Chemical characterization of SOA formed from aqueous-phase reactions of phenols with the triplet excited state of carbonyl and hydroxyl radical
Abstract
Phenolic compounds, which are emitted in significant amounts from biomass burning, can undergo fast reactions in atmospheric aqueous phases to form secondary organic aerosol (aqSOA). In this study, we investigate the reactions of phenol (compound with formula C6H5OH)), guaiacol (2-methoxyphenol), and syringol (2,6-dimethoxyphenol) with two major aqueous-phase oxidants – the triplet excited states of an aromatic carbonyl (3C*) and hydroxyl radical (· OH). We thoroughly characterize the low-volatility species produced from these reactions and interpret their formation mechanisms using aerosol mass spectrometry (AMS), nanospray desorption electrospray ionization mass spectrometry (nano-DESI MS), and ion chromatography (IC). A large number of oxygenated molecules are identified, including oligomers containing up to six monomer units, functionalized monomer and oligomers with carbonyl, carboxyl, and hydroxyl groups, and small organic acid anions (e.g., formate, acetate, oxalate, and malate). The average atomic oxygen-to-carbon (O / C) ratios of phenolic aqSOA are in the range of 0.85–1.23, similar to those of low-volatility oxygenated organic aerosol (LV-OOA) observed in ambient air. The aqSOA compositions are overall similar for the same precursor, but the reactions mediated by 3C* are faster than · OH-mediated reactions and produce more oligomers and hydroxylated species at the point when 50% of the phenolic compoundmore »
- Authors:
- Publication Date:
- Sponsoring Org.:
- USDOE Office of Science (SC), Biological and Environmental Research (BER)
- OSTI Identifier:
- 1198014
- Grant/Contract Number:
- AC06-76RL0 1830
- Resource Type:
- Published Article
- Journal Name:
- Atmospheric Chemistry and Physics (Online)
- Additional Journal Information:
- Journal Name: Atmospheric Chemistry and Physics (Online) Journal Volume: 14 Journal Issue: 24; Journal ID: ISSN 1680-7324
- Publisher:
- Copernicus Publications, EGU
- Country of Publication:
- Germany
- Language:
- English
Citation Formats
Yu, L., Smith, J., Laskin, A., Anastasio, C., Laskin, J., and Zhang, Q. Chemical characterization of SOA formed from aqueous-phase reactions of phenols with the triplet excited state of carbonyl and hydroxyl radical. Germany: N. p., 2014.
Web. doi:10.5194/acp-14-13801-2014.
Yu, L., Smith, J., Laskin, A., Anastasio, C., Laskin, J., & Zhang, Q. Chemical characterization of SOA formed from aqueous-phase reactions of phenols with the triplet excited state of carbonyl and hydroxyl radical. Germany. https://doi.org/10.5194/acp-14-13801-2014
Yu, L., Smith, J., Laskin, A., Anastasio, C., Laskin, J., and Zhang, Q. Tue .
"Chemical characterization of SOA formed from aqueous-phase reactions of phenols with the triplet excited state of carbonyl and hydroxyl radical". Germany. https://doi.org/10.5194/acp-14-13801-2014.
