A year-round observation of δ13C of dicarboxylic acids and related compounds in fine aerosols: Implications from Central European background site.

Isotopic analysis of specific compounds in aerosols can be a useful tool when studying atmospheric processes. Here, we present the results of stable carbon isotope ratio (δ13C) measurements performed on a one-year set (n = 96, Sep. 2013-Aug. 2014) of dicarboxylic acids and related compounds in PM1 at a rural Central European background site, Kosetice (Czech Republic). The most 13C enriched acid was oxalic (C2, annual average = -16.6 ± 5.0‰) followed by malonic (C3, avg. = -19.9 ± 6.6‰) and succinic (C4, avg. = -21.3 ± 4.6‰) acids. Thus, δ13C values decreased with an increase in carbon numbers. Azelaic acid (C9, avg. = -27.2 ± 3.6‰) was found to be the least 13C enriched. A comparison of δ13C of dicarboxylic acids from other background sites, especially in Asia, shows similar values to those from the European site. This comparison also showed that C2 is more 13C enriched at background sites than at urban ones. In general, we did not observe significant seasonal differences in δ13C values of dicarboxylic acids at the Central European station. We observed statistically significant differences (p value < 0.05) between winter and summer δ13C values solely for C4, glyoxylic acid (ωC2), glutaric acid (C5) and suberic acid (C8). The only significant correlations between δ13C of C2 and δ13C of C3 were found in spring and summer, suggesting that the oxidation of C3 to C2 is significant in these months with a strong contribution from biogenic aerosols. The strongest season-independent annual correlation was observed in δ13C values between C2 and C4, the two dominant dicarboxylic acids. Therefore, C4 appears to be the main intermediate precursor of C2 throughout the whole year.

Formation of Amino Acids and Carboxylic Acids in Weakly Reducing Planetary Atmospheres by Solar Energetic Particles from the Young Sun.

Life most likely started during the Hadean Eon; however, the environmental conditions which contributed to the complexity of its chemistry are poorly known. A better understanding of various environmental conditions, including global (heliospheric) and local (atmospheric, surface, and oceanic), along with the internal dynamic conditions of the early Earth, are required to understand the onset of abiogenesis. Herein, we examine the contributions of galactic cosmic rays (GCRs) and solar energetic particles (SEPs) associated with superflares from the young Sun to the formation of amino acids and carboxylic acids in weakly reduced gas mixtures representing the early Earth's atmosphere. We also compare the products with those introduced by lightning events and solar ultraviolet light (UV). In a series of laboratory experiments, we detected and characterized the formation of amino acids and carboxylic acids via proton irradiation of a mixture of carbon dioxide, methane, nitrogen, and water in various mixing ratios. These experiments show the detection of amino acids after acid hydrolysis when 0.5% (v/v) of initial methane was introduced to the gas mixture. In the set of experiments with spark discharges (simulation of lightning flashes) performed for the same gas mixture, we found that at least 15% methane was required to detect the formation of amino acids, and no amino acids were detected in experiments via UV irradiation, even when 50% methane was used. Carboxylic acids were formed in non-reducing gas mixtures (0% methane) by proton irradiation and spark discharges. Hence, we suggest that GCRs and SEP events from the young Sun represent the most effective energy sources for the prebiotic formation of biologically important organic compounds from weakly reducing atmospheres. Since the energy flux of space weather, which generated frequent SEPs from the young Sun in the first 600 million years after the birth of the solar system, was expected to be much greater than that of GCRs, we conclude that SEP-driven energetic protons are the most promising energy sources for the prebiotic production of bioorganic compounds in the atmosphere of the Hadean Earth.

Physical and chemical properties of PM1 in Delhi: A comparison between clean and polluted days.

