In Situ Surface Tension Measurement of Deliquesced Aerosol Particles.

The surface tension of aerosol particles can potentially affect cloud droplet activation. Hence, direct measurement of the surface tensions of deliquesced aerosol particles is essential but is challenging. Here, we report in situ surface tension measurements based on a novel method that couples a linear quadrupole electrodynamic balance (EDB) with quasi-elastic light scattering (QELS). The EDB-QELS is validated using surface tension measurements of atmospherically relevant inorganic and organic droplets. The surface tension results reasonably agree with the reference values in the range of ∼50-90 mN m-1. We find a significant size dependence for sodium chloride droplets containing surface-active species (sodium dodecyl sulfate) in the size range of ∼5-18 µm. The surface tension increases from ∼55 to 80 mN m-1 with decreased size. Relative humidity (RH)-dependent surface tensions of mixed ammonium sulfate (AS) and polyethylene glycol droplets reveal the onset of liquid-liquid phase separation. Droplets containing water-soluble matter extracted from ambient aerosol samples and 2.3-2.9 M AS exhibit a ∼30% reduction in surface tension in the presence of ∼50 mmol-C L-1 water-soluble organic carbon, compared to pure water (∼72 mN m-1). The approach can offer size-resolved and RH-dependent surface tension measurements of deliquesced aerosol particles.

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.

Seasonal and temporal variations of ambient aerosols in a deciduous broadleaf forest from northern Japan: Contributions of biomass burning and biological particles.

Total suspended particulate (TSP) samples were collected in a deciduous broadleaf forest in Sapporo, Hokkaido, Japan, from January to December 2010 to understand the molecular composition and abundance of sugar compounds (SCs) in atmospheric aerosols. We analyzed the samples for anhydrosugars, primary sugars, and sugar alcohols using a gas chromatograph-mass spectrometer. The annual mean concentrations of total SCs ranged from 16.1 to 1748 ng m-3 (avg. 311 ng m-3) with maxima in spring (avg. 484 ng m-3) and minima in winter (avg. 28.2 ng m-3). Primary sugars and sugar alcohols followed the seasonal pattern of total SCs. High levels of anhydrosugars in winter (avg. 22.9 ng m-3) suggest a contribution of biomass burning from domestic heating due to lower ambient temperature. The high levels of arabitol and mannitol in spring followed by summer and autumn denote the contribution from multiple sources, i.e., growing vegetation and fungal spores in Sapporo forest. We observed an enhanced contribution of bioaerosols emitted from plant blossoms in spring and leaf decomposition in autumn. The identical seasonal trends of glucose and trehalose implied their similar sources in forest aerosols. Conversely, the highest concentration of sucrose in spring was due to the pollen emissions by blooming plants. Positive matrix factorization (PMF) analyses of the SCs suggested that organic aerosols in the deciduous forest are associated with the emissions from multiple sources, including vegetation, microbes, pollens, and wintertime biomass burning. The PMF analysis also suggested that vegetation is the primary carbon source in the forest atmosphere. The diagnostic mass ratios of levoglucosan to mannosan demonstrated the dominance of softwood burning. We noted that the meteorological parameters substantially affect the emission sources and seasonal concentrations of SCs in the deciduous forest.

New index of organic mass enrichment in sea spray aerosols linked with senescent status in marine phytoplankton.

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 (OMSSA). Here we show a new index to present OMSSA using concentrations of Chl a and chlorophyllide (Chllide) a, which is a breakdown product of Chl a and has been used as a biomarker of senescent algal cells. The index was compared with submicrometer OMSSA, based on surface seawater and aerosol samples obtained during the pre-bloom in the western subarctic Pacific. Our results showed that the OMSSA was highly correlated with this unique index, suggesting that the OMSSA was closely linked with senescent algal cells and/or cell lysis. Furthermore, the hygroscopicity parameters κ derived from water-extracted SSA samples implied a reduction in the SSA hygroscopicity with increasing senescent status of phytoplankton. The index can represent OMSSA on a timescale of a day during the pre-bloom period, which should be further examined over different oceanic regions.

Aerosol Liquid Water Promotes the Formation of Water-Soluble Organic Nitrogen in Submicrometer Aerosols in a Suburban Forest.

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-3) and ALW exhibited peaks during nighttime, which showed a significant positive correlation, suggesting that ALW significantly contributed to WSON formation. Further, the thermodynamic predictions by ISORROPIA-II suggest that ALW was primarily driven by anthropogenic sulfate. Our analysis, including positive matrix factorization, suggests that aqueous-phase reactions of ammonium and reactive nitrogen with biogenic volatile organic compounds (VOCs) play a key role in WSON formation in submicrometer particles, which is particularly significant in nighttime, at the suburban forest site. The formation of WSON associated with biogenic VOCs and ALW was partly supported by the molecular characterization of WSON. The overall result suggests that ALW is an important driver for the formation of aerosol WSON through a combination of anthropogenic and biogenic sources.

Chemical transfer of dissolved organic matter from surface seawater to sea spray water-soluble organic aerosol in the marine atmosphere.