@article{osti_1198014,
title = {Chemical characterization of SOA formed from aqueous-phase reactions of phenols with the triplet excited state of carbonyl and hydroxyl radical},
author = {Yu, L. and Smith, J. and Laskin, A. and Anastasio, C. and Laskin, J. and Zhang, Q.},
abstractNote = {Phenolic compounds, which are emitted in significant amounts from biomass burning, can undergo fast reactions in atmospheric aqueous phases to form secondary organic aerosol (aqSOA). In this study, we investigate the reactions of phenol (compound with formula C6H5OH)), guaiacol (2-methoxyphenol), and syringol (2,6-dimethoxyphenol) with two major aqueous-phase oxidants – the triplet excited states of an aromatic carbonyl (3C*) and hydroxyl radical (· OH). We thoroughly characterize the low-volatility species produced from these reactions and interpret their formation mechanisms using aerosol mass spectrometry (AMS), nanospray desorption electrospray ionization mass spectrometry (nano-DESI MS), and ion chromatography (IC). A large number of oxygenated molecules are identified, including oligomers containing up to six monomer units, functionalized monomer and oligomers with carbonyl, carboxyl, and hydroxyl groups, and small organic acid anions (e.g., formate, acetate, oxalate, and malate). The average atomic oxygen-to-carbon (O / C) ratios of phenolic aqSOA are in the range of 0.85–1.23, similar to those of low-volatility oxygenated organic aerosol (LV-OOA) observed in ambient air. The aqSOA compositions are overall similar for the same precursor, but the reactions mediated by 3C* are faster than · OH-mediated reactions and produce more oligomers and hydroxylated species at the point when 50% of the phenolic compound has reacted. Profiles determined using a thermodenuder indicate that the volatility of phenolic aqSOA is influenced by both oligomer content and O / C ratio. In addition, the aqSOA shows enhanced light absorption in the UV–visible region, suggesting that aqueous-phase reactions of phenols may contribute to formation of secondary brown carbon in the atmosphere, especially in regions influenced by biomass burning.},
doi = {10.5194/acp-14-13801-2014},
journal = {Atmospheric Chemistry and Physics (Online)},
number = 24,
volume = 14,
place = {Germany},
year = {Tue Dec 23 00:00:00 EST 2014},
month = {Tue Dec 23 00:00:00 EST 2014}
}
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.5194/acp-14-13801-2014
https://doi.org/10.5194/acp-14-13801-2014
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 147 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Reactions of hydroxyl and nitrogen trioxide radicals with phenol, cresols, and 2-nitrophenol at 296 .+-. 2 K
journal, July 1992
- Atkinson, Roger; Aschmann, Sara M.; Arey, Janet
- Environmental Science & Technology, Vol. 26, Issue 7
Secondary Organic Aerosol Production from Aqueous Reactions of Atmospheric Phenols with an Organic Triplet Excited State
journal, January 2014
- Smith, Jeremy D.; Sio, Vicky; Yu, Lu
- Environmental Science & Technology, Vol. 48, Issue 2
A generalised method for the extraction of chemically resolved mass spectra from Aerodyne aerosol mass spectrometer data
journal, July 2004
- Allan, James D.; Delia, Alice E.; Coe, Hugh
- Journal of Aerosol Science, Vol. 35, Issue 7
Decon2LS: An open-source software package for automated processing and visualization of high resolution mass spectrometry data
journal, January 2009
- Jaitly, Navdeep; Mayampurath, Anoop; Littlefield, Kyle
- BMC Bioinformatics, Vol. 10, Issue 1
Secondary organic aerosol formation in cloud droplets and aqueous particles (aqSOA): a review of laboratory, field and model studies
journal, January 2011
- Ervens, B.; Turpin, B. J.; Weber, R. J.
- Atmospheric Chemistry and Physics, Vol. 11, Issue 21
PM-10 high-volume collection and quantitation of semi- and nonvolatile phenols, methoxylated phenols, alkanes, and polycyclic aromatic hydrocarbons from winter urban air and their relationship to wood smoke emissions
journal, November 1992
- Hawthorne, Steven B.; Miller, David J.; Langenfeld, John J.
- Environmental Science & Technology, Vol. 26, Issue 11
Elemental composition and oxidation of chamber organic aerosol
journal, January 2011
- Chhabra, P. S.; Ng, N. L.; Canagaratna, M. R.
- Atmospheric Chemistry and Physics, Vol. 11, Issue 17
Higher-Order Mass Defect Analysis for Mass Spectra of Complex Organic Mixtures
journal, June 2011
- Roach, Patrick J.; Laskin, Julia; Laskin, Alexander
- Analytical Chemistry, Vol. 83, Issue 12
Oxidative demethoxylation of methoxylated phenols and hydroxybenzoic acids by the hydroxyl radical. An in situ electron spin resonance, conductometric pulse radiolysis and product analysis study
journal, March 1977
- Steenken, Steen; O'Neill, Peter
- The Journal of Physical Chemistry, Vol. 81, Issue 6
Detection of particle-phase polycyclic aromatic hydrocarbons in Mexico City using an aerosol mass spectrometer
journal, June 2007
- Dzepina, Katja; Arey, Janet; Marr, Linsey C.