Considering the significance of PM1 aerosol in assessing health impacts of air pollution, an extensive analysis of PM1 samples collected at an urban site in Delhi is presented in this study. Overall, PM1 contributed to about 50 % of PM2.5 mass which is alarming especially in Delhi where particle mass loadings are usually higher than prescribed limits. Major portion of PM1 consisted of organic matter (OM) that formed nearly 47 % of PM1 mass. Elemental carbon (EC) contributed to about 13 % of PM1 mass, whereas SO42- (16 %), NH4+ (10 %), NO3- (4 %) and Cl- (3 %) were the major inorganic ions present. Sampling was performed in two distinctive campaign periods (in terms of meteorological conditions and heating (fire) activities), during the year 2019, each spanning two-week time, i.e. (i) September 3rd-16th (clean days), and (ii) November 22nd-December 5th (polluted days). Additionally, PM2.5 and black carbon (BC) were measured simultaneously for subsequent analysis. The 24-h averaged mean concentrations of PM2.5 and BC during clean days (polluted days) were 70.6 ± 26.9 and 3.9 ± 1.0 µg m-3 (196 ± 104 and 7.6 ± 4.1 µg m-3), respectively, which were systematically lower (higher) than that of the annual mean (taken from studies conducted at same site in 2019) of 142 and 5.7 µg m-3, respectively. Changes in characteristic ratios (i.e., organic carbon (OC)/elemental carbon (EC) and K+/EC) of chemical species detected in PM1 show an increase in biomass emissions during polluted days. Increase in biomass emission can be attributed to increase in heating practices (burning of biofuels such as wood logs, straw, and cow-dung cake) in- and around- Delhi because of fall in temperature during second campaign. Furthermore, a significant increase in NO3- fraction of PM1 is observed during second campaign which shows fog processing of NOX due to conducive meteorological conditions in winters. Also, comparatively stronger correlation of NO3- with K+ during second campaign (r = 0.98 as compared to r = 0.5 during first campaign) suggests the increased heating practices to be a contributing factor for increased fraction of NO3- in PM1. We observed that during polluted days, meteorological parameters such as dispersion rate also played a major role in intensifying the impact of increased local emissions due to heating activities. Apart from this, change in the direction of regional emission transport to study site and the topology of Delhi are the possible reasons for the elevated pollution level, especially PM1 during winter in Delhi. This study also suggests that black carbon measurement techniques used in current study (optical absorbance with heated inlet and evolved carbon techniques) can be used as reference techniques to determine the site-specific calibration constant of optical photometers for urban aerosol.

Size distributions of molecular markers for biogenic secondary organic aerosol in urban Beijing.

To understand the source, formation, and seasonality of biogenic secondary organic aerosol (BSOA), a nine-stage cascade impactor was utilized to collect size-segregated particulate samples from April 2017 to January 2018 in Beijing, China. BSOA tracers derived from isoprene, monoterpene, and sesquiterpene were measured with gas chromatography-mass spectrometry. Isoprene and monoterpene SOA tracers exhibited significant seasonal variations, with a summer maximum and a winter minimum. Dominance of 2-methyltetrols (isoprene SOA tracers) with a good correlation with levoglucosan (a biomass burning tracer), which was combined with the detection of methyltartaric acids (possible indicators for aged isoprene) in summer, implies possible biomass burning and long-range transport. In contrast, sesquiterpene SOA tracer (ß-caryophyllinic acid) was dominant in winter and was probably associated with the local burning of biomass. Bimodal size distributions were observed for most isoprene SOA tracers, consistent with previous laboratory experiments and field studies showing that they can be formed not only in the aerosol phase but also in the gas phase. Monoterpene SOA tracers cis-pinonic acid and pinic acid showed a coarse-mode peak (5.8-9.0 µm) in four seasons due to their volatile nature. Sesquiterpene SOA tracer ß-caryophyllinic acid showed a unimodal pattern with a major fine-mode peak (1.1-2.1 µm), which is linked to local biomass burning. The tracer-yield method was used to quantify the contributions of isoprene, monoterpene, and sesquiterpene to secondary organic carbon (SOC) and SOA. The highest isoprene SOC and SOA concentrations occurred in summer (2.00 µgC m-3 and 4.93 µg m-3, respectively), contributing to 1.61% of OC and 5.22% of PM2.5, respectively. These results suggest that BSOA tracers are promising tracers for understanding the source, formation, and seasonality of BSOA.

