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Biomass-burning organic aerosol(s) (BBOA) are rich in brown carbon, which significantly absorbs solar irradiation and potentially accelerates global warming. Despite its importance, the multiphase photochemistry of BBOA after light absorption remains poorly understood due to challenges in determining the oxidant concentrations and the reaction kinetics within aerosol particles. In this study, we explored the photochemical reactivity of BBOA particles in multiphase S(IV) oxidation to sulfate. We found that sulfate formation in BBOA particles under light is predominantly driven by photosensitization involving the triplet excited states ( 3 BBOA * ) instead of iron, nitrate, and S(IV) photochemistry. Rates in BBOA particles are three orders of magnitude higher than those observed in the bulk solution, primarily due to the fast interfacial reactions. Our results highlight that the chemistry of 3 BBOA * in particles can greatly contribute to the formation of sulfate, as an example of the secondary pollutants. Photosensitization of BBOA will likely become increasingly crucial due to the intensified global wildfires., Competing Interests: Competing interests statement:The authors declare no competing interest.

The oxidation mechanism of methylglyoxal (CH 3 COCHO) in the aqueous phase plays a crucial role in the formation of secondary organic aerosols (SOA). To date, the investigations of reaction mechanisms of MG in the aqueous phase still needs to be refined, and the oxidation mechanisms of MG in the existence of various oxidants (e.g., H 2 O 2 , O 3, ∙NO 3 , etc.) are in controversy. In this paper, we investigated the hypothesis that small-molecule organic acids are the primary products in cloud water and fog droplets, while large-molecule organic acids and oligomers play crucial roles in wet aerosols. Specifically, the hydration reaction, oxidation mechanism and oligomerization reaction of MG in aqueous phase were investigated on a theoretical basis. It has been indicated that the hydration reaction is a significant initiating reaction of MG in the atmospheric aqueous phase, whose generated hydrated compounds played a critical part in the process of forming oligomers. The aqueous oxidation reaction of MG could form a variety of organic acids, including pyruvic acid, formic acid, acetic acid, and oxalic acid. In the presence of OH radicals, pyruvic acid was the main first-generation production, which undergoes further reactions to form acetic acid, oxalic acid, and mesoxalic acid. Acetic acid was mainly derived from the reaction of OH radicals with pyruvic acid, whereas oxalic and mesoxalic acids were mainly generated by the OH radical reaction for MG and pyruvic acid. Of these, the formation of acetic acid was thermodynamically most favorable. Additionally, the reactions of MG with other oxidants also provided the possible pathways for pyruvic acid production. At 298 K, we calculated the rate constants for the reaction of MGHY with NO 3 , OH, HO 2 radicals, and O 3 to be 4.48 × 10 8 , 2.54 × 10 7 , 1.26 × 10 -2 , and 4.38 × 10 -4  M -1  s -1 , with atmospheric aqueous phase lifetimes (τ) of 4.43, 3.12 × 10 3 , 2.21 × 10 11 , and 3.17 × 10 8  h, respectively. The theoretical results from this work will facilitate the explanation for the MG reaction process in the aqueous phase so as to further correctly estimate the relationship between the aqueous phase chemistry of MG and the formation of SOA., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Many phenolic compounds (PhCs) in biomass burning and fossil fuel combustion emissions can partition into atmospheric aqueous phases ( e.g. , cloud/fog water and aqueous aerosols) and undergo reactions to form secondary organic aerosols (SOAs) and brown carbon (BrC). Redox-active transition metals, particularly Fe and Cu, are ubiquitous species in atmospheric aqueous phases known to participate in Fenton/Fenton-like chemistry as a source of aqueous ˙OH. However, even though the concentrations of water-soluble Cu are close to those of water-soluble Fe in atmospheric aqueous phases in some areas, unlike Fe, the effects that Cu have on SOA and BrC formation in atmospheric aqueous phases have scarcely been studied and remain poorly understood. We investigated the effects of Cu(II) on PhC reaction rates and BrC formation during the aqueous oxidation of four PhCs (guaiacol, catechol, syringol, and vanillin) by ˙OH generated from Fenton-like chemistry under different pH conditions. While the PhCs reacted when both H 2 O 2 and Cu(II) were present in the absence ( i.e. , dark oxidation) and presence ( i.e. , photooxidation) of light, the reaction rates were at least one order of magnitude higher during photooxidation. Higher PhC reaction rates were measured at higher pH during both dark oxidation and photooxidation as a result of higher ˙OH concentrations produced by Fenton-like chemistry. Only water-soluble BrC was formed during dark oxidation and photooxidation when Cu(II) was present. Mass absorption coefficients (10 3 to 10 4 cm 2 g -1 ) comparable to those of biomass burning BrC were measured during dark oxidation and photooxidation when Cu(II) was present. Light absorption was enhanced at higher pH during dark oxidation and photooxidation, which indicated that higher quantities and/or more absorbing BrC chromophores were formed at higher pH. The effects that Cu(II) had on the PhC reaction rates and the composition of SOAs and BrC formed depended on the PhC base structure ( i.e. , benzenediol vs. methoxyphenol). Overall, these results show how aqueous reactions involving Cu(II), H 2 O 2 , and PhCs can be an efficient source of daytime and nighttime water-soluble BrC and SOAs, which can have significant implications for how the atmospheric fates of PhCs are modeled for areas with substantial concentrations of water-soluble Cu in highly to moderately acidic cloud/fog water and aqueous aerosols.

Volatile chemical products (VCPs) are increasingly recognized as significant sources of volatile organic compounds (VOCs) in urban atmospheres, potentially serving as key precursors for secondary organic aerosol (SOA) formation. This study investigates the formation and physicochemical transformations of VCP-derived SOA, produced through ozonolysis of VOCs evaporated from a representative room deodorant air freshener, focusing on the effects of aerosol evaporation on its molecular composition, light absorption properties, and reactive oxygen species (ROS) generation. Following aerosol evaporation, solutes become concentrated, accelerating reactions within the aerosol matrix that lead to a 42% reduction in peroxide content and noticeable browning of the SOA. This process occurs most effectively at moderate relative humidity (∼40%), reaching a maximum solute concentration before aerosol solidification. Molecular characterization reveals that evaporating VCP-derived SOA produces highly conjugated nitrogen-containing products from interactions between existing or transformed carbonyl compounds and reduced nitrogen species, likely acting as chromophores responsible for the observed brownish coloration. Additionally, the reactivity of VCP-derived SOA was elucidated through heterogeneous oxidation of sulfur dioxide (SO 2 ), which revealed enhanced photosensitized sulfate production upon drying. Direct measurements of ROS, including singlet oxygen ( 1 O 2 ), superoxide (O 2 •- ), and hydroxyl radicals ( • OH), showed higher abundances in dried versus undried SOA samples under light exposure. Our findings underscore that drying significantly alters the physicochemical properties of VCP-derived SOA, impacting their roles in atmospheric chemistry and radiative balance.

A comprehensive understanding of the full volatility spectrum of organic oxidation products from the benzene series precursors is important to quantify the air quality and climate effects of secondary organic aerosol (SOA) and new particle formation (NPF). However, current models fail to capture the full volatility spectrum due to the absence of important reaction pathways. Here, we develop a novel unified model framework, the integrated two-dimensional volatility basis set (I2D-VBS), to simulate the full volatility spectrum of products from benzene series precursors by simultaneously representing first-generational oxidation, multigenerational aging, autoxidation, dimerization, nitrate formation, etc. The model successfully reproduces the volatility and O/C distributions of oxygenated organic molecules (OOMs) as well as the concentrations and the O/C of SOA over wide-ranging experimental conditions. In typical urban environments, autoxidation and multigenerational oxidation are the two main pathways for the formation of OOMs and SOA with similar contributions, but autoxidation contributes more to low-volatility products. NO x can reduce about two-thirds of OOMs and SOA, and most of the extremely low-volatility products compared to clean conditions, by suppressing dimerization and autoxidation. The I2D-VBS facilitates a holistic understanding of full volatility product formation, which helps fill the large gap in the predictions of organic NPF, particle growth, and SOA formation.

