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Linking the amount of organic matter (OM) in sea spray aerosols (SSAs) to biological processes in ocean surface is essential for understanding marine aerosol formation and their potential to affect cloud formation. To date, chlorophyll (Chl) a concentration has been widely used as a surrogate for surface phytoplankton biomass or productivity to predict the relative abundance of OM in SSAs (OM

Organic aerosol (OA), a major component of atmospheric aerosol, is considered to be one of the key players in atmospheric radiative balance and climate change. Chromophoric OA, termed as brown carbon (BrC), is a component that can absorb solar radiation in the ultraviolet and short-wavelength visible regions and is composed of a wide range of poorly characterized compounds. Whereas light absorption properties were analyzed to characterize chromophoric OA, fluorescent properties also provide information on them. In this study, the fluorescence property of solvent extractable organics in submicron aerosol particles collected in a forest in the cool-temperate zone of northern Japan, was characterized.Aerosol samples were collected on quartz filters (cut-off diameter: ≤0.95 micrometer) in Tomakomai Experimental Forest of Hokkaido University. Organic aerosol components in the samples were extracted and fractionated on the basis of their polarity by the combination of solvent extraction and solid-phase extraction methods. Water-soluble organic matter (WSOM) and water-insoluble organic matter (WISOM) were extracted sequentially by using multiple solvents. Two fractions, humic-like substance (HULIS) and highly-polar water-soluble organic matter (HP-WSOM), were fractionated from WSOM by solid phase extraction. The excitation−emission matrices (EEMs) were measured using a fluorescence spectrometer, and the fluorescence property of the extracts was characterized by the classification of EEM profiles using a Parallel Factor (PARAFAC) model.From the PARAFAC analysis, five types of fluorescent components were identified for each of WSOM and WISOM fractions. A fluorescence component with the characteristics reported to be associated with (HULIS) accounted for large fractions of the fluorescence from WSOM and WISOM (mean: 68% and 84%, respectively). The relative contribution of the fluorescent components for WSOM shows a clear seasonal variation of the characteristics of WSOM. Furthermore, from each of HULIS and HP-WSOM fractions, five types of fluorescent components were identified. Fluorescence components with the characteristics of protein-like compounds identified in previous EEM studies accounted for a large fraction of the fluorescence from HP-WSOM (mean: 53%), whereas the contribution of protein-like compounds was smaller in the case of the HULIS fraction (mean: 23%).

Water-soluble organic nitrogen (WSON) affects the formation, chemical transformations, hygroscopicity, and acidity of organic aerosols as well as biogeochemical cycles of nitrogen. However, large uncertainties exist in the origins and formation processes of WSON. Submicrometer aerosol particles were collected at a suburban forest site in Tokyo in summer 2015 to investigate the relative impacts of anthropogenic and biogenic sources on WSON formations and their linkages with aerosol liquid water (ALW). The concentrations of WSON (ave. 225 ± 100 ngN m

Biogenic organic aerosols can affect cloud condensation nuclei (CCN) properties, and subsequently impact climate change. Large uncertainties exist in how the difference in the types of terrestrial biogenic sources and the abundance of organics relative to sulfate affect CCN properties. For the submicron water-soluble aerosols collected for two years in a cool-temperate forest in northern Japan, we show that the hygroscopicity parameter κCCN (0.44 ± 0.07) exhibited a distinct seasonal trend with a minimum in autumn (κCCN = 0.32–0.37); these κCCN values were generally larger than that of ambient particles, including water-insoluble fractions. The temporal variability of κCCN was controlled by the water-soluble organic matter (WSOM)-to-sulfate ratio (R2 > 0.60), where the significant reduction of κCCN in autumn was linked to the increased WSOM/sulfate ratio. Positive matrix factorization analysis indicates that α-pinene-derived secondary organic aerosol (SOA) substantially contributed to the WSOM mass (~75%) in autumn, the majority of which was attributable to emissions from litter/soil microbial activity near the forest floor. These findings suggest that WSOM, most likely α-pinene SOA, originated from the forest floor can significantly suppress the aerosol CCN activity in cool-temperate forests, which have implications for predicting climate effects by changes in biogenic emissions in future.

Change in secondary organic aerosols (SOAs) has been predicted to be highly uncertain in the future atmosphere in Asia. To better quantify the SOA change, we examine the sub-decadal (2001–2008) trend in major surrogate compounds (C2–C10 diacids) of SOA in atmospheric aerosols from Gosan site on Cheju Island, South Korea. The Gosan site is influenced by pollution outflows from eastern Asia. The molecular distributions of diacids were characterized by the predominance of oxalic (C2) acid followed by malonic (C3) and succinic (C4) acids in each year. The seasonal variations in diacids in each year were characterized by the highest concentrations of saturated diacids in spring and unsaturated diacids in winter. The consistent molecular distributions and seasonal variations along with significantly similar air mass transport patterns are indicative of similar pollution sources for diacids in eastern Asia on a sub-decadal scale. However, the intensity of the pollution sources has increased as evidenced by the increases in major diacids at the rate of 3.9–47.4 % per year, particularly in April. The temporal variations in atmospheric tracer compounds (carbon monoxide, levoglucosan, 2-methyltetrols, pinic acid, glyoxylic acid, glyoxal and methylglyoxal) suggest that the increases in diacids are due to enhanced precursor emissions associated with more anthropogenic than biogenic activities followed by the compounds' chemical processing in the atmosphere. The trends in diacids contrast with the reported decreases in sulfate, nitrate and ammonium in recent years in eastern Asia. This study demonstrates that recent pollution control strategies in eastern Asia were not able to decrease organic acidic species in the atmosphere. The increases in water-soluble organic acid fraction could modify the aerosol organic composition and its sensitivity to climate relevant physical properties.

