Year-round observations of stable carbon isotopic composition of carboxylic acids, oxoacids and α-Dicarbonyls in fine aerosols at Tianjin, North China: Implications for origins and aging.

To better understand the origins and photochemical processing (aging) of organic aerosols (OA), we studied fine aerosols (PM2.5) collected at urban (Nankai District (ND)) and suburban (Haihe Education Park (HEP)) Tianjin, North China over a one-year period (2018-2019) for stable carbon isotopic composition (δ13C) of water-soluble diacids, oxoacids, α-dicarbonyls and fatty acids. Maleic (M, -18.3 ± 10.9‰ at ND and -23.5 ± 10.2‰ at HEP) and fumaric (F, -22.0 ± 12.1‰ at ND and -22.5 ± 10.5‰ at HEP) acids were found to be most enriched with 13C followed by oxalic acid (C2, -24.7 ± 3.9‰ at ND and -25.9 ± 4.7‰ at HEP) during the campaign. Based on seasonal changes in δ13C of selected marker species: C6 and C9 diacids, phthalic, glyoxylic and pyruvic acids and glyoxal, and their comparison with the source signatures, we found that water-soluble OA in Tianjin were mainly originated from fossil fuel combustion and biomass burning emissions and were subjected for significant aging. The contribution from fossil fuel combustion including coal combustion was high in autumn and winter, especially at ND. Considering the enrichment of 13C in specific species together with linear relations of δ13C of selected species with their concentrations, with mass ratios and with the relative abundance of C2 diacid, we inferred that the photochemical transformations of longer-chain diacids, oxidation of α-dicarbonyls (Gly and mGly), preferably in gas phase, were important in warm period (March-September), whereas the oxidation of Gly, mGly and other precursors in aqueous phase were major in cold period (October-February).

Distribution characteristics of organosulfates (OSs) in PM2.5 in Tianjin, Northern China: Quantitative analysis of total and three OS species.

Organosulfates (OSs) are important secondary organic aerosol (SOA) species in atmospheric fine particles (PM2.5) and can be considered as molecular indicators of SOA. To understand their seasonal and diurnal distribution characteristics and formation mechanism in northern China, PM2.5 samples collected in daytime and nighttime in winter and summer 2019 in Tianjin, China were studied for total OSs and three OS species (methyl sulfate (MS), glycolic acid sulfate (GAS), benzyl sulfate (BS)). The S contents of total OSs (SOSs) in winter and summer were 0.6 ± 1 µg m-3 and 0.4 ± 0.3 µg m-3, respectively, in PM2.5. BS found to be less abundant among the measured species, and accounted for only 0.8%-4.8% of methyl sulfate (MS), and 0.01%-0.3% of glycolic acid sulfate (GAS). Average content of GAS was higher in summer than in winter, while that of MS and BS were opposite. The fractions of MS, GAS, and BS in SOSs were higher in daytime than that in night during winter, despite their concentrations were higher in nighttime, indicating that the concentrations of unidentified OS species were much higher in nighttime than in daytime. Such diurnal variations implied that relative humidity (RH) played a major role in the formation processes of OSs, especially biogenic OSs and the acid catalyzed reaction of SO42- might be a main pathway of OSs formation during winter. High T, RH and O3 determined biological GAS in summer, while NO2 and SO2 determined anthropogenic OSs in winter. We also found that the fractions of SOSs in S contents of organic sulfur (SOS) and the S contents of MS + GAS+BS (SMS+GAS+BS) in SOSs were accounted for only less than 10% and 5%, respectively. Therefore, this study suggests the components of OS and OSs in PM2.5 have not been discovered fully yet and needs further research.

Molecular characterization and spatial distribution of dicarboxylic acids and related compounds in fresh snow in China.