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

Incense burning is a common practice in Asian cultures, releasing hazardous particulate organics. Inhaling incense smoke can result in adverse health effects, yet the molecular compositions of incense-burning organics have not been well investigated due to the lack of measurement of intermediate-volatility and semi-volatile organic compounds (I/SVOCs). To elucidate the detailed emission profile of incense-burning particles, we conducted a non-target measurement of organics emitted from incense combustion. Quartz filters were utilized to trap particles, and organics were analyzed by a comprehensive two-dimensional gas chromatography-mass spectrometer (GC × GC-MS) coupled with a thermal desorption system (TDS). To deal with the complex data obtained by GC × GC-MS, homologs are identified mainly by the combination of selected ion chromatograms (SICs) and retention indexes. SICs of 58, 60, 74, 91, and 97 were utilized to identify 2-ketones, acids, fatty acid methyl esters, fatty acid phenylmethyl esters, and alcohols, respectively. Phenolic compounds contribute the most to emission factors (EFs) among all chemical classes, taking up 24.5 % ± 6.5 % of the total EF (96.1 ± 43.1 μg g -1 ). These compounds are largely derived from the thermal degradation of lignin. Biomarkers like sugars (mainly levoglucosan), hopanes, and sterols are extensively detected in incense combustion fumes. Incense materials play a more important role in shaping emission profiles than incense forms. Our study provides a detailed emission profile of particulate organics emitted from incense burning across the full-volatility range, which can be used in the health risk assessments. The data processing procedure in this work could also benefit those with less experience in non-target analysis, especially GC × GC-MS data processing., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Incense burning is a common religious activity that emits abundant gaseous and particulate pollutants into the atmosphere. During their atmospheric lifetime, these gases and particles are subjected to oxidation, leading to the formation of secondary pollutants. We examined the oxidation of incense burning plumes under O 3 exposure and dark condition using an oxidation flow reactor connected to a single particle aerosol mass spectrometer (SPAMS). Nitrate formation was observed in incense burning particles, mainly attributable to the ozonolysis of nitrogen-containing organic compounds. With UV on, nitrate formation was significantly enhanced, likely due to HNO 3 /HNO 2 /NOx uptake triggered by OH chemistry, which is more effective than ozone oxidation. The extent of nitrate formation is insensitive to O 3 and OH exposure, possibly due to the diffusion limitation on interfacial uptake. The O 3 -UV-aged particles are more oxygenated and functionalized than O 3 -Dark-aged particles. Oxalate and malonate, two typical secondary organic aerosol (SOA) components, were found in O 3 -UV-aged particles. Our work reveals that nitrate, accompanied by SOA, can rapidly form in incense-burning particles upon photochemical oxidation in the atmosphere, which could deepen our understanding of air pollution caused by religious activities., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Elevated particulate sulfate concentrations have been frequently observed in coastal areas when air masses are influenced by continental emissions, especially combustion sources like biomass burning. We studied the SO 2 uptake by laboratory-generated droplets containing incense smoke extracts and sodium chloride (IS-NaCl) under irradiation and found enhanced sulfate production over pure NaCl droplets, attributable to photosensitization induced by constituents in IS. Low relative humidity and high light intensity facilitated sulfate formation and increased the SO 2 uptake coefficient by IS-NaCl particles. Aging of the IS particles further enhanced sulfate production, attributable to the enhanced secondary oxidant production promoted by increased proportions of nitrogen-containing CHN and oxygen- and nitrogen-containing CHON species under light and air. Experiments using model compounds of syringaldehyde, pyrazine, and 4-nitroguaiacol verified the enhancements of CHN and CHON species in sulfate formation. This work provides experimental evidence of enhanced sulfate production in laboratory-generated IS-NaCl droplets via enhanced secondary oxidant production triggered by photosensitization in multiphase oxidation processes under light and air. Our results can shed light on the possible interactions between sea salt and biomass burning aerosols in enhancing sulfate production.

Viruses in built environments (BEs) raise public health concerns, yet they are generally less studied than bacteria. To better understand viral dynamics in BEs, this study assesses viromes from 11 habitats across four types of BEs with low to high occupancy. The diversity, composition, metabolic functions, and lifestyles of the viromes are found to be habitat dependent. Caudoviricetes species are ubiquitous on surface habitats in the BEs, and some of them are distinct from those present in other environments. Antimicrobial resistance genes are identified in viruses inhabiting surfaces frequently touched by occupants and in viruses inhabiting occupants' skin. Diverse CRISPR/Cas immunity systems and anti-CRISPR proteins are found in bacterial hosts and viruses, respectively, consistent with the strongly coupled virus-host links. Evidence of viruses potentially aiding host adaptation in a specific-habitat manner is identified through a unique gene insertion. This work illustrates that virus-host interactions occur frequently in BEs and that viruses are integral members of BE microbiomes., (© 2023. The Author(s).)

The domestic emission control area (DECA) policy has been implemented in China since 2017. However, its impact on ship emissions and in turn urban air quality is still unclear. In this study, real-time single particle measurements were carried out at a site in urban Guangzhou, about 1 km downwind of Huangpu Port, the largest maritime transport hub in southern China, in the summer of 2020 using a single particle aerosol mass spectrometer (SPAMS). During the campaign, the hourly averaged number fraction of ship emitted particles, using vanadium as a chemical indicator, varied from 0 to 14% with an average of 2 ± 1%. Ship emitted single particles contain organic carbon (OC), elemental carbon (EC), metals, sulfate and nitrate. More than 95% of ship emitted particles were sulfate-containing particles and the relative peak areas (RPAs) of sulfate and vanadium in the hourly average mass spectra of ship emitted particles were highly correlated (R 2  = 0.85), suggesting the potential contribution of ship emissions to sulfate production in coastal cities. The relative abundance of OC and EC-related components in ship emitted particles varied and it was likely attributed to the different blending fluids used in the production of low sulfur fuels. The results from this study provide evidence for evaluating the effectiveness of the current regulations and guidance for future policy-making regarding the low sulfur fuel quality regulation and multiple-component control strategies., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022. Published by Elsevier B.V.)

Elemental carbon is often found in ambient particulate matter (PM), and it contributes to the PM's oxidative potential (OP) and thus poses great health concerns. Previous review articles mainly focused on the methodologies in evaluating OP in PM and its relationship with selected chemical constituents, including metal ions, PAHs, and inorganic species. In recent years, growing attention has been paid to the effect of atmospheric aging processes on the OP of EC-containing airborne particles (ECCAPs). This review investigates more than 150 studies concerning the OP measurements and physico-chemical properties of both fresh and aged ECCAPs such as laboratory-generated elemental carbon (LGEC), carbon black (CB), soot (black carbon), and engineered carbon-containing nanomaterials (ECCBNs). Specifically, we summarize the characteristics of water-soluble and insoluble organic species, PAHs, quinone, and oxygen-containing functional groups (OFGs), and EC crystallinity. Both water-soluble organic carbon (WSOC) and water-insoluble organic carbon (WIOC) contribute to the OP. Low molecular weight (MW) PAHs show a higher correlation with OP than high MW PAHs. Furthermore, oxidative aging processes introduce OFGs, where quinone (CO) and epoxide (O-C-O) increase the OP of ECCAPs. In contrast, carboxyl (-COOH) and hydroxyl (-OH) slightly change the OP. The low crystallinity of EC favors the oxygen addition and forms active OFG quinone, thus increasing the OP. More detailed analyses for the EC microstructures and the organic coatings are needed to predict the OP of ECCAPs.