Terrestrial biogenic emissions of organic matter can affect the optical properties of atmospheric aerosols and thus impact the radiation budget. To investigate this, the chemical parameters of submicrometer water-soluble aerosols (WSA) collected on filters were compared to optical properties measured by a sky radiometer at a cool-temperate forest site in northern Japan. From June to December 2015, the WSA samples were collected within the forest canopy, while aerosol optical depth (AOD), single scattering albedo (SSA), absorption Angstrom exponent (AAE), and scattering Angstrom exponent (SAE) were retrieved above the canopy. The optical properties were compared with the filter-based chemical parameters only when the vertical transport of aerosol particles from the forest canopy to the air above it was significant. The result showed that the AOD and the mass concentrations of WSA exhibited similar and distinct seasonal variations with peaks in summer and autumn. In summer, sulfate accounted for 60% of the mass of WSA, which was linked to a high SSA (>0.95), low AAE (1.15 ± 0.84), and low SAE (1.25 ± 0.22). In contrast, water-soluble organic matter (WSOM) accounted for 70% of the mass of WSA in autumn. This large fraction of WSOM was associated with a decrease in SSA (0.90–0.95) and an increase in AAE (2.45 ± 0.91) and SAE (1.46 ± 0.15). The results suggest that in summer, aerosol particles with a greater size range corresponded to aerosol chemical compositions dominated by sulfate. In contrast, smaller particles with a strong light absorption at shorter wavelengths, were likely important in autumn and associated with a composition dominated by WSOM. The majority of WSOM in autumn has previously been associated with emissions of α-pinene from the forest floor and the subsequent formation of biogenic secondary organic aerosols (BSOA). This study indicates that α-pinene-derived SOAs, mostly originating from the forest floor, were associated with a summer to autumn decrease in SSA. This process can modulate the radiative effect on a regional scale.

Thirty water-soluble organic species, including dicarboxylic acids, ketocarboxylic acids, α-dicarbonyls, fatty acids and benzoic acid were determined as well as organic carbon (OC), elemental carbon (EC) and water-soluble organic carbon (WSOC) in PM2.5 samples collected during the Campaign of Air Quality Research in Beijing 2007 (CAREBeijing-2007) in the urban and suburban areas of Beijing. The objective of this study is to identify the influence of traffic emissions and regional transport to the atmosphere in Beijing during summer. PM2.5 samples collected with or without traffic restriction in Beijing are selected to evaluate the effectiveness of local traffic restriction measures on air pollution reduction. The average concentrations of the total quantified bifunctional organic compounds (TQBOCs), total fatty acids and benzoic acid during the entire sampling period were 1184±241, 597±159 and 1496±511 ng m−3 in Peking University (PKU), and 1050±303, 475±114 and 1278±372 ng m−3 in Yufa, Beijing. Oxalic acid (C2) was found as the most abundant dicarboxylic acid at PKU and Yufa followed by phthalic acid (Ph). A strong even carbon number predominance with the highest level at stearic acid (C18:0), followed by palmitic acid (C16:0) was found for fatty acids. According to the back trajectories modeling results, the air masses were found to originate mainly from the northeast, passing over the southeast or south of Beijing (heavily populated, urbanized and industrialized areas), during heavier pollution events, whereas they are mainly from the north or northwest sector (mountain areas without serious anthropogenic pollution sources) during less pollution events. The data with wind only from the same sector (minimizing the difference from regional contribution) but with and without traffic restriction in Beijing were analyzed to evaluate the effectiveness of local traffic restriction measures on the reduction of local air pollution in Beijing. The results suggested that the traffic restriction measures can reduce the air pollutants, but the decrease of pollutants is generally smaller in Yufa compared to that in PKU. Moreover, an enhancement of EC value indicates more elevated primary emissions in Yufa during restriction periods than in non-restriction periods. This study demonstrates that even when primary exhaust was controlled by traffic restriction, the contribution of secondary organic species formed from photochemical processes was critical with long-range atmospheric transport of pollutants.