Organic aerosols in the inland Tibetan Plateau: New insights from molecular tracers.

Aerosols affect the radiative forcing of the global climate and cloud properties. Organic aerosols are among the most important, yet least understood, components of the sensitive Tibetan Plateau atmosphere. Here, the concentration of and the seasonal and diurnal variations in biomass burning and biogenic aerosols, and their contribution to organic aerosols in the inland Tibetan Plateau were investigated using molecular tracers. Biomass burning tracers including levoglucosan and its isomers, and aromatic acids showed higher concentrations during winter than in summer. Molecular tracers of primary and secondary biogenic organic aerosols were more abundant during summer than those in winter. Meteorological conditions were the main factors influencing diurnal variations in most organic molecular tracers during both seasons. According to the tracer-based method, we found that biogenic secondary organic aerosols (38.5 %) and fungal spores (14.4 %) were the two dominant contributors to organic aerosols during summer, whereas biomass burning (15.4 %) was an important aerosol source during winter at remote continental background site. Results from the positive matrix factor source apportionment also demonstrate the importance of biomass burning and biogenic aerosols in the inland Tibetan Plateau. During winter, the long-range transport of biomass burning from South Asia contributes to organic aerosols. In contrast, the precursors, biogenic secondary organic aerosols, and fungal spores from local emissions/long-range transport are the major sources of organic aerosols during summer. Further investigation is required to distinguish between local emissions and the long-range transport of organic aerosols. In-depth insights into the organic aerosols in the Tibetan Plateau are expected to reduce the uncertainties when evaluating aerosol effects on the climate system in the Tibetan Plateau.

Sulfate-associated liquid water amplifies the formation of oxalic acid at a semi-arid tropical location over peninsular India during winter.

Aerosol liquid water (ALW) can serve as an aqueous-phase medium for numerous chemical reactions and consequently enhance the formation of secondary aerosols in a highly humid atmosphere. However, the aqueous-phase formation of secondary organic aerosols (SOAs) is not well understood in the Indian regions, particularly in tropical peninsular India. In this study, we collected total suspended particulate samples (n = 30) at a semiarid station (Ballari; 15.15°N, 76.93°E; 495 m asl) in tropical peninsular India during the winter of 2016. Homologous series of dicarboxylic acids (C2-C12), oxoacids (ωC2-ωC9), pyruvic acid (Pyr), and glyoxal (Gly) were determined by employing a water-extraction of aerosol and analyzed using capillary gas chromatography (GC). Results show that oxalic acid (C2) was the most abundant organic acid, followed by succinic (C4), malonic (C3), azelaic (C9), and glyoxylic (ωC2) or phthalic (Ph) acids. Total diacids-C accounted for 1.7-5.8 % of water-soluble organic carbon (WSOC) and 0.6-3.6 % of total carbon (TC). ALW, estimated from the ISORROPIA 2.1 model, showed a strong linear relationship with sulfate (SO42-), C2, C3, C4, ωC2, Pyr, and Gly. Based on molecular distribution, specific mass ratios (C2/C3, C2/C4, C2/Gly, and Ph/C9), linear relationships among the measured organic acids, ALW, organic (levoglucosan and oleic acid), and inorganic (SO42-) marker compounds, we emphasize that diacids and related organic compounds, especially C2, majorly form via aqueous-phase oxidation of precursor compounds including aromatic hydrocarbons (HCs) and unsaturated fatty acids (FAs) originated from biomass burning and combustion-related sources. The present study demonstrates that sulfate driven ALW largely enhances the formation of SOAs via the aqueous-phase reactions over tropical peninsular India during winter.

Diurnal variations in primary and secondary organic aerosols in an eastern China coastal city: The impact of land-sea breezes.

