Interfacial Dark Aging Is an Overlooked Source of Aqueous Secondary Organic Aerosol

Fei Zhang; Manh Thuong Nguyen; Yao Fu; Xiao Ying Yu

doi:10.3390/atmos13020188

Interfacial Dark Aging Is an Overlooked Source of Aqueous Secondary Organic Aerosol

Fei Zhang
, Manh Thuong Nguyen
, Yao Fu
, Xiao Ying Yu

Research output: Contribution to journal › Article › peer-review

3 Scopus citations

Abstract

In this work, the relative yields of aqueous secondary organic aerosols (aqSOAs) at the air–liquid (a–l) interface are investigated between photochemical and dark aging using in situ time-offlight secondary ion mass spectrometry (ToF-SIMS). Our results show that dark aging is an important source of aqSOAs despite a lack of photochemical drivers. Photochemical reactions of glyoxal and hydroxyl radicals (•OH) produce oligomers and cluster ions at the aqueous surface. Interestingly, different oligomers and cluster ions form intensely in the dark at the a–l interface, contrary to the notion that oligomer formation mainly depends on light irradiation. Furthermore, cluster ions form readily during dark aging and have a higher water molecule adsorption ability. This finding is supported by the observation of more frequent organic water cluster ion formation. The relative yields of water clusters in the form of protonated and hydroxide ions are presented using van Krevelen diagrams to explore the underlying formation mechanisms of aqSOAs. Large protonated and hydroxide water clusters (e.g., (H₂O)nH⁺, 17 < n ≤ 44) have reasonable yields during UV aging. In contrast, small protonated and hydroxide water clusters (e.g., (H₂O)nH⁺, 1 ≤ n ≤ 17) form after several hours of dark aging. Moreover, cluster ions have higher yields in dark aging, indicating the overlooked influence of dark aging interfacial products on aerosol optical properties. Molecular dynamic simulation shows that cluster ions form stably in UV and dark aging. AqSOAs molecules produced from dark and photochemical aging can enhance UV absorption of the aqueous surface, promote cloud condensation nuclei (CCN) activities, and affect radiative forcing.

Original language	English
Article number	188
Journal	Atmosphere
Volume	13
Issue number	2
DOIs	https://doi.org/10.3390/atmos13020188
State	Published - Feb 2022
Externally published	Yes

Funding

Funding: The experimental work was supported by the Earth and Biological Sciences Directorate (EBSD) Mission Seed Laboratory Directed Research and Development (LDRD) funding of the Pacific Northwest National Laboratory (PNNL). Xiao-Ying Yu thanks the Office of Science, Office of Basic Energy Sciences, of the U.S. DOE through the Direct Air Capture (DAC) Program for partial support in writing this manuscript, which was jointly supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Divisions of Chemical Sciences, Geosciences, and Biosciences (CSGB) and Materials Sciences and Engineering (MSE) under FWP 76830. Computer resources were provided by the National Energy Research Scientific Computing Center (NERSC), a DOE Office of Science User Facility operated under Contract DE-AC02-05CH11231. Fei Zhang was partially supported by State Environmental Protection Key Laboratory of Formation and Prevention of Urban Air Pollution Complex (no. CX2020080581). F.Z. is grateful for the fellowship support from the PNNL Alternate Sponsored Fellowship (ASF) and Chinese Scholar Council (CSC) programs. The opinions expressed are solely based on the research results of the authors. Acknowledgments: PNNL is operated by Battelle for the DOE under Contract DE-AC05-76RL01830.

Keywords

Ab initio molecular dynamics simulation
Aqueous SOA
Cluster ion
Dark aging
Glyoxal
Van Krevelen diagram
Water cluster

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10.3390/atmos13020188

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title = "Interfacial Dark Aging Is an Overlooked Source of Aqueous Secondary Organic Aerosol",

abstract = "In this work, the relative yields of aqueous secondary organic aerosols (aqSOAs) at the air–liquid (a–l) interface are investigated between photochemical and dark aging using in situ time-offlight secondary ion mass spectrometry (ToF-SIMS). Our results show that dark aging is an important source of aqSOAs despite a lack of photochemical drivers. Photochemical reactions of glyoxal and hydroxyl radicals (•OH) produce oligomers and cluster ions at the aqueous surface. Interestingly, different oligomers and cluster ions form intensely in the dark at the a–l interface, contrary to the notion that oligomer formation mainly depends on light irradiation. Furthermore, cluster ions form readily during dark aging and have a higher water molecule adsorption ability. This finding is supported by the observation of more frequent organic water cluster ion formation. The relative yields of water clusters in the form of protonated and hydroxide ions are presented using van Krevelen diagrams to explore the underlying formation mechanisms of aqSOAs. Large protonated and hydroxide water clusters (e.g., (H2O)nH+, 17 < n ≤ 44) have reasonable yields during UV aging. In contrast, small protonated and hydroxide water clusters (e.g., (H2O)nH+, 1 ≤ n ≤ 17) form after several hours of dark aging. Moreover, cluster ions have higher yields in dark aging, indicating the overlooked influence of dark aging interfacial products on aerosol optical properties. Molecular dynamic simulation shows that cluster ions form stably in UV and dark aging. AqSOAs molecules produced from dark and photochemical aging can enhance UV absorption of the aqueous surface, promote cloud condensation nuclei (CCN) activities, and affect radiative forcing.",