It is critical to understand how variations in chemical composition in surface seawater (SSW) affect the chemistry of marine atmospheric aerosols. We investigated the sea-to-air transfer of dissolved organic carbon (DOC) via cruise measurements of both ambient aerosols and SSW in the Oyashio and its coastal regions, the western subarctic Pacific during early spring. Sea spray aerosols (SSAs) were selected based on the stable carbon isotope ratio of water-soluble organic carbon (WSOC) (δ13CWSOC) and concentrations of glucose as a molecular tracer in marine aerosols together with local surface wind speed data. For both SSA and SSW samples, excitation-emission matrices were obtained to examine the transfer of fluorescent organic material. We found that the ratios of fluorescence intensity of humic-like and protein-like substances in the submicrometer SSAs were significantly larger than those in the bulk SSW (~63%). This ratio was also larger for the supermicrometer SSAs than for the SSW. The results suggest significant decomposition of protein-like DOC on a timescale of <12-24 h and/or preferential production of humic-like substances in the atmospheric aerosols regardless of the particle size. This study provides unique insights into the complex transfer of DOC from the ocean surface to the atmosphere.

Evidence of a reduction in cloud condensation nuclei activity of water-soluble aerosols caused by biogenic emissions in a cool-temperate forest.

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.

Characterization of Chromophoric Water-Soluble Organic Matter in Urban, Forest, and Marine Aerosols by HR-ToF-AMS Analysis and Excitation-Emission Matrix Spectroscopy.

Chromophoric water-soluble organic matter in atmospheric aerosols potentially plays an important role in aqueous reactions and light absorption by organics. The fluorescence and chemical-structural characteristics of the chromophoric water-soluble organic matter in submicron aerosols collected in urban, forest, and marine environments (Nagoya, Kii Peninsula, and the tropical Eastern Pacific) were investigated using excitation-emission matrices (EEMs) and a high-resolution aerosol mass spectrometer. A total of three types of water-soluble chromophores, two with fluorescence characteristics similar to those of humiclike substances (HULIS-1 and HULIS-2) and one with fluorescence characteristics similar to those of protein compounds (PLOM), were identified in atmospheric aerosols by parallel factor analysis (PARAFAC) for EEMs. We found that the chromophore components of HULIS-1 and -2 were associated with highly and less-oxygenated structures, respectively, which may provide a clue to understanding the chemical formation or loss of organic chromophores in atmospheric aerosols. Whereas HULIS-1 was ubiquitous in water-soluble chromophores over different environments, HULIS-2 was abundant only in terrestrial aerosols, and PLOM was abundant in marine aerosols. These findings are useful for further studies regarding the classification and source identification of chromophores in atmospheric aerosols.

Secondary production of organic aerosols from biogenic VOCs over Mt. Fuji, Japan.

We investigated organic molecular compositions of summertime aerosols collected at the summit of Mt. Fuji (3776 m a.s.l.) in July-August 2009. More than 120 organic species were identified using GC/MS. Concentrations of both primary and secondary organic aerosol (SOA) tracers in whole-day samples were 4-20 times higher than those in nighttime samples, suggesting that valley breeze is an efficient mechanism to uplift the aerosols and precursors from the ground surface to mountaintop in daytime. Using a tracer-based method, we estimated the concentrations of secondary organic carbon (SOC) derived from isoprene, α/ß-pinene, and ß-caryophyllene to be 2.2-51.2 ngC m(-3) in nighttime and 227-1120 ngC m(-3) during whole-day. These biogenic SOCs correspond to 0.80-31.9% and 26.8-57.4% of aerosol organic carbon in nighttime and whole-day samples, respectively. This study demonstrates that biogenic SOA, which is controlled by the valley breeze, is a significant fraction of free tropospheric aerosols over Mt. Fuji in summer.

Performance of a newly designed continuous soot monitoring system (COSMOS).

We designed a continuous soot monitoring system (COSMOS) for fully automated, high-sensitivity, continuous measurement of light absorption by black carbon (BC) aerosols. The instrument monitors changes in transmittance across an automatically advancing quartz fiber filter tape using an LED at a 565 nm wavelength. To achieve measurements with high sensitivity and a lower detectable light absorption coefficient, COSMOS uses a double-convex lens and optical bundle pipes to maintain high light intensity and signal data are obtained at 1000 Hz. In addition, sampling flow rate and optical unit temperature are actively controlled. The inlet line for COSMOS is heated to 400 degrees C to effectively volatilize non-refractory aerosol components that are internally mixed with BC. In its current form, COSMOS provides BC light absorption measurements with a detection limit of 0.45 Mm(-1) (0.045 microg m(-3) for soot) for 10 min. The unit-to-unit variability is estimated to be within +/- 1%, demonstrating its high reproducibility. The absorption coefficients determined by COSMOS agreed with those by a particle soot absorption photometer (PSAP) to within 1% (r2 = 0.97). The precision (+/- 0.60 Mm(-1)) for 10 min integrated data was better than that of PSAP and an aethalometer under our operating conditions. These results showed that COSMOS achieved both an improved detection limit and higher precision for the filter-based light absorption measurements of BC compared to the existing methods.