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Title: Molecular transformations of phenolic SOA during photochemical aging in the aqueous phase: competition among oligomerization, functionalization, and fragmentation

Abstract

Organic aerosol is formed and transformed in atmospheric aqueous phases (e.g., cloud and fog droplets and deliquesced airborne particles containing small amounts of water) through a multitude of chemical reactions. Understanding these reactions is important for a predictive understanding of atmospheric aging of aerosols and their impacts on climate, air quality, and human health. In this study, we investigate the chemical evolution of aqueous secondary organic aerosol (aqSOA) formed during reactions of phenolic compounds with two oxidants – the triplet excited state of an aromatic carbonyl (3C*) and hydroxyl radical ( OH). Changes in the molecular composition of aqSOA as a function of aging time are characterized using an offline nanospray desorption electrospray ionization mass spectrometer (nano-DESI MS) whereas the real-time evolution of SOA mass, elemental ratios, and average carbon oxidation state (OSC) are monitored using an online aerosol mass spectrometer (AMS). Our results indicate that oligomerization is an important aqueous reaction pathway for phenols, especially during the initial stage of photooxidation equivalent to ~2 h irradiation under midday winter solstice sunlight in Northern California. At later reaction times functionalization (i.e., adding polar oxygenated functional groups to the molecule) and fragmentation (i.e., breaking of covalent bonds) become moremore » important processes, forming a large variety of functionalized aromatic and open-ring products with higher OSC values. Fragmentation reactions eventually dominate the photochemical evolution of phenolic aqSOA, forming a large number of highly oxygenated ring-opening molecules with carbon numbers (nC) below 6. The average nC of phenolic aqSOA decreases while average OSC increases over the course of photochemical aging. In addition, the saturation vapor pressures (C*) of dozens of the most abundant phenolic aqSOA molecules are estimated. A wide range of C* values is observed, varying from < 10–20 µg m–3 for functionalized phenolic oligomers to > 10 µg m–3 for small open-ring species. Furthermore, the detection of abundant extremely low-volatile organic compounds (ELVOC) indicates that aqueous reactions of phenolic compounds are likely an important source of ELVOC in the atmosphere.« less

Authors:
; ; ORCiD logo; ; ORCiD logo; ; ; ORCiD logo
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
1247187
Alternate Identifier(s):
OSTI ID: 1253872
Report Number(s):
PNNL-SA-114037
Journal ID: ISSN 1680-7324
Grant/Contract Number:  
DEAC06-76RL0 1830; AC05-76RL01830
Resource Type:
Published Article
Journal Name:
Atmospheric Chemistry and Physics (Online)
Additional Journal Information:
Journal Name: Atmospheric Chemistry and Physics (Online) Journal Volume: 16 Journal Issue: 7; Journal ID: ISSN 1680-7324
Publisher:
Copernicus Publications, EGU
Country of Publication:
Germany
Language:
English
Subject:
54 ENVIRONMENTAL SCIENCES; particulate matter; hydroxyl radical; triplet excited state; photochemical aging; molecular transformation; AMS; nano-DESI MS; Environmental Molecular Sciences Laboratory

Citation Formats

Yu, Lu, Smith, Jeremy, Laskin, Alexander, George, Katheryn M., Anastasio, Cort, Laskin, Julia, Dillner, Ann M., and Zhang, Qi. Molecular transformations of phenolic SOA during photochemical aging in the aqueous phase: competition among oligomerization, functionalization, and fragmentation. Germany: N. p., 2016. Web. https://doi.org/10.5194/acp-16-4511-2016.
Yu, Lu, Smith, Jeremy, Laskin, Alexander, George, Katheryn M., Anastasio, Cort, Laskin, Julia, Dillner, Ann M., & Zhang, Qi. Molecular transformations of phenolic SOA during photochemical aging in the aqueous phase: competition among oligomerization, functionalization, and fragmentation. Germany. https://doi.org/10.5194/acp-16-4511-2016
Yu, Lu, Smith, Jeremy, Laskin, Alexander, George, Katheryn M., Anastasio, Cort, Laskin, Julia, Dillner, Ann M., and Zhang, Qi. Wed . "Molecular transformations of phenolic SOA during photochemical aging in the aqueous phase: competition among oligomerization, functionalization, and fragmentation". Germany. https://doi.org/10.5194/acp-16-4511-2016.
@article{osti_1247187,
title = {Molecular transformations of phenolic SOA during photochemical aging in the aqueous phase: competition among oligomerization, functionalization, and fragmentation},
author = {Yu, Lu and Smith, Jeremy and Laskin, Alexander and George, Katheryn M. and Anastasio, Cort and Laskin, Julia and Dillner, Ann M. and Zhang, Qi},
abstractNote = {Organic aerosol is formed and transformed in atmospheric aqueous phases (e.g., cloud and fog droplets and deliquesced airborne particles containing small amounts of water) through a multitude of chemical reactions. Understanding these reactions is important for a predictive understanding of atmospheric aging of aerosols and their impacts on climate, air quality, and human health. In this study, we investigate the chemical evolution of aqueous secondary organic aerosol (aqSOA) formed during reactions of phenolic compounds with two oxidants – the triplet excited state of an aromatic carbonyl (3C*) and hydroxyl radical (•OH). Changes in the molecular composition of aqSOA as a function of aging time are characterized using an offline nanospray desorption electrospray ionization mass spectrometer (nano-DESI MS) whereas the real-time evolution of SOA mass, elemental ratios, and average carbon oxidation state (OSC) are monitored using an online aerosol mass spectrometer (AMS). Our results indicate that oligomerization is an important aqueous reaction pathway for phenols, especially during the initial stage of photooxidation equivalent to ~2 h irradiation under midday winter solstice sunlight in Northern California. At later reaction times functionalization (i.e., adding polar oxygenated functional groups to the molecule) and fragmentation (i.e., breaking of covalent bonds) become more important processes, forming a large variety of functionalized aromatic and open-ring products with higher OSC values. Fragmentation reactions eventually dominate the photochemical evolution of phenolic aqSOA, forming a large number of highly oxygenated ring-opening molecules with carbon numbers (nC) below 6. The average nC of phenolic aqSOA decreases while average OSC increases over the course of photochemical aging. In addition, the saturation vapor pressures (C*) of dozens of the most abundant phenolic aqSOA molecules are estimated. A wide range of C* values is observed, varying from < 10–20 µg m–3 for functionalized phenolic oligomers to > 10 µg m–3 for small open-ring species. Furthermore, the detection of abundant extremely low-volatile organic compounds (ELVOC) indicates that aqueous reactions of phenolic compounds are likely an important source of ELVOC in the atmosphere.},
doi = {10.5194/acp-16-4511-2016},
journal = {Atmospheric Chemistry and Physics (Online)},
number = 7,
volume = 16,
place = {Germany},
year = {2016},
month = {4}
}

Journal Article:
Free Publicly Available Full Text
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https://doi.org/10.5194/acp-16-4511-2016

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Cited by: 10 works
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