Cooking is an important source of organic aerosols (OA), particularly in urban areas, but it has not been explicitly included in current emission inventories in China. This study estimated the organic aerosol emissions from cooking during winter over the Pearl River Delta (PRD) region, China. Using the retrieved hourly cooking organic aerosol (COA) concentrations at two sites in Hong Kong and Guangzhou, population density, and daily per capita COA emissions, we determined the spatial and temporal distribution of COA emissions over the PRD region based on two approaches by treating COA as non-volatile (NVCOA) and semi-volatile (SVCOA), respectively. By using the estimated COA emissions and the Weather Research and Forecasting model coupled with chemistry (WRF-Chem) model, we reproduced the diurnal cycles of COA concentrations at the PolyU site in Hong Kong and Panyu site in Guangzhou. We also resolved the different patterns of COA between weekdays and weekends. The mean COA concentration during wintertime over the urban areas of the PRD region was 0.7 μg m -3 and 0.9 μg m -3 for the NVCOA and SVCOA cases, respectively, contributing 5.1% and 6.9% to the urban OA concentrations. The total COA emissions in winter over the PRD region were estimated to be 3.5 × 10 8  g month -1 and 3.8 × 10 8  g month -1 for the NVCOA and SVCOA cases, respectively, adding 34.8% and 37.8% to the total primary organic aerosol emissions. Considering COA emissions in the model increased the mean regional OA concentrations by 4.6% and 7.4% for the NVCOA and SVCOA cases, respectively. Our study therefore highlights the importance of cooking activities to OA concentrations in winter over the PRD region., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

A prominent source of hydroxyl radicals ( • OH), nitrous acid (HONO) plays a key role in tropospheric chemistry. Apart from direct emission, HONO (or its conjugate base nitrite, NO 2 - ) can be formed secondarily in the atmosphere. Yet, how secondary HONO forms requires elucidation, especially for heterogeneous processes involving numerous organic compounds in atmospheric aerosols. We investigated nitrite production from aqueous photolysis of nitrate for a range of conditions (pH, organic compound, nitrate concentration, and cation). Upon adding small oxygenates such as ethanol, n -butanol, or formate as • OH scavengers, the average intrinsic quantum yield of nitrite [Φ(NO 2 - )] was 0.75 ± 0.15%. With near-UV-light-absorbing vanillic acid (VA), however, the effective Φ(NO 2 - ) was strongly pH-dependent, reaching 8.0 ± 2.1% at a pH of 8 and 1.5 ± 0.39% at a more atmospherically relevant pH of 5. Our results suggest that brown carbon (BrC) may greatly enhance the nitrite production from the aqueous nitrate photolysis through photosensitizing reactions, where the triplet excited state of BrC may generate solvated electrons, which reduce nitrate to NO 2 for further conversion to nitrite. This photosensitization process by BrC chromophores during nitrate photolysis under mildly acidic conditions may partly explain the missing HONO in urban environments.

Cooking is an important source of primary organic aerosol (POA) in urban areas, and it may also generate abundant non-methane organic gases (NMOGs), which form oxidized organic aerosol (OOA) after atmospheric oxidation. Edible fats play an important role in a balanced diet and are part of various types of cooking. We conducted laboratory studies to examine the primary emissions of POA and NMOGs and OOA formation using an oxidation flow reactor (OFR) for three animal fats (i.e., lard, beef and chicken fats) heated at two different temperatures (160 and 180 °C). Positive matrix factorization (PMF) revealed that OOA formed together with POA loss after photochemical aging, suggesting the conversion of some POA to OOA. The maximum OOA production rates (PRs) from heated animal fats, occurring under OH exposures (OHexp) of 8.3-15 × 10 10 molecules cm -3 s, ranged from 8.9 to 24.7 μg min -1 , 1.6-14.5 times as high as initial POA emission rates (ERs). NMOG emissions from heated animal fats were dominated by aldehydes, which contributed 14-71% of the observed OOA. We estimated that cooking-related OOA could contribute to as high as ~10% of total organic aerosol (OA) in an urban area in Hong Kong, where cooking OA (COA) dominated the POA. This study provides insights into the potential contribution of cooking to urban OOA, which might be especially pronounced when cooking contributions dominate the primary emissions., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Complying with stricter emissions standards, a new generation of heavy-duty trucks (HDTs) has gradually increased its market share and now accounts for a large percentage of on-road mileage. The potential to improve air quality depends on an actual reduction in both emissions and subsequent formation of secondary pollutants. In this study, the emissions in real-world traffic from Euro VI-compliant HDTs were compared to those from older classes, represented by Euro V, using high-resolution time-of-flight chemical ionization mass spectrometry. Gas-phase primary emissions of several hundred species were observed for 70 HDTs. Furthermore, the particle phase and secondary pollutant formation (gas and particle phase) were evaluated for a number of HDTs. The reduction in primary emission factors (EFs) was evident (∼90%) and in line with a reduction of 28-97% for the typical regulated pollutants. Secondary production of most gas- and particle-phase compounds, for example, nitric acid, organic acids, and carbonyls, after photochemical aging in an oxidation flow reactor exceeded the primary emissions (EF Aged /EF Fresh ratio ≥2). Byproducts from urea-selective catalytic reduction systems had both primary and secondary sources. A non-negative matrix factorization analysis highlighted the issue of vehicle maintenance as a remaining concern. However, the adoption of Euro VI has a significant positive effect on emissions in real-world traffic and should be considered in, for example, urban air quality assessments.

We assessed the contribution of transboundary air pollutants (TAPs) transported from China to Tokyo using the Pb (0.5 /Cu (2.5 index. We conducted intensive observations over four seasons during 2014-2015 and analyzed ionic components and thirteen elements in size-segregated aerosols collected at the top of a 30-m-high tower in a hilly forested area of the Field Museum Tamakyuryo (FM Tama), in a western suburb of Tokyo. In order to evaluate if the Pb (0.5 /Cu (2.5 ratio can be applied in Tokyo as the megacity, the annual average concentration of Pb at Cape Hedo, Kumamoto city, on the west side of Japan, was higher than that of Pb at Tokyo, on the east side; this result indicates that TAPs affect western Japan more than eastern Japan. We inferred the main source of Cu to be braking abrasion from cars at local scale on the basis of its enrichment factor and size distribution. From the Pb (0.5 /Cu (2.5 ratio and sulfate concentration, we inferred that the highest contribution of TAPs to the total mass concentration in Tokyo occurred in spring, when TAPs accounted for 55%, 72%, and 53% of the total mass concentration in the 0.1 < Dp < 0.5, 0.5 < Dp < 1, and 1 < Dp < 2.5 fractions, respectively. These results can contribute to assessment of TAPs in Tokyo., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Atmospheric particles can be viscous. The limitation in diffusion impedes the mass transfer of oxidants from the gas phase to the particle phase and hinders multiphase oxidation processes. On the other hand, nitrate photolysis has been found to be effective in producing oxidants such as OH radicals within the particles. Whether nitrate photolysis can effectively proceed in viscous particles and how it may affect the physicochemical properties of the particle have not been much explored. In this study, we investigated particulate nitrate photolysis in mixed sucrose-nitrate-sulfate particles as surrogates of atmospheric viscous particles containing organic and inorganic components as a function of relative humidity (RH) and the molar fraction of sucrose to the total solute ( F SU ) with an in situ micro-Raman system. Sucrose suppressed nitrate crystallization, and high photolysis rate constants (∼10 -5 s -1 ) were found, irrespective of the RH. For F SU = 0.5 and 0.33 particles under irradiation at 30% RH, we observed morphological changes from droplets to the formation of inclusions and then likely "hollow" semisolid particles, which did not show Raman signal at central locations. Together with the phase states of inorganics indicated by the full width at half-maxima (FWHM), images with bulged surfaces, and size increase of the particles in optical microscopic imaging, we inferred that the hindered diffusion of gaseous products (i.e., NO x , NO y ) from nitrate photolysis is a likely reason for the morphological changes. Atmospheric implications of these results are also presented.

