Fluorescent water-soluble organic aerosols in the High Arctic atmosphere

Water-soluble organic aerosols (OA) are an important component of air particles and one of the key drivers that impact both climate and human health. Understanding the processes involving water-soluble OA depends on how well the chemical composition of this aerosol component is decoded. Yet, obtaining detailed information faces several challenges, including water-soluble OA collection, extraction, and chemical complexity. This review highlights the multidimensional non-targeted analytical strategies that have been developed and employed for providing new insights into the structural and molecular features of water-soluble organic components present in air particles. First, the most prominent high-resolution mass spectrometric methods for near real-time measurements of water-soluble OA and their limitations are discussed. Afterward, a special emphasis is given to the degree of compositional information provided by offline multidimensional analytical techniques, namely excitation–emission (EEM) fluorescence spectroscopy, high-resolution mass spectrometry and two-dimensional nuclear magnetic resonance (NMR) spectroscopy and their hyphenation with chromatographic systems. The major challenges ahead on the application of these multidimensional analytical strategies for OA research are also addressed so that they can be used advantageously in future studies.

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Characterisation of water-soluble organic aerosols at a site on the southwest coast of India

Journal of Atmospheric Chemistry ◽

10.1007/s10874-015-9322-4 ◽

2015 ◽

Vol 73 (2) ◽

pp. 181-205 ◽

Cited By ~ 8

Author(s):

Prashant Hegde ◽

Kimitaka Kawamura ◽

I. A. Girach ◽

Prabha R. Nair

Keyword(s):

Organic Aerosols ◽

Water Soluble ◽

Southwest Coast Of India ◽

Southwest Coast ◽

A Site

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Exploring water-soluble organic aerosols structures in urban atmosphere using advanced solid-state 13C NMR spectroscopy

Atmospheric Environment ◽

10.1016/j.atmosenv.2020.117503 ◽

2020 ◽

Vol 230 ◽

pp. 117503

Author(s):

Regina M.B.O. Duarte ◽

Pu Duan ◽

Jingdong Mao ◽

Wenying Chu ◽

Armando C. Duarte ◽

...

Keyword(s):

Solid State ◽

Nmr Spectroscopy ◽

13C Nmr ◽

Organic Aerosols ◽

13C Nmr Spectroscopy ◽

Water Soluble ◽

Urban Atmosphere ◽

Solid State 13C Nmr

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Contribution of dissolved organic matter to submicron water-soluble organic aerosols in the marine boundary layer over the eastern equatorial Pacific

10.5194/acp-2016-164 ◽

2016 ◽

Cited By ~ 1

Author(s):

Yuzo Miyazaki ◽

Sean Coburn ◽

Kaori Ono ◽

David T. Ho ◽

R. Bradley Pierce ◽

...

Keyword(s):

Boundary Layer ◽

Organic Carbon ◽

Marine Boundary Layer ◽

Organic Aerosols ◽

Equatorial Pacific ◽

Water Soluble ◽

Total Carbon ◽

Stable Carbon ◽

Study Region ◽

Eastern Equatorial Pacific

Abstract. Stable carbon isotopic compositions of water-soluble organic carbon (WSOC) and organic molecular markers were measured to investigate the relative contributions of the sea-surface sources to the water-soluble fraction of submicron organic aerosols collected over the eastern equatorial Pacific during the Tropical Ocean tRoposphere Exchange of Reactive halogens and Oxygenated VOCs (TORERO)/KA-12-01 cruise. On average, the water-soluble organic fraction of the total carbon (TC) mass in submicron aerosols was ~ 30–35 % in the open oceans, whereas it was ~ 60 % in the coastal oceans. The average stable carbon isotope ratio of WSOC (δ13CWSOC) was −19.8 ± 2.0 ‰, which was systematically higher than that of TC (δ13CTC) (−21.8 ± 1.4 ‰). We found that in both coastal and open oceans, the δ13CWSOC was close to the typical values of δ13C for dissolved organic carbon (DOC), ranging from −22 ‰ to −20 ‰ in surface seawater of tropical Pacific oceans. This suggests an enrichment of marine biological products in WSOC aerosols in the study region regardless of the oceanic area. In particular, enhanced levels of WSOC and biogenic organic marker compounds together with high values of WSOC/TC (~ 60 %) and δ13CWSOC were observed over upwelling areas and phytoplankton blooms, which was attributed to planktonic tissues being more enriched in δ13C. The δ13C analysis estimated that on average, marine sources contribute ~ 90 ± 25 % of the aerosol carbon, indicating the predominance of marine-derived carbon in the submicron WSOC. This conclusion is supported by Lagrangian trajectory analysis, which suggests that the majority of the sampling points on the ship had been exposed to marine boundary layer air for more than 80 % of the time during the previous 7 days. The combined analysis of the δ13C and monosaccharides, such as glucose and fructose, indicated that DOC concentration was the major factor controlling the concentration levels of the submicron WSOC regardless of the oceanic areas over the study region.