The land-sea breeze circulation significantly impacts the atmospheric transport of organic aerosols in coastal regions. However, the links between organic aerosols and land-sea breezes remain poorly understood. In this study, organic marker compounds for biomass burning, primary biological aerosols, biogenic and anthropogenic secondary organic aerosols (SOA) in fine particles from a coastal city in East China were analysed using gas chromatography-mass spectrometry. Land-sea breeze circulations were identified to explore their potential influence on organic molecular compositions. Organic marker compounds showed obvious diurnal/seasonal patterns. Surprisingly, due to the combined influence of weakened East Asian monsoons and land-sea breezes, all detected organic markers decreased except α/ß-pinene SOA markers during land-sea breeze periods in early autumn; whereas, all the organic markers increased except α/ß-pinene SOA markers, pollen and plant debris markers during land-sea breeze periods in early spring. Furthermore, the reaction pathway and aging of biogenic SOA were also related to land-sea breezes. During the land-sea breeze periods, the ratios of 2-methylglyceric acid (2-MGA) to 2-methyltetrols increased in early autumn, indicating that more isoprene-derived SOA generated from the high-NOx (nitrogen oxides) pathway when the land-sea breezes occurred; while the ratios decreased in early spring, this may be related to the chemical transformation of 2-MGA to 2-MGA sulfates. Changes in the ratio of monoterpene SOA markers demonstrate that monoterpene SOA was relatively aged during sea breeze periods, while it was fresher when the land breeze occurred. Although boundary layer height, emissions, gas/particle partitioning, etc. are important reasons for the diurnal variations of organic aerosols, night/day ratios of molecular markers increased obviously when land-sea breezes occurred in both early autumn and early spring. Our results provide new insights into the shift in the chemical composition of organic aerosols over coastal areas that are influenced by land-sea breezes.

Geochemical studies of low molecular weight organic acids in the atmosphere: sources, formation pathways, and gas/particle partitioning.

Low molecular weight monocarboxylic acids (LMW monoacids, C1-C10) are the most abundant gaseous organic compound class in the atmosphere. Formic or acetic acid is the dominant volatile organic compound (VOC) in Earth's atmosphere. They can largely contribute to rainwater acidity, especially in the tropical forest, and react with alkaline metals, ammonia, and amines, contributing to new particle formation and secondary organic aerosol production. Gaseous and particulate LMW monoacids were abundantly reported in China. They can be directly emitted from fossil fuel combustion and biomass burring; however, the secondary formation is more important than primary emissions via the photochemical oxidation of anthropogenic and biogenic VOCs. In this paper, we review the distributions of LMW monoacids from urban, mountain, and marine sites as well as from rainwater and alpine snow samples and discuss their sources and formation mechanisms in the atmosphere. We also discuss their importance as cloud condensation nuclei (CCN) and provide future perspectives of LMW monoacids study in the warming world.

Seasonal characteristics of biogenic secondary organic aerosol tracers in a deciduous broadleaf forest in northern Japan.

We collected total suspended particulate (TSP) samples from January 2010 to December 2010 at Sapporo deciduous forest to understand the oxidation processes of biogenic volatile organic compounds (BVOCs). The gas chromatography-mass spectrometric technique was applied to determine biogenic secondary organic aerosols (BSOAs) in the TSP samples. We found the predominance of the isoprene SOA (iSOA) tracers (20.6 ng m-3) followed by α/ß-pinene SOA (pSOA) tracers (8.25 ng m-3) and ß-caryophyllene SOA (cSOA) tracer (1.53 ng m-3) in the forest aerosols. The results showed large isoprene fluxes and relatively high levels of oxidants in the forest atmosphere. The iSOA and pSOA tracers showed a clear seasonal trend with summer and autumn maxima and winter and spring minima. Their seasonal trends were mainly controlled by BVOCs emission from the local broadleaf deciduous forest. Additionally, the regional level of isoprene emissions from the oceanic sources may also be contributed during summertime aerosols. cSOA tracer showed high concentrations in the winter and spring, possibly due to an additional contribution of biomass burning (BB) aerosols from the local or regional BB activities. The biogenic secondary organic carbon (BSOC) was contributed mainly by the oxidation products of isoprene (136 ngC m-3) followed by ß-caryophyllene (63.0 ngC m-3) and α/ß-pinene (35.9 ngC m-3). The mass concentration ratio (0.92) of pinonic acid + pinic acid and 3-methyl-1,2,3-butanetricarboxylic acid ((PNA + PA)/3-MBTCA) indicates the photochemical transformation of first-generation oxidation products to the higher generation oxidation products. The average ratios of isoprene to α/ß-pinene (1.64) and ß-caryophyllene (18.6) oxidation products suggested a large difference in the emissions of isoprene and α/ß-pinene compared to ß-caryophyllene. The cSOA tracers in the forest aerosols are also contributed by BB during the winter and spring. Positive matrix factorization analyses of the BSOA tracers confirmed that organic aerosols of deciduous forests are mostly related to isoprene emissions. This study suggests that isoprene is a more significant precursor for the BSOA than α/ß-pinene and ß-caryophyllene in a broadleaf deciduous forest.