Particulate nitrate photolysis can produce oxidants (i.e., OH, NO 2 , and NO 2 - /HNO 2 ) in aqueous droplets and may play a potential role in increased atmospheric oxidative capacity. Our earlier works have reported on the SO 2 oxidation promoted by nitrate photolysis to produce sulfate. Here, we used glyoxal as a model precursor to examine the role of particulate nitrate photolysis in the formation of secondary organic aerosol (SOA) from particle-phase oxidation of glyoxal by OH radicals. Particles containing sodium nitrate and glyoxal were irradiated at 300 nm. Interestingly, typical oxidation products of oxalic acid, glyoxylic acid, and higher-molecular-weight products reported in the literature were not found in the photooxidation process of glyoxal during nitrate photolysis in the particle phase. Instead, formic acid/formate production was found as the main oxidation product. At glyoxal concentration higher than 3 M, we found that the formic acid/formate production rate increases significantly with increasing glyoxal concentration. Such results suggest that oxidation of glyoxal at high concentrations by OH radicals produced from nitrate photolysis in aqueous particles may not contribute significantly to SOA formation since formic acid is a volatile species. Furthermore, recent predictions of formic acid/formate concentration from the most advanced chemical models are lower than ambient observations at both the ground level and high altitude. The present study reveals a new insight into the production of formic acid/formate as well as a sink of glyoxal in the atmosphere, which may partially narrow the gap between model predictions and field measurements in both species.

Megacities are metropolitan areas with populations over 10 million, and many of them are facing significant global environmental challenges such as air pollution. Intense economic and human activities in megacities result in air pollution emissions, inducing high levels of air pollutants in the atmosphere that harm human health, cause regional haze and acid deposition, damage crops, influence regional air quality, and contribute to climate change. Since the Great London Smog and the first recognized episode of Los Angeles photochemical smog seventy years ago, substantial progress has been achieved in improving the scientific understanding of air pollution and in developing emissions reduction technologies and control measures. However, much remains to be understood about the complex processes of atmospheric transport and reaction mechanisms; the formation and evolution of secondary particles, especially those containing organic species; and the influence of emerging emissions sources and changing climate on air quality and health. Molina (DOI: ) has provided an excellent overview of the sources of emissions in megacities, atmospheric physicochemical processes, air quality trends and management, and the impacts on health and climate for the introductory lecture of this Faraday Discussion.

Many field studies have investigated the formation mechanisms of organic aerosol (OA) based on bulk analysis, yet the source and formation process of individual organic particles may be quite different due to the diversity of chemical composition and mixing state in single particles. Here we present the observation results of chemical composition and mixing state of carbonaceous single particles at an urban site in Guangzhou. The carbonaceous particles accounted for 74.6% of the total detected single particles, and were grouped into four types including elemental carbon-aged (EC-aged), elemental and organic carbon (ECOC), organic carbon-rich (OC-rich) and secondary ions-rich (SEC) particles. The formation of EC-aged particles was closely associated with the absorption of organics onto fresh EC particles from primary sources, and the further enrichment of organics in EC-aged particles resulted in the production of ECOC particles. In the daytime OC-rich and SEC particles were mainly produced from the photochemical reactions, while in the nighttime their sharp increases were found along with the enrichment of nitrate and organic nitrogen fragments, suggesting the heterogeneous formation of nitrate and organic nitrogen in OC-rich and SEC particles. The production rates of carbonaceous particles were also investigated in an episodic event, and the EC-aged particles showed the highest production rate compared to the other carbonaceous particles both in the daytime and nighttime, suggesting a significant role of EC in the formation and aging process of carbonaceous particles. The results from this work have revealed different formation processes and production rates of carbonaceous particles due to their diversity in mixing state, providing further insights into the formation mechanisms of OA in field studies., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

A fast mobility particle sizer operating at a one-second time resolution was used to measure aerosol particle number size distribution (5.6-560 nm) in marine conditions over the South China Sea (SCS) from 29 March to 2 May 2017 and in the tropic zone of the Northwest Pacific Ocean (NWPO) from 10 to 29 October 2018. The clean background number concentration of nucleation mode atmospheric particles (<30 nm) was approximately 0.6 × 10 3  cm -3 in these areas. Two nighttime and five daytime strong new particle formation (NPF) events were observed to occur extending over a spatial scale from 2 to 140 km in the SCS, with a net increase of nucleation mode particles of 4.5 × 10 4  cm -3  ± 3.4 × 10 4  cm -3 during five of the seven events. Nighttime NPF events were unlikely associated with sulfuric acid vapor because of lack of photochemical reactions. Daytime NPF events share several common features with nighttime NPF events, e.g., dramatic spatiotemporal variations in the number concentration of the nucleation mode particles. Without aerosol precursor measurements we cannot address the vapors driving the formation process. However, our results show no banana-shaped growth of the particles. The growth into larger particle sizes seems to be restricted by the availability of condensable components in the gas phase. The nucleation mode was observed and sometimes even dominated the number concentration over other particle modes in the marine atmosphere over the tropic zone of the NWPO. In addition, more data obtained during the two campaigns and other campaigns were also applied to strengthen the analysis in terms of origins, formation and absent growth of nucleation mode particles in the marine atmospheres over the two tropic zones., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Nitrate and sulfate are two key components of airborne particulate matter (PM). While multiple formation mechanisms have been proposed for sulfate, current air quality models commonly underestimate its concentrations and mass fractions during northern China winter haze events. On the other hand, current models usually overestimate the mass fractions of nitrate. Very recently, laboratory studies have proposed that nitrous acid (N(III)) produced by particulate nitrate photolysis can oxidize sulfur dioxide to produce sulfate. Here, for the first time, we parameterize this heterogeneous mechanism into the state-of-the-art Community Multi-scale Air Quality (CMAQ) model and quantify its contributions to sulfate formation. We find that the significance of this mechanism mainly depends on the enhancement effects (by 1-3 orders of magnitude as suggested by the available experimental studies) of nitrate photolysis rate constant ( J NO 3 - ) in aerosol liquid water compared to that in the gas phase. Comparisons between model simulations and in-situ observations in Beijing suggest that this pathway can explain about 15% (assuming an enhancement factor (EF) of 10) to 65% (assuming EF = 100) of the model-observation gaps in sulfate concentrations during winter haze. Our study strongly calls for future research on reducing the uncertainty in EF., Competing Interests: Disclaimer The authors declare no competing financial interest. The views expressed in this paper are those of the authors and do not necessarily represent the views or policies of the U.S. EPA. This manuscript has gone through review process within the Agency and cleared for publication.

Photolysis of iron chlorides is a well-known photolytic source of Cl • in environmental waters. However, the role of particulate chlorine radicals (Cl • and Cl 2 •- ) in their multiphase oxidative potential has been much less explored. Herein, we examine the effect of Cl • /Cl 2 •- produced from photolysis of particulate iron chlorides on atmospheric multiphase oxidation. As a model system, experiments on multiphase oxidation of SO 2 by Cl • /Cl 2 •- were performed. Fast sulfate production from SO 2 oxidation was observed with reactive uptake coefficients of ∼10 -5 , comparable to the values necessary for explaining the observations in the haze events in China. The experimental and modeling results found a good positive correlation between the uptake coefficient, γ SO2 , and the Cl • production rate, d[Cl • ]/dt, as γ SO2 = 5.3 × 10 -6 × log(d[Cl • ]/dt) + 4.9 × 10 -5 . When commonly found particulate dicarboxylic acids (oxalic acid or malonic acid) were added, sulfate production was delayed due to the competition of Fe 3+ between chloride and the dicarboxylic acid for its complexation at the initial stage. After the delay, comparable sulfate production was observed. The present study highlights the importance of photochemistry of particulate iron chlorides in multiphase oxidation processes in the atmosphere.