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High time-resolved measurement of stable carbon isotope composition in water-soluble organic aerosols: method optimization and a case study during winter haze in East China

10.5194/acp-2018-1056 ◽

2018 ◽

Author(s):

Wenqi Zhang ◽

Yan-Lin Zhang ◽

Fang Cao ◽

Yankun Xiang ◽

Yuanyuan Zhang ◽

...

Keyword(s):

Organic Carbon ◽

Carbon Isotope ◽

Isotope Composition ◽

Stable Carbon Isotope ◽

Organic Aerosols ◽

Carbon Isotope Composition ◽

Water Soluble ◽

High Time ◽

Stable Carbon ◽

Air Mass

Abstract. Water soluble organic carbon (WSOC) is a significant fraction of organic carbon (OC) in atmospheric aerosols. WSOC is of great interest due to its significant effects on atmospheric chemistry, the Earth’s climate and human health. Stable carbon isotope (δ13C) can be used to track the potential sources and investigate atmospheric processes of organic aerosols. In this study, a method of simultaneously measuring the mass concentration and δ13C values of WSOC from aerosol samples is established by coupling the Gas Bench II preparation device with isotopic ratio mass spectrometry. The precision and accuracy of isotope determination is better than 0.17 ‰ and 0.5 ‰, respectively, for samples containing carbon larger than 5 μg. This method is then applied for the high time-resolution aerosol samples during a severe wintertime haze period in Nanjing, East China. WSOC varies between 3–32 μg m−3, whereas δ13C-WSOC ranges from −26.24 ‰ to −23.35 ‰. Three different episodes (e.g., namely the Episode 1, the Episode 2, the Episode 3) are identified in the sampling period, showing a different tendency of δ13C-WSOC with the accumulation process of WSOC aerosols. The increases in both the WSOC mass concentrations and the δ13C-WSOC values in the Episode 1 indicate that WSOC is subject to a substantial photochemical aging during the air mass transport. In the Episode 2, the decline of the δ13C-WSOC is accompanied by the increase in the WSOC mass concentrations, which is associated with regional-transported biomass burning emissions. In the Episode 3, heavier isotope (13C) is exclusively enriched in total carbon (TC) compares to WSOC aerosols. This suggests that water-insoluble carbon may contain 13C-enriched components such as dust carbonate which is supported by the enhanced Ca2+ concentrations and air mass trajectories analysis. The present study provides a novel method to determine stable carbon isotope composition of WSOC and it offers a great potential to better understand the source emission, the atmospheric aging and the secondary production of water soluble organic aerosols.

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Evidence of formation of submicrometer water-soluble organic aerosols at a deciduous forest site in northern Japan in summer

Journal of Geophysical Research Atmospheres ◽

10.1029/2012jd018250 ◽

2012 ◽

Vol 117 (D19) ◽

pp. n/a-n/a ◽

Cited By ~ 25

Author(s):

Yuzo Miyazaki ◽

Jinsang Jung ◽

Pingqing Fu ◽

Yasuko Mizoguchi ◽

Katsumi Yamanoi ◽

...

Keyword(s):

Deciduous Forest ◽

Organic Aerosols ◽

Water Soluble ◽

Forest Site ◽

Northern Japan

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Structural signatures of water-soluble organic aerosols in contrasting environments in South America and Western Europe

Environmental Pollution ◽

10.1016/j.envpol.2017.05.011 ◽

2017 ◽

Vol 227 ◽

pp. 513-525 ◽

Cited By ~ 14

Author(s):

Regina M.B.O. Duarte ◽

João T.V. Matos ◽

Andreia S. Paula ◽

Sónia P. Lopes ◽

Guilherme Pereira ◽

...

Keyword(s):

South America ◽

Western Europe ◽

Organic Aerosols ◽

Water Soluble

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Origin of water-soluble organic aerosols at the Maïdo high-altitude observatory, Réunion Island in the tropical Indian Ocean

10.5194/acp-2021-277 ◽

2021 ◽

Author(s):

Sharmine Akter Simu ◽

Yuzo Miyazaki ◽

Eri Tachibana ◽

Henning Finkenzeller ◽

Jérôme Brioude ◽

...