Large contribution of fossil-derived components to aqueous secondary organic aerosols in China.

Incomplete understanding of the sources of secondary organic aerosol (SOA) leads to large uncertainty in both air quality management and in climate change assessment. Chemical reactions occurring in the atmospheric aqueous phase represent an important source of SOA mass, yet, the effects of anthropogenic emissions on the aqueous SOA (aqSOA) are not well constrained. Here we use compound-specific dual-carbon isotopic fingerprints (δ13C and Δ14C) of dominant aqSOA molecules, such as oxalic acid, to track the precursor sources and formation mechanisms of aqSOA. Substantial stable carbon isotope fractionation of aqSOA molecules provides robust evidence for extensive aqueous-phase processing. Contrary to the paradigm that these aqSOA compounds are largely biogenic, radiocarbon-based source apportionments show that fossil precursors produced over one-half of the aqSOA molecules. Large fractions of fossil-derived aqSOA contribute substantially to the total water-soluble organic aerosol load and hence impact projections of both air quality and anthropogenic radiative forcing. Our findings reveal the importance of fossil emissions for aqSOA with effects on climate and air quality.

Abundance, chemical structure, and light absorption properties of humic-like substances (HULIS) and other organic fractions of forest aerosols in Hokkaido.

Atmospheric organic aerosol (OA) are considered as a significant contributor to the light absorption of OA, but its relationship with abundance, composition and sources are not understood well. In this study, the abundance, chemical structural characteristics, and light absorption property of HULIS and other low-to-high polar organics in PM0.95 collected in Tomakomai Experimental Forest (TOEF) were investigated with consideration of their possible sources. HULIS were the most abundant (51%), and correlation analysis revealed that biogenic secondary organic aerosols significantly contribute to HULIS. The mass spectra obtained using a high-resolution aerosol mass spectrometer (HR-AMS) showed that HULIS and highly polar water-soluble organic matter (HP-WSOM) were substantially oxygenated organic aerosol fractions, whereas water-insoluble organic matter (WISOM) had a low O/C ratio and more hydrocarbon-like structures. The WISOM fraction was the predominant light-absorbing organics. HULIS and WISOM showed a noticeable seasonal change in mass absorption efficiency (MAE365), which was highest in winter. Further, HULIS were shown to be less absorbing than those reported for urban sites. The findings in this study provide insights into the contribution of biogenic secondary OA on aerosol property and radiative forcing under varying contributions from other types of OA.

Tracing the biomass burning emissions over the Arabian Sea in winter season: Implications from the molecular distributions and relative abundances of sugar compounds.