The relative humidity (RH) history that manifests the cycling of dehydration (water evaporation) and hydration (water uptake) may affect particle-phase reactions, products from which have strong influences on the physical properties and thus climatic effects of atmospheric particles. Using single-trapped particles, we show herein hygroscopic growths of mixed particles with reactive species undergoing three types of RH cycles, simulating different degrees of particle-phase reactions in the atmosphere. The reactive species are the widely known α-dicarbonyl glyoxal (GLY), and five reduced nitrogenous species, ammonium sulfate (AS), glycine (GC), l-alanine (AL), dimethylamine (DMA), and diethylamine (DEA). The results showed that the mixed particles after reactions generally had altered efflorescence relative humidity (ERH) and deliquescence relative humidity (DRH) values and reduced hygroscopic growths at moderately high RH (>80%) conditions. For example, with an additional slow drying step, the mean mass growth factors at 90% RH during dehydration dropped from 2.56 to 2.02 for GC/GLY mixed particles and from 2.45 to 1.23 for AL/GLY mixed particles. The reduced hygroscopicity with more RH cycling will thus lead to less efficient light scattering of the mixed particles, thereby resulting in less cooling and exacerbating direct heating due to light absorption by the products formed.

In 2019, Wexler showed that, by applying Raoult's law rigorously to aqueous solutions and properly accounting for hydration of solutes, equations can be derived that accurately describe solute and solvent activity over the full range of concentrations from infinitely dilute to pure solutes. One feature of this theory is that it also predicts the amount of water that is free and the amount that is bound to the solute. In 2004 and 2005, Choi and co-workers used an electrodynamic balance to measure (i) the concentration of a range of organic and electrolyte solutes as a function of water activity and (ii) the amount of free and bound water in these solutions using the fluorescence of pyranine as a probe. In the current work, we compare the predictions of Wexler's theory to the measurements of Choi. After the adjustments to the amount of free water obtained by these measurements, the predictions of Wexler's theory match the measurements of Choi. The potential reasons for the adjustments are discussed., Competing Interests: The authors declare no competing financial interest., (Copyright © 2020 American Chemical Society.)

Heterogeneous oxidation of SO 2 is an effective production pathway of sulfate in the atmosphere. We recently reported a novel pathway for the heterogeneous oxidation of SO 2 by in-particle oxidants (OH, NO 2 , and NO 2 - /HNO 2 ) produced from particulate nitrate photolysis ( Environ. Sci. Technol. 2019 , 53 , 8757-8766). Particulate nitrate is often found to coexist with chloride and other halide ions, especially in aged sea-salt aerosols and combustion aerosols. Reactive uptake experiments of SO 2 with UV-irradiated nitrate particles showed that sulfate production rates were enhanced by a factor of 1.4, 1.3, and 2.0 in the presence of Cl - , Br - , and I - , respectively, compared to those in the absence of halide ions. The larger sulfate production was attributed to enhanced nitrate photolysis promoted by the increased incomplete solvation of nitrate at the air-particle interface due to the presence of surface-active halide ions. Modeling results based on the experimental data showed that the nitrate photolysis rate constants increased by a factor of 2.0, 1.7, and 3.7 in the presence of Cl - , Br - , and I - , respectively. A linear relation was found between the nitrate photolysis rate constant, j NO3- , and the initial molar ratio of Cl - to NO 3 - , [Cl - ] 0 /[NO 3 - ] 0 , as j NO3- = 9.7 × 10 -5 [Cl - ] 0 /[NO 3 - ] 0 + 1.9 × 10 -5 at [Cl - ] 0 /[NO 3 - ] 0 below 0.2. The present study demonstrates that the presence of halide ions enhances sulfate production produced during particulate nitrate photolysis and provides insights into the enhanced formation of in-particle oxidants that may increase atmospheric oxidative capacity.

This paper reports the long term observation of particle-associated polycyclic aromatic hydrocarbons (PAHs) at Cape Hedo Atmosphere and Aerosol Monitoring Station, a remote site in the Western Pacific Ocean, from 2008 to 2015. This is the first long-term study that evaluated the contribution of long-range transport of PAHs in East Asia. No obvious trend (P > 0.05) was found in a particular season over the years. However, there are seasonal variations of PAH concentrations with higher in spring and winter. The higher PAH are attributed to air masses from the area including part of China. Source apportionment using three different approaches, i.e., PAH compositional pattern analysis, PAH diagnostic ratio analysis and positive matrix factorization modeling, showed the combined high contribution of biomass burning (18%, 14%) and coal combustion (33%, 24%) in spring and winter. In addition, the contribution of ship emissions (35%) was relatively high in spring, whereas that of vehicle emissions (36%) was relatively high in winter. The contribution of coal combustion to PAH has decreased throughout the years, likely due to changes in energy structure in China. The contribution of biomass burning to PAH has showed no trend, being stable, and that of vehicular emissions has increased.

Heterogeneous oxidation of SO 2 is one of the promising mechanisms to account for high loading of sulfate during severe haze periods in China. Our earlier work reported on the SO 2 oxidation by OH and NO 2 produced during 250 nm nitrate photolysis ( Environ. Sci. Technol. Lett . 2019 , 6 , 86-91). Here, we extend that work to examine sulfate production during nitrate photolysis at 300 nm irradiation, which can additionally generate NO 2 - or HNO 2 , N(III). Flow cell/in situ Raman experiments showed that the reactive uptake coefficient of SO 2 , γ SO 2 , can be expressed as γ SO 2 = 1.64 × p NO3- , where p NO3- is the nitrate photolysis rate in the range of (1.0-8.0) × 10 -5 M s -1 . Our kinetic model with the p NO3- predicts that N(III) is the main contributor to the SO 2 oxidation, followed by NO 2 contribution. Furthermore, the addition of OH scavengers (e.g., glyoxal or oxalic acid) does not suppress the sulfate production because of the reduced N(III)-consuming reactions and the high particle pH sustained by their presence. Our calculations illustrate that under characteristic haze conditions, the nitrate photolysis mechanism can produce sulfate at ∼1 μg m -3 h -1 at pH 4-6 and p NO3- = 10 -5 M s -1 . The present study highlights the importance of in-particle nitrate photolysis in heterogeneous oxidation of SO 2 by reactive nitrogen (NO 2 - /HNO 2 and NO 2 ) under atmospherically relevant actinic irradiation. However, the nitrate photolysis rate constant needs to be better constrained for ambient aerosols.

Motor vehicle emissions are an important but poorly constrained source of secondary organic aerosol (SOA). Here, we investigated in situ SOA formation from urban roadside air in Hong Kong during winter time using an oxidation flow reactor (OFR), with equivalent atmospheric oxidation ranging from several hours to several days. The campaign-average mass enhancement of OA, nitrate, sulfate, and ammonium upon OFR aging was 7.0, 7.2, 0.8, and 2.6 μg m -3 , respectively. To investigate the sources of SOA formation potential, we performed multilinear regression analysis between measured peak SOA concentrations from OFR and the concentrations of toluene that represent motor vehicle emissions and cooking OA from positive matrix factorization (PMF) analysis of ambient OA. Traffic-related SOA precursors contributed 92.3%, 92.4%, and 83.1% to the total SOA formation potential during morning rush hours, noon and early afternoon, and evening meal time, respectively. The SOA production factor (PF) was approximately 5.2 times of primary OA (POA) emission factor (EF) and the secondary particulate matter (PM) PF was approximately 2.6 times of primary particles EF. This study highlights the potential benefit of reducing secondary PM production from motor vehicle emissions in mitigating PM pollutions.