- International Journal of Mass Spectrometry, Vol. 263, Issue 2-3
Toward Understanding Amines and Their Degradation Products from Postcombustion CO 2 Capture Processes with Aerosol Mass Spectrometry
journal, April 2014
- Ge, Xinlei; Shaw, Stephanie L.; Zhang, Qi
- Environmental Science & Technology, Vol. 48, Issue 9
Aromatic Carbonyl Compounds as Aqueous-Phase Photochemical Sources of Hydrogen Peroxide in Acidic Sulfate Aerosols, Fogs, and Clouds. 1. Non-Phenolic Methoxybenzaldehydes and Methoxyacetophenones with Reductants (Phenols)
journal, January 1997
- Anastasio, Cort; Faust, Bruce C.; Rao, C. Janakiram
- Environmental Science & Technology, Vol. 31, Issue 1
Collection and quantitation of methoxylated phenol tracers for atmospheric pollution from residential wood stoves
journal, April 1989
- Hawthorne, Steven B.; Krieger, Mark S.; Miller, David J.
- Environmental Science & Technology, Vol. 23, Issue 4
FT–IR study of the ring-retaining products from the reaction of OH radicals with phenol, o-, m-, and p-cresol
journal, August 2002
- Olariu, Romeo Iulian; Klotz, Björn; Barnes, Ian
- Atmospheric Environment, Vol. 36, Issue 22
Levoglucosan, a tracer for cellulose in biomass burning and atmospheric particles
journal, January 1999
- Simoneit, B. R. T.; Schauer, J. J.; Nolte, C. G.
- Atmospheric Environment, Vol. 33, Issue 2
Glyoxal Induced Atmospheric Photosensitized Chemistry Leading to Organic Aerosol Growth
journal, February 2014
- Rossignol, Stéphanie; Aregahegn, Kifle Z.; Tinel, Liselotte
- Environmental Science & Technology, Vol. 48, Issue 6
Evidence for Oligomer Formation in Clouds: Reactions of Isoprene Oxidation Products
journal, August 2006
- Altieri, Katye E.; Carlton, Annmarie G.; Lim, Ho-Jin
- Environmental Science & Technology, Vol. 40, Issue 16
FT-IR quantification of the carbonyl functional group in aqueous-phase secondary organic aerosol from phenols
journal, January 2015
- George, Kathryn M.; Ruthenburg, Travis C.; Smith, Jeremy
- Atmospheric Environment, Vol. 100
Single-particle mass spectrometry of tropospheric aerosol particles: TROPOSPHERIC AEROSOL PARTICLES
journal, September 2006
- Murphy, D. M.; Cziczo, D. J.; Froyd, K. D.
- Journal of Geophysical Research: Atmospheres, Vol. 111, Issue D23
Gas-Phase CO 2 Subtraction for Improved Measurements of the Organic Aerosol Mass Concentration and Oxidation Degree by an Aerosol Mass Spectrometer
journal, November 2013
- Collier, S.; Zhang, Q.
- Environmental Science & Technology, Vol. 47, Issue 24
O/C and OM/OC Ratios of Primary, Secondary, and Ambient Organic Aerosols with High-Resolution Time-of-Flight Aerosol Mass Spectrometry
journal, June 2008
- Aiken, Allison C.; DeCarlo, Peter F.; Kroll, Jesse H.
- Environmental Science & Technology, Vol. 42, Issue 12
Secondary organic aerosol formation in cloud and fog droplets: a literature evaluation of plausibility
journal, January 2000
- Blando, James D.; Turpin, Barbara J.