The widespread haze pollution over South Asia typically occurs in winter, affecting the abundance of organic aerosols (OA) over the Arabian Sea due to prevailing meteorology. We determined the concentrations of biomass burning (BB) derived anhydrosugars (levoglucosan: Lev, galactosan: Gal, and mannosan: Man), sugars (glucose, fructose, sucrose, and trehalose) and sugar alcohols (arabitol, mannitol, erythritol, and inositol) over the Arabian Sea during a winter cruise (6-24 December 2018). Molecular distributions revealed predominance of levoglucosan or sucrose. Besides, levoglucosan strongly correlated with mannosan, galactosan, sugar alcohols and elemental carbon, emphasizing their BB-origin. Backward air mass trajectories intercepted by the satellite-based fire counts over the Indo-Gangetic Plain together with relationship between stable carbon isotopic composition of TC (δ13CTC) and levoglucosan-C to organic carbon (%), confirmed the impact of BB-derived OA. A comparison of Lev/Man (av. 16.2) and Lev/K+ (av. 0.27) ratios over the Arabian Sea with the source-emissions revealed their origin from crop-residue burning. Rather high concentrations of Lev over the Arabian Sea compared to those documented over the Bay of Bengal, East China Sea, Sea of Japan and the western North Pacific further suggests a stronger impact of BB in the continental outflow over this marine basin. Besides, Lev/K+ ratios in marine aerosols exponentially decreased with an apparent increase in ambient relative humidity and temperature over the Arabian Sea during the South Asian outflow, implying a photochemical oxidation of BBOA. Such field-based relationship of Lev with the meteorological parameters can be useful for modelling the impact of BBOA on the surface Ocean. Besides, the aeolian input of sugar-C and water-soluble organic carbon (WSOC) accounted for 83 % and 92 % of that riverine supply to the Arabian Sea, respectively. This means atmospheric dry-deposition of sugars is an important external source of dissolved organic compounds to the surface water.

Tracer-based characterization of fine carbonaceous aerosol in Beijing during a strict emission control period.

Strict emission controls were implemented in Beijing and the surrounding regions in the North China Plain to guarantee good air quality during the 2014 Asia-Pacific Economic Cooperation (APEC) summit. Thus, the APEC period provides a good opportunity to study the sources and formation processes of atmospheric organic aerosol. Here, fine particles (PM2.5, particulate matter with a diameter of 2.5 µm or less) collected in urban Beijing before and during the APEC period were analyzed for molecular tracers of primary and secondary organic aerosol (SOA). The primary organic carbon (POC) and secondary organic carbon (SOC) were also reconstructed using a tracer-based method. The concentrations of biogenic SOA tracers ranged from 1.09 to 34.5 ng m-3 (mean 10.3 ± 8.51 ng m-3). Monoterpene oxidation products were the largest contributor to biogenic SOA, followed by isoprene- and sesquiterpene-derived SOA. The concentrations of biogenic SOA tracers decreased by 50 % during the APEC, which was largely attributed to the implementation of emission controls by the Chinese government. The increasing mass fractions of biogenic SOA tracers from isoprene and sesquiterpene during the pollution episodes implied that their photooxidation processes contributed to the poor air quality in urban Beijing. The reconstructed biogenic and anthropogenic SOC and POC concentrations were 89.6 ± 96.8 ng m-3, 570 ± 611 ng m-3, and 2.49 ± 2.08 µg m-3, respectively, accounting for 21.9 ± 11.4 % of OC in total. Biomass-burning derived OC was the largest contributor to carbonaceous aerosol over the North China Plain. By comparing the results before and during the APEC, the emission controls effectively mitigated about 34 % of the estimated OC and were more effective at reducing SOC than POC. This suggests that the reduction of the primary organic aerosol loading is harder than SOA over the North China Plain.

Aerosol Proteinaceous Matter in Coastal Okinawa, Japan: Influence of Long-Range Transport and Photochemical Degradation.

The characteristics, sources, and atmospheric oxidation processes of marine aerosol proteinaceous matter (APM), including total proteins and free amino acids (FAAs), were investigated using a set of 1 year total suspended particulate (TSP) samples collected in the coastal area of Okinawa Island in the western North Pacific rim. The concentrations of APM at this site (total proteins: 0.16 ± 0.10 µg m-3 and total FAAs: 9.7 ± 5.6 ng m-3, annual average) are comparable to those of marine APM. The major FAA species of APM are also similar to previously reported marine APM with glycine as the dominant species (31%). Based on the different seasonal trends and weak correlations of total proteins and FAAs, we found that they were contributed by different sources, especially with the influence of long-range transport from the Asian continent of northern China and Mongolia and the oceanic area of the Bohai Sea, Yellow Sea, and East China Sea. The photochemical oxidation processes of high-molecular-weight proteins releasing FAAs (especially glycine) were also considered as an important factor influencing the characteristics of APM at this site. In addition, we propose a degradation process based on the correlation with ozone and ultraviolet radiation, emphasizing their roles in the degradation of proteins. Our findings help to deepen the understanding of atmospheric photochemical reaction processes of organic aerosols.