The toxic effects of lead on human health and the environment have long been a focus of research. To explore sources of lead in Guangzhou, China, we investigated atmospheric lead-containing particles (LCPs) during wintertime using a single particle aerosol mass spectrometer (SPAMS). Based on mass spectral features, LCPs were classified into eight major particle types, including Pb-Cl and Pb-Cl-Li (coal combustion and waste incineration), Pb-Cl-EC and Pb-Cl-OC (diesel trucks and coal combustion), Pb-Cl-Fe (iron and steel industry), Pb-Cl-AlSi (dust), Pb-Sec (secondary formation), and Pb-Cl-Zn (industrial process); these sources (in parentheses) were identified by comparing atmospheric LCP mass spectra with authentic Pb emission source mass spectra. Sampling periods with LCP number fractions (NFs) more than three times the average LCP NF (APF = 4.35%) and below the APF were defined as high LCP NF periods (HLFPs: H1, H3, and H5) and low LCP NF APF periods (LLFPs: L2 and L4), respectively. Diurnal patterns and high Pb-Sec content during LLFPs indicate that photochemical activity and heterogeneous reactions may have controlled Pb-Sec particle formation. The inverse Pb-Cl and Pb-Sec particle diurnal trends during LLFPs suggest the replacement of Cl by sulfate and nitrate. On average over the five periods, ~ 76% of the LCPs likely arose from coal combustion and/or waste incineration, which were dominant sources during all five periods, followed by diesel trucks during LLFPs and iron- and steel-related sources during HLFPs; HLFP LCPs arose mainly from primary emissions. These results can be used to more efficiently control Pb emission sources and prevent harm to human and environmental health from Pb toxicity., (Copyright © 2018 Elsevier Inc. All rights reserved.)

Particle density is an important physical property of atmospheric particles. The information on high time-resolution size-resolved particle density is essential for understanding the atmospheric physical and chemical aging processes of aerosols particles. In the present study, a centrifugal particle mass analyzer (CPMA) combined with a differential mobility analyzer (DMA) was deployed to determine the size-resolved effective density of 50 to 350nm particles at a rural site of Beijing during summer 2016. The measured particle effective densities decreased with increasing particle sizes and ranged from 1.43 to 1.55g/cm 3 , on average. The effective particle density distributions were dominated by a mode peaked at around 1.5g/cm 3 for 50 to 350nm particles. Extra modes with peaks at 1.0, 0.8, and 0.6g/cm 3 for 150, 240, and 350nm particles, which might be freshly emitted soot particles, were observed during intensive primary emissions episodes. The particle effective densities showed a diurnal variation pattern, with higher values during daytime. A case study showed that the effective density of Aitken mode particles during the new particle formation (NPF) event decreased considerably, indicating the significant contribution of organics to new particle growth., (Copyright © 2018. Published by Elsevier B.V.)

Despite its emerging significant public health concern, the presence of antibiotic resistance genes (ARGs) in urban air has not received significant attention. Here, we profiled relative abundances (as a fraction, normalized by 16S rRNA gene) of 30 ARG subtypes resistant to seven common classes of antibiotics, which are quinolones, β-lactams, macrolides, tetracyclines, sulfonamides, aminoglycosides, and vancomycins, in ambient total particulate matter (PM) using a novel protocol across 19 world cities. In addition, their longitudinal changes in PM 2.5 samples in Xi'an, China as an example were also studied. Geographically, the ARGs were detected to vary by nearly 100-fold in their abundances, for example, from 0.07 (Bandung, Indonesia) to 5.6 (San Francisco, USA). The β-lactam resistance gene blaTEM was found to be most abundant, seconded by quinolone resistance gene qepA; and their corresponding relative abundances have increased by 178% and 26%, respectively, from 2004 to 2014 in Xi'an. Independent of cities, gene network analysis indicates that airborne ARGs were differentially contributed by bacterial taxa. Results here reveal that urban air is being polluted by ARGs, and different cities are challenged with varying health risks associated with airborne ARG exposure. This work highlights the threat of urban airborne transmission of ARGs and the need of redefining our current air quality standards in terms with public health.

We investigate the effects of sulfate and nitrate on the formation and evolution of secondary organic aerosol formed in the aqueous phase (aqSOA) from photooxidation of two phenolic carbonyls emitted from wood burning. AqSOA was formed efficiently from the photooxidation of both syringaldehyde (C 9 H 10 O 4 ) and acetosyringone (C 10 H 12 O 4 ) in ammonium sulfate and ammonium nitrate solutions, with mass yields ranging from 30% to 120%. Positive matrix factorization on the organic mass spectra acquired by an Aerosol Mass Spectrometer revealed a combination of functionalization, oligomerization, and fragmentation processes in the chemical evolution of aqSOA. Functionalization and oligomerization dominated in the first 4 h of reaction, with phenolic oligomers and their derivatives significantly contributing to aqSOA formation; and oxidation of the first-generation products led to an abundance of oxygenated ring-opening products. Degradation rates of syringaldehyde and acetosyringone in nitrate solutions were 1.5 and 3.5 times faster than rates in sulfate solutions, and aqSOA yields in nitrate experiments are twice as high as in sulfate experiments. Nitrate likely promoted the reactions because it is a photolytic source of OH radicals, while sulfate is not, highlighting the importance of aerosol-phase nitrate in the formation of aqSOA by facilitating the photooxidation of organic precursors.

Reactions between dissolved ammonia and carbonyls, which form light-absorbing species in atmospheric particles, can be accelerated by actively removing water from the reaction system. Here, we examine the effects of relative humidity (RH) on the reactive uptake of glyoxal (Gly) by aqueous particles of ammonium sulfate (AS), ammonium bisulfate, sodium sulfate, magnesium sulfate, ammonium nitrate (AN), and sodium nitrate. In situ Raman analysis was used to quantify particle-phase Gly and a colored product, 2,2'-biimidazole (BI), as a function of uptake time. Overall, the Gly uptake rate increases with decreasing RH, reflecting the "salting-in" effect. The BI formation rate increases significantly with decreasing RH or aerosol liquid water (ALW). Compared to that at 75% RH, the BI formation rate is enhanced by factors of 29 at 60% RH and 330 at 45% RH for AS particles and 65 at 60% RH, 210 at 45% RH, and 460 at 30% RH for AN particles. These enhancement factors are much larger than those estimated from increased reactant concentrations due to decreases in RH and ALW alone. We postulate that the reduction in ALW at low RH increases the Gly uptake rate via the "salting-in" effect and the BI formation rate by facilitating dehydration reactions.

Exhaled volatile organic compounds (VOCs) have aroused considerable interest, since they can serve as biomarkers for disease diagnosis and environmental exposure in a non-invasive manner. In this work, we present a protocol to characterize the exhaled VOCs in real time by using secondary nanoelectrospray ionization coupled to high resolution mass spectrometry (Sec-nanoESI-HRMS). The homemade Sec-nanoESI source was readily set up based on a commercial nanoESI source. Hundreds of peaks were observed in the background-subtracted mass spectra of exhaled breath, and the mass accuracy values are -4.0-13.5 ppm and -20.3-1.3 ppm in the positive and negative ion detection modes, respectively. The peaks were assigned with accurate elemental composition according to the accurate mass and isotopic pattern. Less than 30 s is used for one exhalation measurement, and it takes approximately 7 min for six replicated measurements.

Cooking is an important source of volatile organic compounds (VOCs) and a potential source of secondary organic aerosol (SOA) both indoors and outdoors. In this study, VOC emissions from heating corn oil and stir-frying spices (i.e. garlic, ginger, myrcia and zanthoxylum piperitum (Sichuan pepper)) were characterized using an on-line membrane inlet vacuum ultraviolet single-photon ionization time-of-flight mass spectrometer (VUV-SPI-TOFMS). VOC emissions from heating corn oil were dominated by aldehydes, which were enhanced by factors of one order of magnitude when stir-frying spices. Stir-frying any of the spices studied generated large amounts of methylpyrrole (m/z 81). In addition, stir-frying garlic produced abundant dihydrohydroxymaltol (m/z 144) and diallyldisulfide (DADS) (m/z 146), while stir-frying ginger, myrcia and zanthoxylum piperitum produced abundant monoterpenes (m/z 136) and terpenoids (m/z 152, 154). SOA formed from emissions of stir-frying spices through reactions with excess ozone in a flow reactor as well as primary organic aerosol (POA) emissions were characterized using a scanning mobility particle sizer (SMPS) and a high-resolution time-of-flight aerosol mass spectrometer (HR-TOF-AMS). Stir-frying garlic and ginger generated similar POA concentrations to those from heating corn oil while stir-frying myrcia and zanthoxylum piperitum generated double the amount of emissions. No SOA was observed from stir-frying garlic and ginger. The rates of SOA production from stir-frying myrcia and zanthoxylum piperitum were 1.8μgmin -1 g spice -1 and 8.7μgmin -1 g spice -1 , equivalent to 13.4% and 53.1% of their own POA emission rates, respectively. Therefore, the contribution of stir-frying spices to ambient organic aerosol levels is likely dominated by POA. The rates of total terpene emission from stir-frying myrcia and zanthoxylum piperitum were estimated to be 5.1μgmin -1 g spice -1 and 24.9μgmin -1 g spice -1 , respectively. Our results suggest that stir-frying spices could be an important source of terpenes in indoor environments in Hong Kong, at least during cooking., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Atmospheric aerosol particles of sizes less than 2.5 microns affect public health in cities. Understanding the fine structures of aerosol particles is important to decipher their source. Here, we use a novel spectroscopic and mechanical microscopy technique of 10 nm spatial resolution to reveal the nanoscale structures of individual aerosol particles.