keywords = "Ab initio molecular dynamics simulation, Aqueous SOA, Cluster ion, Dark aging, Glyoxal, Van Krevelen diagram, Water cluster",

author = "Fei Zhang and Nguyen, \{Manh Thuong\} and Yao Fu and Yu, \{Xiao Ying\}",

note = "Publisher Copyright: {\textcopyright} 2022 by the authors. Licensee MDPI, Basel, Switzerland.",

year = "2022",

month = feb,

doi = "10.3390/atmos13020188",

language = "English",

volume = "13",

journal = "Atmosphere",

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AU - Zhang, Fei

AU - Nguyen, Manh Thuong

AU - Fu, Yao

AU - Yu, Xiao Ying

PY - 2022/2

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N2 - In this work, the relative yields of aqueous secondary organic aerosols (aqSOAs) at the air–liquid (a–l) interface are investigated between photochemical and dark aging using in situ time-offlight secondary ion mass spectrometry (ToF-SIMS). Our results show that dark aging is an important source of aqSOAs despite a lack of photochemical drivers. Photochemical reactions of glyoxal and hydroxyl radicals (•OH) produce oligomers and cluster ions at the aqueous surface. Interestingly, different oligomers and cluster ions form intensely in the dark at the a–l interface, contrary to the notion that oligomer formation mainly depends on light irradiation. Furthermore, cluster ions form readily during dark aging and have a higher water molecule adsorption ability. This finding is supported by the observation of more frequent organic water cluster ion formation. The relative yields of water clusters in the form of protonated and hydroxide ions are presented using van Krevelen diagrams to explore the underlying formation mechanisms of aqSOAs. Large protonated and hydroxide water clusters (e.g., (H2O)nH+, 17 < n ≤ 44) have reasonable yields during UV aging. In contrast, small protonated and hydroxide water clusters (e.g., (H2O)nH+, 1 ≤ n ≤ 17) form after several hours of dark aging. Moreover, cluster ions have higher yields in dark aging, indicating the overlooked influence of dark aging interfacial products on aerosol optical properties. Molecular dynamic simulation shows that cluster ions form stably in UV and dark aging. AqSOAs molecules produced from dark and photochemical aging can enhance UV absorption of the aqueous surface, promote cloud condensation nuclei (CCN) activities, and affect radiative forcing.

AB - In this work, the relative yields of aqueous secondary organic aerosols (aqSOAs) at the air–liquid (a–l) interface are investigated between photochemical and dark aging using in situ time-offlight secondary ion mass spectrometry (ToF-SIMS). Our results show that dark aging is an important source of aqSOAs despite a lack of photochemical drivers. Photochemical reactions of glyoxal and hydroxyl radicals (•OH) produce oligomers and cluster ions at the aqueous surface. Interestingly, different oligomers and cluster ions form intensely in the dark at the a–l interface, contrary to the notion that oligomer formation mainly depends on light irradiation. Furthermore, cluster ions form readily during dark aging and have a higher water molecule adsorption ability. This finding is supported by the observation of more frequent organic water cluster ion formation. The relative yields of water clusters in the form of protonated and hydroxide ions are presented using van Krevelen diagrams to explore the underlying formation mechanisms of aqSOAs. Large protonated and hydroxide water clusters (e.g., (H2O)nH+, 17 < n ≤ 44) have reasonable yields during UV aging. In contrast, small protonated and hydroxide water clusters (e.g., (H2O)nH+, 1 ≤ n ≤ 17) form after several hours of dark aging. Moreover, cluster ions have higher yields in dark aging, indicating the overlooked influence of dark aging interfacial products on aerosol optical properties. Molecular dynamic simulation shows that cluster ions form stably in UV and dark aging. AqSOAs molecules produced from dark and photochemical aging can enhance UV absorption of the aqueous surface, promote cloud condensation nuclei (CCN) activities, and affect radiative forcing.

KW - Ab initio molecular dynamics simulation

KW - Aqueous SOA

KW - Cluster ion

KW - Dark aging

KW - Glyoxal

KW - Van Krevelen diagram

KW - Water cluster

UR - https://www.scopus.com/pages/publications/85124093831

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DO - 10.3390/atmos13020188

M3 - Article

AN - SCOPUS:85124093831

SN - 2073-4433

VL - 13

JO - Atmosphere

JF - Atmosphere

IS - 2

M1 - 188

ER -

Interfacial Dark Aging Is an Overlooked Source of Aqueous Secondary Organic Aerosol

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