Unraveling the sources of atmospheric organic aerosols over the Arabian Sea: Insights from the stable carbon and nitrogen isotopic composition.

The isotopic composition of stable carbon (δ13C) and nitrogen (δ15N) in marine aerosols influenced by the continental outflows are useful proxies for understanding the aging and secondary formation processes. Every winter, the haze pollutants transported from South Asia significantly affect the chemical composition of marine atmospheric boundary layer of the Arabian Sea. Here, we assessed the δ13C of total carbon (TC) and δ15N of total nitrogen (TN) in marine aerosols collected over the Arabian Sea during a winter cruise (6-24 December 2018). TC (2.1-13.4 µg m-3) is strongly correlated with TN (0.9-5.0 µg m-3), likely because of their common source-emissions, biomass burning and fossil-fuel combustion in the Indo-Gangetic Plain and South Asia (corroborated by backward-air mass trajectories and satellite fire counts). Besides, the linear relationship between the mass ratios of water-soluble organic carbon (WSOC) to TC (0.04-0.65) and δ13CTC (-25.1‰ to -22.9‰) underscores the importance of aging process. This means oxidation of organic aerosols during transport not only influences the WSOC levels but also affects their δ13CTC. Likewise, the prevalent inverse linear relationship between the equivalent mass ratio of (NH4+/non-sea-salt- or nss-SO42-) and δ15NTN (+15.3‰ to +25.1‰) emphasizes the overall significance of neutralization reactions between major acidic ([nss-SO42-] ≫ [NO3-]) and alkaline species (NH4+) in aerosols. Higher δ15NTN values in winter than the spring inter-monsoon clearly emphasizes the significance of the anthropogenic combustion sources (i.e., biomass burning) in the South Asian outflow. A comparison of δ13CTC and δ15NTN with the source emissions revealed that crop-residue burning emissions followed by the coal fired power plants mostly dictate the atmospheric abundance of organic aerosols in the wider South Asian outflow.

Seasonal changes in stable carbon isotopic composition in the bulk aerosol and gas phases at a suburban site in Prague.

Isotope fractionation between the gas and aerosol phases is an important phenomenon for studying atmospheric processes. Here, for the first time, seasonally resolved stable carbon isotope ratio (δ13C) values are systematically used to study phase interactions in bulk aerosol and gaseous carbonaceous samples. Seasonal variations in the δ13C of total carbon (TC; δ13CTC) and water-soluble organic carbon (WSOC; δ13CWSOC) in fine aerosol particles (PM2.5) as well as in the total carbon of part of the gas phase (TCgas; δ13CTCgas) were studied at a suburban site in Prague, Czech Republic, Central Europe. Year-round samples were collected for the main and backup filters from 14 April 2016 to 1 May 2017 every 6 days with a 48 h sampling period (n = 66). During all seasons, the highest 13C enrichment was found in WSOC, followed by particulate TC, whereas the highest 13C depletion was found in gaseous TC. We observed a clear seasonal pattern for all δ13C, with the highest values in winter (avg. δ13CTC = -25.5 ± 0.8‰, δ13CWSOC = -25.0 ± 0.7‰, δ13CTCgas = -27.7 ± 0.5‰) and the lowest values in summer (avg. δ13CTC = -27.2 ± 0.5‰, δ13CWSOC = -26.4 ± 0.3‰, δ13CTCgas = -28.9 ± 0.3‰). This study supports the existence of different aerosol sources at the site during the year. Despite the different seasonal compositions of carbonaceous aerosols, the isotope difference (Δδ13C) between δ13CTC (aerosol) and δ13CTCgas (gas phase) was similar during the seasons (year avg. 1.97 ± 0.50‰). Moreover, Δδ13C between WSOC and TC in PM2.5 showed a difference between spring and winter, but in general, these values were also similar year-round (year avg. 0.71 ± 0.37‰). During the entire period, TCgas and WSOC were the most 13C-depleted and most 13C-enriched fractions, respectively, and although the resulting difference Δ(δ13CWSOC - Î´13CTCgas) was significant, it was almost invariant throughout the year (2.67 ± 0.44‰). The present study suggests that the stable carbon isotopic fractionation between the bulk aerosol and gas phases is probably not entirely dependent on the chemical composition of individual carbonaceous compounds from different sources.