Short-chain alkyl amines can undergo gas-to-particle partitioning via reactive uptake by ammonium salts, whose phases have been thought to largely influence the extent of amine uptake. Previous studies mainly focused on particles of single ammonium salt at either dry or wet conditions without any addition of organic compounds. Here we report the uptake of dimethylamine (DMA) by ammonium sulfate (AS) and AS-sucrose mixed particles at different relative humidities (RHs) using an electrodynamic balance coupled with in situ Raman spectroscopy. DMA is selected as a representative of short-chain alkyl amines, and sucrose is used as a surrogate of viscous and hydrophilic organics. Effective DMA uptake was observed for most cases, except for the water-limiting scenario at <5% RH and the formation of an ultraviscous sucrose coating at 10% RH and below. DMA uptake coefficients (γ) were estimated using the particle mass measurements during DMA uptake. Addition of sucrose can increase γ by absorbing water or inhibiting AS crystallization and decrease γ by elevating the particle viscosity and forming a coating layer. DMA uptake can be facilitated for crystalline AS or retarded for aqueous AS with hydrophilic viscous organics (e.g., secondary organic material formed via the oxidation of biogenic volatile organic compounds) present in aerosol particles.

MicroRNA-21 (miR-21) is consistently up-regulated in various neurological disorders, including epilepsy. Here, we show that the biogenesis of miR-21 is altered following pilocarpine-induced status epilepticus (SE) with an increase in precursor miR-21 (pre-miR-21) in rats. We demonstrate that pre-miR-21 has an energetically favorable site overlapping with the miR-21 binding site and competes with mature miR-21 for binding in the 3'UTR of TGFBR2 mRNA, but not NT-3 mRNA in vitro. This binding competition influences miR-21-mediated repression in vitro and correlates with the increase in TGFBR2 and decrease in NT-3 following SE. Polysome profiling reveals co-localization of pre-miR-21 in the ribosome fraction with translating mRNAs in U-87 cells. The current work suggests that pre-miR-21 may post-transcriptionally counteract miR-21-mediated suppression following SE and could potentially lead to prolonged TGF-β receptor expression impacting epileptogenesis. The study further supports that the ratio of the pre to mature miRNA may be important in determining the regulatory effects of a miRNA gene., (Copyright © 2016 Elsevier Inc. All rights reserved.)

Alkyl aminium sulfates (AASs) can affect the physicochemical properties of atmospheric aerosols such as hygroscopicity. Previous laboratory experiments have shown that the water content in AAS bulk solutions is higher than in aqueous ammonium sulfate solution in the range of 60-95% relative humidity (RH). Furthermore, amine was found to evaporate from the solution during the preparation of AASs from the parent amine and sulfuric acid solutions. Here we report the hygroscopicities of deposited particles of four AASs at different aminium-to-sulfate molar ratios (A/Ss) in the range of <3-90% RH using air-flow cells coupled with in situ micro-Raman spectroscopy. Normalized integrated areas of O-H stretching peaks in the Raman spectra were converted to water-to-solute molar ratios (WSRs) at various RH values. Evaporation of amine was also observed in most cases and the exact A/Ss of sample particles or solutions were determined by ion chromatography. Mono-methylaminium sulfate (MMAS) and mono-ethylaminium sulfate (MEAS) particles were stable at A/S = 2.0, but di-methylaminium sulfate (DMAS) and tri-methylaminium sulfate (TMAS) suffered from DMA and TMA evaporation and eventually equilibrated to the A/S of 1.5 and 1.0, respectively. At these stable compositions MMAS and MEAS exhibited phase transitions in the super-saturation region, while DMAS and TMAS showed a continuous and reversible water uptake. Besides, an approach to estimate the hygroscopicities of DMAS and TMAS particles at an initial A/S larger than that of the stable compositions was presented. In the range of 60-95% RH, the WSRs of all the studied AAS particles were consistent with a previous study based on experimental values and the extended Zdanovskii-Stokes-Robinson equation. In general, all the studied AASs were more hygroscopic than their corresponding ammonium counterparts within the studied RH range and evaporation of amine needs to be corrected in studying unstable AAS particles.

Particles larger than 50-100 nm in diameter have been considered to be effective cloud condensation nuclei (CCN) under typical atmospheric conditions. We studied the growth of newly formed particles (NPs) in the atmosphere and the conditions for these particles to grow beyond 50 nm at a suburban coastal site in Hong Kong. Altogether, 17 new particle formation events each lasting over 1 h were observed in 17 days during 8 Mar-28 Apr and 1 Nov-30 Dec 2011. In 12 events, single-stage growth of NPs was observed in daytime when the median mobility diameter of NPs (Dp) increased up to ∼40 nm but did not increase further. In three events, two-stage particle growth to 61-97 nm was observed at nighttime. The second stage growth was preceded by a first-stage growth in daytime when the Dp reached 43 ± 4 nm. In all these 15 events, organics and sulfuric acid were major contributors to the first-stage growth in daytime. Ammonium nitrate unlikely contributed to the growth in daytime, but it was correlated with the second-stage growth of ∼40 nm NPs to CCN sizes at nighttime. The remaining two events apparently showed second-stage growth in late afternoon but were confirmed to be due to mixing of NPs with pre-existing particles. We conclude that daytime NP growth cannot reach CCN sizes at our site, but nighttime NP growth driven by organics and NH4NO3 can.

Organic sulfur compounds have been identified in ambient secondary organic aerosols, but their contribution to organic mass is not well quantified. In this study, using a high-resolution time-of-flight aerosol mass spectrometer (AMS), concentrations of organic sulfur compounds were estimated based on the high-resolution fragmentation patterns of methanesulfonic acid (MSA), and organosulfates (OS), including alkyl, phenyl, and cycloalkyl sulfates, obtained in laboratory experiments. Mass concentrations of MSA and minimum mass concentrations of OS were determined in a field campaign conducted at a coastal site of Hong Kong in September 2011. MSA and OS together accounted for at least 5% of AMS detected organics. MSA is of marine origin with its formation dominated by local photochemical activities and enhanced by aqueous phase processing. OS concentrations are better correlated with particle liquid water content (LWC) than with particle acidity. High-molecular-weight OS were detected in the continental influenced period probably because they had grown into larger molecules during long-range transport or they were formed from large anthropogenic precursors. This study highlights the importance of both aqueous-phase processing and regional influence, i.e., different air mass origins, on organic sulfur compound formation in coastal cities like Hong Kong.

The second messengers cAMP and cGMP modulate attraction and repulsion mediated by neuronal guidance cues. We find that the Drosophila receptor guanylyl cyclase Gyc76C genetically interacts with Semaphorin 1a (Sema-1a) and physically associates with the Sema-1a receptor plexin A (PlexA). PlexA regulates Gyc76C catalytic activity in vitro, and each distinct Gyc76C protein domain is crucial for regulating Gyc76C activity in vitro and motor axon guidance in vivo. The cytosolic protein dGIPC interacts with Gyc76C and facilitates Sema-1a-PlexA/Gyc76C-mediated motor axon guidance. These findings provide an in vivo link between semaphorin-mediated repulsive axon guidance and alteration of intracellular neuronal cGMP levels.