- Atmospheric Environment, Vol. 34, Issue 10
A General Scavenging Rate Constant for Reaction of Hydroxyl Radical with Organic Carbon in Atmospheric Waters
journal, August 2013
- Arakaki, Takemitsu; Anastasio, Cort; Kuroki, Yukiko
- Environmental Science & Technology, Vol. 47, Issue 15
Ubiquity and dominance of oxygenated species in organic aerosols in anthropogenically-influenced Northern Hemisphere midlatitudes: UBIQUITY AND DOMINANCE OF OXYGENATED OA
journal, July 2007
- Zhang, Q.; Jimenez, J. L.; Canagaratna, M. R.
- Geophysical Research Letters, Vol. 34, Issue 13
Organic aerosol and global climate modelling: a review
journal, January 2005
- Kanakidou, M.; Seinfeld, J. H.; Pandis, S. N.
- Atmospheric Chemistry and Physics, Vol. 5, Issue 4
Evolution of Organic Aerosols in the Atmosphere
journal, December 2009
- Jimenez, J. L.; Canagaratna, M. R.; Donahue, N. M.
- Science, Vol. 326, Issue 5959
Characterization of colored products formed during irradiation of aqueous solutions containing H2O2 and phenolic compounds
journal, February 2010
- Chang, Jonathan L.; Thompson, Jonathan E.
- Atmospheric Environment, Vol. 44, Issue 4
Size-resolved aerosol chemistry on Whistler Mountain, Canada with a high-resolution aerosol mass spectrometer during INTEX-B
journal, January 2009
- Sun, Y.; Zhang, Q.; Macdonald, A. M.
- Atmospheric Chemistry and Physics, Vol. 9, Issue 9
Interpretation of organic components from Positive Matrix Factorization of aerosol mass spectrometric data
journal, January 2009
- Ulbrich, I. M.; Canagaratna, M. R.; Zhang, Q.
- Atmospheric Chemistry and Physics, Vol. 9, Issue 9
Chemical and microphysical characterization of ambient aerosols with the aerodyne aerosol mass spectrometer
journal, January 2007
- Canagaratna, M. R.; Jayne, J. T.; Jimenez, J. L.
- Mass Spectrometry Reviews, Vol. 26, Issue 2
The formation, properties and impact of secondary organic aerosol: current and emerging issues
journal, January 2009
- Hallquist, M.; Wenger, J. C.; Baltensperger, U.
- Atmospheric Chemistry and Physics, Vol. 9, Issue 14
Organic aerosol formation photo-enhanced by the formation of secondary photosensitizers in aerosols
journal, January 2013
- Aregahegn, Kifle Z.; Nozière, Barbara; George, Christian
- Faraday Discussions, Vol. 165
Alternative pathway for atmospheric particles growth
journal, April 2012
- Monge, M. E.; Rosenorn, T.; Favez, O.
- Proceedings of the National Academy of Sciences, Vol. 109, Issue 18
Light-absorbing secondary organic material formed by glyoxal in aqueous aerosol mimics
journal, January 2009
- Shapiro, E. L.; Szprengiel, J.; Sareen, N.
- Atmospheric Chemistry and Physics, Vol. 9, Issue 7
Applications of High-Resolution Electrospray Ionization Mass Spectrometry to Measurements of Average Oxygen to Carbon Ratios in Secondary Organic Aerosols
journal, July 2012
- Bateman, Adam P.; Laskin, Julia; Laskin, Alexander
- Environmental Science & Technology, Vol. 46, Issue 15
Physico-chemical characterization of SOA derived from catechol and guaiacol – a model substance for the aromatic fraction of atmospheric HULIS
journal, January 2011
- Ofner, J.; Krüger, H. -U.; Grothe, H.
- Atmospheric Chemistry and Physics, Vol. 11, Issue 1
Response of an aerosol mass spectrometer to organonitrates and organosulfates and implications for atmospheric chemistry
journal, March 2010
- Farmer, D. K.; Matsunaga, A.; Docherty, K. S.