Latitudinal difference in the molecular distributions of lipid compounds in the forest atmosphere in China.

Lipids are important biogenic markers to indicate the sources and chemical process of aerosol particles in the atmosphere. To better understand the influences of biogenic and anthropogenic sources on forest aerosols, total suspended particles (TSP) were collected at Mt. Changbai, Shennongjia, and Xishuangbanna that are located at different climatic zones in northeastern, central and southwestern China. n-Alkanes, fatty acids and n-alcohols were detected in the forest aerosols based on gas chromatography-mass spectrometry. The total concentrations of aliphatic compounds ranged from 15.3 ng m-3 to 566 ng m-3, and fatty acids were the most abundant (44-95%) followed by n-alkanes and n-alcohols. Low molecular weight- (LFAs) and unsaturated fatty acids (UnFAs) showed diurnal variation with higher concentrations during the nighttime in summer, indicating the potential impact from microbial activities on forest aerosols. The differences of oleic acid (C18:1) and linoleic acid (C18:2) concentrations between daytime and nighttime increased at lower latitude, indicating more intense photochemical degradation occurred at lower latitude regions. High levels of n-alkanes during daytime in summer with higher values of carbon preference indexes, combining the strong odd carbon number predominance with a maximum at C27 or C29, implied the high contributions of biogenic sources, e.g., higher plant waxes. In contrast, higher concentrations of low molecular weight n-alkanes were detected in winter forest aerosols. Levoglucosan showed a positive correlation (R2 > 0.57) with high- and low molecular weight aliphatic compounds in Mt. Changbai, but such a correlation was not observed in Shennongjia and Xishuangbanna. These results suggest the significant influence of biomass burning in Mt. Changbai, and fossil fuel combustion might be another important anthropogenic source of forest aerosols. This study adds useful information to the current understanding of forest organic aerosols at different geographical locations in China.

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.

Terrestrial lipid biomarkers in marine aerosols over the western North Pacific during 1990-1993 and 2006-2009.

Terrestrial lipid biomarkers are one of the key tracers in the studies of atmospheric aerosols. Here, we investigated such organic compounds in marine aerosols collected at Chichijima Island, the western North Pacific for two 4-year periods: 1990-1993 and 2006-2009. A homologous series of lipid biomarkers including C18-C37n-alkanes, C9-C34 fatty acids, and C14-C35 fatty alcohols were determined by gas chromatography/mass spectrometry (GC/MS). The atmospheric levels of these tracers increased from 1990-1993 to 2006-2009. Their seasonal trends were clearly characterized by winter-spring maxima and summer-fall minima. The relative abundance of the high-molecular-weight (HMW) n-alkanes (C25-C37) and n-alcohols (C20-C35) in total HMW lipids peaked in winter and winter/fall, respectively, whereas those of HMW fatty acids (C20-C34) peaked in summer. Air-mass backward trajectory analyses suggest that the Asian continent, Southeast Asia including tropical regions, and the Central Pacific are the main source regions. The seasonal shift and distribution of the carbon preference index and average chain length for the HMW lipids were controlled by the changes in climatic factors and source regions. The higher abundance of terrestrial lipids during 2006-2009 than 1990-1993 indicates a higher emission from terrestrial plantation in the 2000s than in the early 1990s in upwind regions of East Asia. Furthermore, HMW lipid compounds exhibited much stronger positive correlations with levoglucosan, a biomass-burning tracer, during 2006-2009 than 1990-1993, suggesting that biomass-burning emissions contributed more significantly in this century.