Keyword(s):

Indian Ocean ◽

High Altitude ◽

Radiative Forcing ◽

Numerical Models ◽

Stable Carbon Isotope ◽

Organic Aerosols ◽

Dry Season ◽

Water Soluble ◽

Spatial And Temporal Variation ◽

Wet Season

Abstract. The tropical and subtropical Indian Ocean (IO) is expected to be a significant source of water-soluble organic aerosols (WSOAs), which are important factors relevant to cloud condensation nuclei and ice nuclei of aerosol particles. Current atmospheric numerical models significantly underestimate the budget of organic aerosols and their precursors, especially over tropical oceans. This is primarily due to poor knowledge of sources and the paucity of observations of these parameters considering spatial and temporal variation over the tropical open ocean. To evaluate the contribution of sources to WSOA as well as their formation processes, submicrometer aerosol sampling was conducted at the high-altitude Maïdo observatory (21.1° S, 55.4° E, 2,160 m a.s.l), located on the remote island of La Réunion in the southwest IO. The aerosol samples were continuously collected during local daytime and nighttime, which corresponded to the ambient conditions of the marine boundary layer (MBL) and free troposphere (FT), respectively, from March 15 to May 24, 2018. Chemical analysis showed that organic matter was the dominant component of submicrometer water-soluble aerosol (~45 ± 17 %) during the wet season (March 15–April 23), whereas sulfate dominated (~77 ± 17 %) during the dry season (April 24–May 24). Measurements of the stable carbon isotope ratio of water-soluble organic carbon (WSOC) suggested that marine sources contributed significantly to the observed WSOC mass in both the MBL and the FT in the wet season, whereas a mixture of marine and terrestrial sources contributed to WSOC in the dry season. The distinct seasonal changes in the dominant source of WSOC were also supported by Lagrangian trajectory analysis. Positive matrix factorization analysis suggested that marine secondary OA dominantly contributed to the observed WSOC mass (~70 %) during the wet season, whereas mixtures of marine and terrestrial sources contributed during the dry season in both MBL and FT. Overall, this study demonstrates that the effect of marine secondary sources is likely important up to the FT in the wet season, which may be responsible for cloud formation as well as direct radiative forcing over oceanic regions.

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A molecular-level approach for characterizing water-insoluble components of ambient organic aerosol particulates using ultra-high resolution mass spectrometry

Atmospheric Chemistry and Physics Discussions ◽

10.5194/acpd-14-10393-2014 ◽

2014 ◽

Vol 14 (7) ◽

pp. 10393-10427

Author(s):

A. S. Willoughby ◽

A. S. Wozniak ◽

P. G. Hatcher

Keyword(s):

Organic Matter ◽

Chemical Composition ◽

High Resolution Mass Spectrometry ◽

Organic Aerosols ◽

Organic Aerosol ◽

Water Soluble ◽

Proton Nuclear Magnetic Resonance ◽

Aerosol Sample ◽

Resonance Spectroscopy ◽

Ion Cyclotron Resonance

Abstract. The chemical composition of organic aerosols in the atmosphere is strongly influenced by human emissions, and the effect these have on the environment, human health, and climate change is determined by the molecular nature of these chemical species. The complexity of organic aerosol samples limits the ability to study the chemical composition, and, therefore, the associated properties and the impacts they have. Many studies address the water-soluble fraction of organic aerosols, and have had much success in identifying specific molecular formulas for thousands of compounds present. However, little attention is given to the water-insoluble portion, which can contain most of the fossil material that is emitted through human activity. Here we compare the organic aerosols present in water extracts and organic solvent extracts (pyridine and acetonitrile) of an ambient aerosol sample collected in a rural location that is impacted by natural and anthropogenic emission sources. A semi-quantitative method was developed using proton nuclear magnetic resonance spectroscopy to determine that the amount of organic matter extracted by pyridine is comparable to that of water. Electrospray ionization Fourier transform ion cyclotron resonance mass spectra show that pyridine extracts a molecularly unique fraction of organic matter compared to water or acetonitrile, which extract chemically similar organic matter components. The molecular formulas unique to pyridine were less polar, more aliphatic, and reveal formulas containing sulfur to be an important component of insoluble aerosol organic matter.

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