The exchange reaction of ammonia in (NH4)2SO4 with an amine and the corresponding reverse reaction of amines in aminium sulfates with ammonia were investigated using an electrodynamic balance coupled with a Raman spectrometer. The temporal changes in particle mass, chemical composition, and phase state were simultaneously monitored. When the salt particles were in an aqueous state at elevated relative humidities (RHs), the exchange of ammonia/amine vapors in the particle phase was reversible. The exchange rates of aqueous particles were in general higher than those of their corresponding solid counterparts. An aqueous phase was essential for the effective displacement of ammonia and amines. Aminium salts in different phase states and with different evaporation characteristics showed remarkably different reaction behaviors in ammonia vapor. The less compact amorphous aminium sulfate solids were more susceptible to ammonia exchange than the crystalline solids. The aminium salts in a liquid state exhibited substantial amine evaporation at <3% RH and formed acidic bisulfate. Under ammonia exposure, these acidic aminium droplets underwent both neutralization and displacement reactions. Stable solid salts containing ammonium, aminium, sulfate, and bisulfate were formed and hindered further reactions. The result suggests that ambient aminium sulfates may be acidic. Overall, the phase states of the ammonium and aminium salt particles crucially determine the heterogeneous reaction rates and final product properties and identities.

The Drosophila transmembrane semaphorin-1a (Sema-1a) is a repulsive guidance cue that uses the Plexin A (PlexA) receptor during neural development. Sema-1a is required in axons to facilitate motor axon defasciculation at guidance choice points. We found that mutations in the trol gene strongly suppress Sema-1a-mediated repulsive axon guidance. trol encodes the phylogenetically conserved secreted heparan sulfate proteoglycan (HSPG) perlecan, a component of the extracellular matrix. Motor axon guidance defects in perlecan mutants resemble those observed in Sema-1a- and PlexA-null mutant embryos, and perlecan mutants genetically interact with PlexA and Sema-1a. Perlecan protein is found in both the CNS and the periphery, with higher expression levels in close proximity to motor axon trajectories and pathway choice points. Restoring perlecan to mutant motor neurons rescues perlecan axon guidance defects. Perlecan augments the reduction in phospho-focal adhesion kinase (phospho-FAK) levels that result from treating insect cells in vitro with Sema-1a, and genetic interactions among integrin, Sema-1a, and FAK in vivo support an antagonistic relationship between Sema-1a and integrin signaling. Therefore, perlecan is required for Sema-1a-PlexA-mediated repulsive guidance, revealing roles for extracellular matrix proteoglycans in modulating transmembrane guidance cue signaling during neural development.

Longitudinal axon fascicles within the Drosophila embryonic CNS provide connections between body segments and are required for coordinated neural signaling along the anterior-posterior axis. We show here that establishment of select CNS longitudinal tracts and formation of precise mechanosensory afferent innervation to the same CNS region are coordinately regulated by the secreted semaphorins Sema-2a and Sema-2b. Both Sema-2a and Sema-2b utilize the same neuronal receptor, plexin B (PlexB), but serve distinct guidance functions. Localized Sema-2b attraction promotes the initial assembly of a subset of CNS longitudinal projections and subsequent targeting of chordotonal sensory afferent axons to these same longitudinal connectives, whereas broader Sema-2a repulsion serves to prevent aberrant innervation. In the absence of Sema-2b or PlexB, chordotonal afferent connectivity within the CNS is severely disrupted, resulting in specific larval behavioral deficits. These results reveal that distinct semaphorin-mediated guidance functions converge at PlexB and are critical for functional neural circuit assembly., (Copyright © 2011 Elsevier Inc. All rights reserved.)

We investigated the condensed-phase reactions of biogenic VOCs with C double bond C bonds (limonene, C(10)H(16), and terpineol, C(10)H(18)O) catalyzed by sulfuric acid by both bulk solution (BS) experiments and gas-particle (GP) experiments using a flow cell reactor. Product analysis by gas chromatography-mass spectrometry (GC-MS) showed that cationic polymerization led to dimeric and trimeric product formation under conditions of relative humidity (RH) <20% (in the GP experiments) and a sulfuric acid concentration of 57.8 wt % (in the BS experiments), while hydration occurred under conditions of RH > 20% (in the GP experiments) and sulfuric acid concentrations of 46.3 wt % or lower (in the BS experiments). Apparent partitioning coefficients (K(p,rxn)) were estimated from the GP experiments by including the reaction products. Only under extremely low RH conditions (RH < 5%) did the values of K(p,rxn) ( approximately 5 x 10(-6) m(3)/microg for limonene and approximately 2 x 10(-5) m(3)/microg for terpineol) substantially exceed the physical partitioning coefficients (K(p) = 6.5 x 10(-8) m(3)/microg for limonene and =2.3 x 10(-6) m(3)/microg for terpineol) derived from the absorptive partitioning theory. At RH higher than 5%, the apparent partitioning coefficients (K(p,rxn)) of both limonene and terpineol were in the same order of magnitude as the K(p) values derived from the absorptive partitioning theory. Compared with other conditions including VOC concentration and degree of neutralization (by ammonium) of acidic particles, RH is a critical parameter that influences both the reaction mechanisms and the uptake ability (K(p,rxn) values) of these processes. The finding suggests that RH needs to be considered when taking the effects of acid-catalyzed reactions into account in estimating organic aerosol formation from C double bond C containing VOCs.

Berberine is a natural quaternary ammonium alkaloid used clinically in the chloride salt form for the treatment of diarrhea in many Asian countries. Although the hydrate formation of berberine chloride (BCl) is well documented, the associated mechanism and implications in pharmaceutical formulation have not been studied in detail. In this study, pure BCl dihydrate and BCl tetrahydrate were recrystallized from water and their phase transformation behaviors under defined conditions were investigated. Additionally, pharmacopoeial grade BCl material consisting predominantly of the dihydrate form was examined for potential phase changes when being subjected to a conventional wet granulation procedure for tablet production. Results from solubility measurements, thermal analysis, variable temperature-powder X-ray diffraction (VT-PXRD), and variable temperature-Fourier transform infrared spectroscopy (VT-FTIR) confirmed the solid-state interconversions between the tetrahydrate and dihydrate at 30-49 degrees C and between the dihydrate and anhydrate at 70-87 degrees C. Consistent with the observed phase changes of the two pure hydrates, wet massing of the pharmacopoeial grade BCl sample led to a thermodynamics-driven transition to the tetrahydrate form at room temperature while subsequent tray drying at 50 degrees C caused a reversion back to the dihydrate form. The rate and extent of such hydrate conversion depended largely on the water activity of the granulated powder matrix, which in turn was governed by the particular excipients employed. The present findings have important implications in the regulation of the hydrate forms of BCl in the finished products using specific excipients., (2009 Wiley-Liss, Inc. and the American Pharmacists Association)

The effects of the polymorphism of glutaric acid (GA) particles on their deliquescence properties at room temperature were studied. The polymorphic states of GA, including the metastable alpha-form and the thermodynamically stable beta-form, were characterized by Raman spectral measurements. The deliquescence of GA particles was also studied by Raman and optical observations. It was found that the alpha-form deliquesced at 85-86% relative humidity (RH), whereas some alpha-form transformed to the beta-form rather than completing full deliquescence. The beta-form absorbed water slowly at 87-89% RH, which was higher than the deliquescence relative humidity (DRH) of the alpha-form. The water-uptake process was not completed in 5 h, but the particles deliquesced quickly (<15 min) when the RH was increased to about 90%, indicating that mass transfer was delayed in the beta-form and that a higher RH of 90% was needed to cross the kinetic barrier. We showed that polymorphic transformation alters the deliquescence properties of GA particles, which might explain the discrepancies in DRH values of GA particles (83-90%) reported in the literature. This transformation should be taken into account in future laboratory experiments and aerosol thermodynamic models.