Low molecular weight organic compounds are ubiquitous in the atmosphere. However, knowledge on their concentrations and molecular distribution in fresh snow remains limited. Here, twelve fresh snow samples collected at eight sites in China were investigated for dicarboxylic acids and related compounds (DCRCs) including oxocarboxylic acids and α-dicarbonyls. Dissolved organic carbon (DOC) concentrations in the snow samples ranged from 0.99 to 14.6 mg C L-1. Concentrations of total dicarboxylic acids were from 225 to 1970 µg L-1 (av. 650 µg L-1), while oxoacids (28.3-173, av. 68.1 µg L-1) and dicarbonyls (12.6-69.2, av. 31.3 µg L-1) were less abundant, accounting for 4.6-8.5% (6.2%), 0.45-1.4% (0.73%), and 0.12-0.88% (0.46%) of DOC, respectively. Molecular patterns of dicarboxylic acids are characterized by a predominance of oxalic acid (C2) (95.0-1030, av. 310 µg L-1), followed by phthalic (Ph) (9.69-244, av. 69.9 µg L-1) or succinic (C4) (23.8-163, av. 63.7 µg L-1) acid. Higher concentrations of Ph in snow from Beijing and Tianjin than other urban and rural regions suggest significant emissions from vehicular exhausts and other fossil fuel combustion sources in megacities. C2 constituted 40-54% of total diacids, corresponding to 1.5-2.6% of snow DOC. The total measured DCRCs represent 5.5-10% of snow DOC, which suggests that there are large amounts of unknown organics requiring further investigations. The spatial distributions of diacids exhibited higher loadings in megacities than rural and island sites. Molecular distributions of diacids indicated that the photochemical modification was restrained under the weak solar radiation during the snow events, while anthropogenic primary sources had a more significant influence in megacities than rural areas and islands.

Why airborne transmission hasn't been conclusive in case of COVID-19? An atmospheric science perspective.

Airborne transmission is one of the routes for the spread of COVID-19 which is caused by inhalation of smaller droplets1 containing SARS-CoV-2 (i.e., either virus-laden particulate matter: PM and/or droplet nuclei) in an indoor environment. Notably, a significant fraction of the small droplets, along with respiratory droplets, is produced by both symptomatic and asymptomatic individuals during expiratory events such as breathing, sneezing, coughing and speaking. When these small droplets are exposed to the ambient environment, they may interact with PM and may remain suspended in the atmosphere even for several hours. Therefore, it is important to know the fate of these droplets and processes (e.g., physical and chemical) in the atmosphere to better understand airborne transmission. Therefore, we reviewed existing literature focussed on the transmission of SARS-CoV-2 in the spread of COVID-19 and present an environmental perspective on why airborne transmission hasn't been very conclusive so far. In addition, we discuss various environmental factors (e.g., temperature, humidity, etc.) and sampling difficulties, which affect the conclusions of the studies focussed on airborne transmission. One of the reasons for reduced emphasis on airborne transmission could be that the smaller droplets have less number of viruses as compared to larger droplets. Further, smaller droplets can evaporate faster, exposing SARS-CoV-2 within the small droplets to the environment, whose viability may further reduce. For example, these small droplets containing SARS-CoV-2 might also physically combine with or attach to pre-existing PM so that their behaviour and fate may be governed by PM composition. Thus, the measurement of their infectivity and viability is highly uncertain due to a lack of robust sampling system to separately collect virions in the atmosphere. We believe that the present review will help to minimize the gap in our understanding of the current pandemic and develop a robust epidemiological method for mortality assessment.

Nitrogen Speciation and Isotopic Composition of Aerosols Collected at Himalayan Forest (3326 m a.s.l.): Seasonality, Sources, and Implications.

Nitrogenous aerosols are ubiquitous in the environment and thus play a vital role in the nutrient balance as well as the Earth's climate system. However, their abundance, sources, and deposition are poorly understood, particularly in the fragile and ecosensitive Himalayan and Tibetan Plateau (HTP) region. Here, we report concentrations of nitrogen species and isotopic composition (δ15N) in aerosol samples collected from a forest site in the HTP (i.e., Southeast Tibet). Our results revealed that both organic and inorganic nitrogen contribute almost equally with high abundance of ammonium nitrogen (NH4+-N) and water-insoluble organic nitrogen (WION), contributing ∼40% each to aerosol total nitrogen (TN). The concentrations and δ15N exhibit a significant seasonality with ∼2 times higher in winter than in summer with no significant diurnal variations for any species. Moreover, winter aerosols mainly originated from biomass burning emissions from North India and East Pakistan and reached the HTP through a long-range atmospheric transport. The TN dry deposition and total deposition fluxes were 2.04 kg ha-1 yr-1 and 6.12 kg ha-1 yr-1 respectively. Our results demonstrate that the air contamination from South Asia reach the HTP and is most likely impacting the high altitude ecosystems in an accepted scenario of increasing emissions over South Asia.