The seasonal variations in aerosol water-soluble organic nitrogen (WSON) concentrations measured in a deciduous forest canopy over an approximately 30 month period were investigated for possible sources in the forest. The WSON concentrations (average 157 ± 127 ng N m−3) and WSON/water-soluble total nitrogen mass fractions (average 20 ± 11%) in the total suspended particulate matter exhibited a clear seasonal cycle with maxima in early summer. The WSON mass was found to reside mostly in the fine-mode size range (Dp 1.9 µm), which was similar to the size distributions of sugar compounds, indicating that the major WSON sources in autumn are associated with primary biological emissions. The vertical differences in WSON concentrations suggest that the water-soluble organic aerosol is enriched with nitrogen below the canopy level relative to the forest floor. The WSON concentration increased with enhanced hydrogen ion concentrations in aerosol in the early summer, indicating that aerosol acidity associated with anthropogenic sources outside the forest likely plays an important role in the formation of WSON in that season. The study suggests that multiple sources of WSON within the forest canopy may dominate over others in specific seasons, providing insights into WSON formation processes in forest environments.

Organic aerosols are ubiquitous in the earth’s atmosphere. They have been extensively studied in urban, rural and marine environments. However, little is known about the fluorescence properties of water-soluble organic carbon (WSOC) or their transport to and distribution in the polar regions. Here, we present evidence that fluorescent WSOC is a substantial component of High Arctic aerosols. The ratios of fluorescence intensity of protein-like peak to humic-like peak generally increased from dark winter to early summer, indicating an enhanced contribution of protein-like organics from the ocean to Arctic aerosols after the polar sunrise. Such a seasonal pattern is in agreement with an increase of stable carbon isotope ratios of total carbon (δ13CTC) from −26.8‰ to −22.5‰. Our results suggest that Arctic aerosols are derived from a combination of the long-range transport of terrestrial organics and local sea-to-air emission of marine organics, with an estimated contribution from the latter of 8.7–77% (mean 45%).

To better understand the sources of PM10 samples in Mumbai, India, aerosol chemical composition, i.e., total carbon (TC), organic carbon (OC), elemental carbon (EC), water-soluble organic carbon (WSOC), and inorganic ions were studied together with specific markers such as methanesulfonate (MSA), oxalic acid (C2), azelaic acid (C9), and levoglucosan. The results revealed that biofuel/biomass burning and fossil fuel combustion are the major sources of the Mumbai aerosols. Nitrogen-isotopic (δ15N) composition of aerosol total nitrogen, which ranged from 18.1 to 25.4‰, also suggests that biofuel/biomass burning is a predominate source in both the summer and winter seasons. Aerosol mass concentrations of major species increased 3–4 times in winter compared to summer, indicating enhanced emission from these sources in the winter season. Photochemical production tracers, C2 diacid and nssSO42−, do not show diurnal changes. Concentrations of C2 diacid and WSOC show a strong correlation (r2 = 0.95). In addition, WSOC to OC (or TC) ratios remain almost constant for daytime (0.37 ± 0.06 (0.28 ± 0.04)) and nighttime (0.38 ± 0.07 (0.28 ± 0.06)), suggesting that mixing of fresh secondary organic aerosols is not significant and the Mumbai aerosols are photochemically well processed. Concentrations of MSA and C9 diacid present a positive correlation (r2 = 0.75), indicating a marine influence on Mumbai aerosols in addition to local/regional influence. Backward air mass trajectory analyses further suggested that the Mumbai aerosols are largely influenced by long-range continental and regional transport. Stable C-isotopic ratios (δ13C) of TC ranged from −27.0 to −25.4‰, with slightly lower average (−26.5 ± 0.3‰) in summer than in winter (−25.9 ± 0.3‰). Positive correlation between WSOC/TC ratios and δ13C values suggested that the relative increment in 13C of wintertime TC may be caused by prolonged photochemical processing of organic aerosols in this season. This study suggests that in winter, the tropical aerosols are more aged due to longer residence time in the atmosphere than in summer aerosols. However, these conclusions are based on the analysis of a limited number of samples (n=25) and more information on this topic may be needed from other similar coastal sites in future.

To better understand the origins of aerosol nitrogen, we measured concentrations of total nitrogen (TN) and its isotope ratios (?15N) in tropical Indian aerosols (PM10) collected from Chennai (13.04�N; 80.17�E) on day- and night-time basis in winter and summer 2007. We found high ?15N values (+15.7 to +31.2�) of aerosol N (0.3-3.8 ?g m-3), in which NH4 + is the major species (78%) with lesser contribution from NO3 - (6%). Based on the comparison of ?15N in Chennai aerosols with those reported for atmospheric aerosols from mid-latitudes and for the particles emitted from point sources (including a laboratory study), as well as the ?15N ratios of cow-dung samples (this study), we found that the atmospheric aerosol N in Chennai has two major sources; animal excreta and bio-fuel/biomass burning from South and Southeast Asia. We demonstrate that a gas-to-particle conversion of NH3 to NH4HSO4 and (NH4)2SO4 and the subsequent exchange reaction between NH3 and NH4 + are responsible for the isotopic enrichment of 15N in aerosol nitrogen. � 2010 Elsevier Ltd.