submicron aerosols (NR-PM 1 ) was carried out in real time at Kanpur, India. The measurements were performed during the winter (December 2014 to February 2015), and comprised of two very distinct high and low aerosol loading periods coupled with prevalent foggy conditions. The average non-refractory submicron aerosol loading varied significantly from high (HL, ~ 240 μg/m 3 ) to low loading (LL, ~ 100 μg/m 3 ) period and was dominated by organic aerosols (OA) which contributed more than half (~ 60%) of the measured aerosol mass. OA source apportionment via positive matrix factorization (PMF) showed drastic changes in the composition of OA from HL to LL period. Overall, O/C (oxygen to carbon) ratios also varied significantly from HL (= 0.59) to LL (= 0.69) period. Fog episodes (n = 17) studied here seem to be reducing the magnitude of the negative impact of OA loading on O/C ratio (OA loading and O/C ratio are anti-correlated, as higher OA loading allows gas to particle partitioning of relatively less oxidized organics) by 60% via aqueous processing. This study provided new insights into the combined effects of OA loading and fog aqueous processing on the evolution of ambient organic aerosols (OA) for the first time. [ABSTRACT FROM AUTHOR]

Size-segregated aerosol samples were collected in New Delhi, India from March 6 to April 6, 2012. Homologous series of n- alkanes (C 19 C 33 ), n- fatty acids (C 12 C 30 ) and n- alcohols (C 16 C 32 ) were measured using gas chromatography/mass spectrometry. Results showed a high-variation in the concentrations and size distributions of these chemicals during non-haze, haze, and dust storm days. In general, n- alkanes, n- fatty acids and n- alcohols presented a bimodal distribution, peaking at 0.7–1.1 μm and 4.7–5.8 μm for fine modes and coarse modes, respectively. Overall, the particulate matter mainly existed in the coarse mode (≥2.1 μm), accounting for 64.8–68.5% of total aerosol mass. During the haze period, large-scale biomass burning emitted substantial fine hydrophilic smoke particles into the atmosphere, which leads to relatively larger GMDs (geometric mean diameter) of n- alkanes in the fine mode than those during the dust storms and non-haze periods. Additionally, the springtime dust storms transported a large quantity of coarse particles from surrounding or local areas into the atmosphere, enhancing organic aerosol concentration and inducing a remarkable size shift towards the coarse mode, which are consistent with the larger GMDs of most organic compounds especially in total and coarse modes. Our results suggest that fossil fuel combustion (e.g., vehicular and industrial exhaust), biomass burning, residential cooking, and microbial activities could be the major sources of lipid compounds in the urban atmosphere in New Delhi. [ABSTRACT FROM AUTHOR]

Polycyclic aromatic hydrocarbons (PAHs) and their oxygenated (OPAHs) and nitrated (NPAHs) derivatives are main chromophores of the carbonaceous aerosol brown carbon (BrC), which is linked with radiative forcing. Here, we investigated the atmospheric absorption spectra of 64 PAHs, OPAHs, and NPAHs directly over the Chinese megacity of Xi'an, by employing a time-dependent density functional theory (TD-DFT) computational approach and correcting the results for the experimentally determined atmospheric concentration of the studied molecules. The obtained data showed that these molecules contribute more to radiative forcing by absorbing light in the UVA and (sub)visible region of the spectrum. Investigating "daily" absorption spectra revealed major seasonal variation in the intensity of light absorption, but little changes in the shape of the absorption spectra. The observed light absorption can be explained mainly by contributions from PAHs and to a lesser extent by carbonyl-OPAHs, with relatively low contributions of the other OPAHs and NPAHs. Among them, benzo[ b + j + k ]fluoranthenes, benzo[ e ]pyrene, benzo[ a ]pyrene, benzo[ ghi ]perylene, indeno[1,2,3- cd ]pyrene, 6H-benzo[ cd ]pyren-6-one, 7H-benz[ de ]anthracen-7-one, and benz[ a ]anthracene-7,12-dione are highlighted as potentially problematic contributors for radiative forcing over Xi'an. [Display omitted] • The atmospheric absorption spectra of 64 PACs over Xi'an (China) was obtained. • TD-DFT calculations and experimental data were combined to produce the spectra. • PAHs are the most important class of light-absorbing molecules. • Light-absorption is more problematic in the UVA and (sub)visible range. • Light-absorption intensities are significantly affected by seasonal variation. [ABSTRACT FROM AUTHOR]

Accelerator mass spectrometry (AMS) was shown to be applicable for studying the penetration of organic aerosols, inhaled by laboratory mice at ultra-low concentration ca. 10 3 cm −3 . We synthesized polystyrene (PS) beads, composed of radiocarbon-labeled styrene, for testing them as model organic aerosols. As a source of radiocarbon we used methyl alcohol with radioactivity. Radiolabeled polystyrene beads were obtained by emulsifier-free emulsion polymerization of synthesized 14 C-styrene initiated by K 2 S 2 O 8 in aqueous media. Aerosol particles were produced by pneumatic spraying of diluted 14 C-PS latex. Mice inhaled 14 C-PS aerosol consisting of the mix of 10 3 225-nm particles per 1 cm 3 and 5·10 3 25-nm particles per 1 cm 3 for 30 min every day during five days. Several millions of 225-nm particles deposited in the lungs and slowly excreted from them during two weeks of postexposure. Penetration of particles matter was also observed for liver, kidneys and brain, but not for a heart. [ABSTRACT FROM AUTHOR]