Implications for biomass/coal combustion emissions and secondary formation of carbonaceous aerosols in North China.

To understand the origins, secondary formation and seasonality of carbonaceous aerosols in North China, we collected PM2.5 samples on day- and night-time bases in summer and winter 2016 from a typical metropolis, Tianjin, and studied their carbonaceous components and stable carbon isotope ratios of total carbon (δ13CTC). PM2.5 ranged from 21.2 µg m-3 to 74.8 µg m-3 in summer and 25.3-816 µg m-3 in winter. On average, organic carbon (OC) elemental carbon (EC) and water-soluble OC were found to be higher (3-5 times) in winter than that in summer. Secondary organic carbon that estimated by EC-tracer method was enhanced by a factor of 7 in winter compared to that in summer. δ13CTC showed a small enrichment of 13C (average -25.41 ± 0.34‰) in summer compared to that (-24.42 ± 0.44‰) in winter. Linear relations and mass ratios of selected carbonaceous components and δ13CTC imply that the carbonaceous aerosols in Tianjin were mainly derived from biomass burning emissions and photochemical processing in summer. In winter, coal combustion emissions and in situ secondary formation of organics, including water-insoluble OC (WIOC), were dominant. This study warrants a need to understand the formation mechanisms of WIOC in the urban atmosphere and thus to reconcile the atmospheric models.

Enrichment of 13C in diacids and related compounds during photochemical processing of aqueous aerosols: New proxy for organic aerosols aging.

To investigate the applicability of compound specific stable carbon isotope ratios (δ13C) of organics in assessment of their photochemical aging in the atmosphere, batch UV irradiation experiments were conducted on two ambient (anthropogenic and biogenic) aerosol samples in aqueous phase for 0.5-120 h. The irradiated samples were analyzed for δ13C of diacids, glyoxylic acid (ωC2) and glyoxal. δ13C of diacids and related compounds became larger with irradiation time (i.e., aging), except for few cases. In general, δ13C of C2-C4 diacids showed an increasing trend with decreasing chain length. Based on δ13C of diacids and related compounds and their relations to their concentrations, we found that C2 and C3 are enriched with 13C during the photochemical decomposition and production from their higher homologues and oxoacids. Photochemical breakdown of higher (≥C3) to lower diacids is also important in the enrichment of 13C in C3-C9 diacids whereas their production from primary precursors causes depletion of 13C. In case of ωC2 and glyoxal, their photochemical production and further oxidation to highly oxygenated compounds both cause the enrichment of 13C. This study reveals that δ13C of diacids and related compounds can be used as a proxy to trace the aging of organic aerosols during long-range atmospheric transport.

Molecular distributions and compound-specific stable carbon isotopic compositions of lipids in wintertime aerosols from Beijing.

Molecular distributions and stable carbon isotopic compositions (δ(13)C) of n-alkanes, fatty acids and n-alcohols were investigated in urban aerosols from Beijing, northern China to better understand the sources and long-range atmospheric transport of terrestrial organic matter during polluted and clear days in winter. n-Alkanes (C19-C36), fatty acids (C8-C32) and n-alcohols (C16-C32) detected in Beijing aerosols are characterized by the predominance of C23, C16 and C28, respectively. Carbon preference index (CPI) values of n-alkanes, the ratios of the sum of odd-numbered n-alkanes to the sum of even-numbered n-alkanes, are close to 1, indicating a heavy influence of fossil fuel combustion. Relatively higher ratios of C(18:0+16:0)/C(18:n+16:1) (fatty acids) on clear days than polluted days indicate that long-distance transport and/or photochemical aging are more significant during clear days. δ(13)C values of n-alkanes and low molecular weight fatty acids (C16:0, C18:0) ranged from -34.1 to -24.7% and -26.9 to -24.6%, respectively, which are generally heavier on polluted days than those on clear days. Such a wide range suggests that atmospheric lipids in Beijing aerosols originate from multiple sources and encounter complicated atmospheric processes during long-range transport in North China.