- Proceedings of the National Academy of Sciences, Vol. 107, Issue 15
Field-Deployable, High-Resolution, Time-of-Flight Aerosol Mass Spectrometer
journal, December 2006
- DeCarlo, Peter F.; Kimmel, Joel R.; Trimborn, Achim
- Analytical Chemistry, Vol. 78, Issue 24
Kendrick Mass Defect Spectrum: A Compact Visual Analysis for Ultrahigh-Resolution Broadband Mass Spectra
journal, October 2001
- Hughey, Christine A.; Hendrickson, Christopher L.; Rodgers, Ryan P.
- Analytical Chemistry, Vol. 73, Issue 19
An improved low-flow thermodenuder
journal, November 2007
- Fierz, Martin; Vernooij, Martine G. C.; Burtscher, Heinz
- Journal of Aerosol Science, Vol. 38, Issue 11
Molecular Characterization of Organic Aerosols Using Nanospray-Desorption/Electrospray Ionization-Mass Spectrometry †
journal, October 2010
- Roach, Patrick J.; Laskin, Julia; Laskin, Alexander
- Analytical Chemistry, Vol. 82, Issue 19
A mechanistic study of the oxidation of phenol by OH/NO2/NO3 in aqueous solution
journal, June 2002
- Barzaghi, Paolo; Herrmann, Hartmut
- Physical Chemistry Chemical Physics, Vol. 4, Issue 15
Secondary organic aerosol formation from biomass burning intermediates: phenol and methoxyphenols
journal, January 2013
- Yee, L. D.; Kautzman, K. E.; Loza, C. L.
- Atmospheric Chemistry and Physics, Vol. 13, Issue 16
Oxidation of Phenols by Triplet Aromatic Ketones in Aqueous Solution
journal, February 2000
- Canonica, Silvio; Hellrung, Bruno; Wirz, Jakob
- The Journal of Physical Chemistry A, Vol. 104, Issue 6
Trace organic compounds in rain. 4. Identities, concentrations, and scavenging mechanisms for phenols in urban air and rain
journal, November 1985
- Leuenberger, Christian.; Ligocki, Mary P.; Pankow, James F.
- Environmental Science & Technology, Vol. 19, Issue 11
Insights into secondary organic aerosol formed via aqueous-phase reactions of phenolic compounds based on high resolution mass spectrometry
journal, January 2010
- Sun, Y. L.; Zhang, Q.; Anastasio, C.
- Atmospheric Chemistry and Physics, Vol. 10, Issue 10
The direct esterification of phenols
journal, January 1964
- Offenhauer, Robert D.
- Journal of Chemical Education, Vol. 41, Issue 1
Studies on the occurrence and distribution of wood smoke marker compounds in foggy atmospheres
journal, May 1993
- Sagebiel, John C.; Seiber, James N.
- Environmental Toxicology and Chemistry, Vol. 12, Issue 5
Negative Electrospray Ionization via Deprotonation: Predicting the Ionization Efficiency
journal, April 2014
- Kruve, Anneli; Kaupmees, Karl; Liigand, Jaanus
- Analytical Chemistry, Vol. 86, Issue 10
Measurement of Emissions from Air Pollution Sources. 3. C 1 −C 29 Organic Compounds from Fireplace Combustion of Wood
journal, May 2001
- Schauer, James J.; Kleeman, Michael J.; Cass, Glen R.
- Environmental Science & Technology, Vol. 35, Issue 9
Deconvolution and Quantification of Hydrocarbon-like and Oxygenated Organic Aerosols Based on Aerosol Mass Spectrometry
journal, July 2005
- Zhang, Qi; Alfarra, M. Rami; Worsnop, Douglas R.
- Environmental Science & Technology, Vol. 39, Issue 13
Chemically-Resolved Volatility Measurements of Organic Aerosol from Different Sources
journal, July 2009
- Huffman, J. A.; Docherty, K. S.; Mohr, C.
- Environmental Science & Technology, Vol. 43, Issue 14
Isoprene Forms Secondary Organic Aerosol through Cloud Processing: Model Simulations
journal, June 2005
- Lim, Ho-Jin; Carlton, Annmarie G.; Turpin, Barbara J.
- Environmental Science & Technology, Vol. 39, Issue 12
Understanding atmospheric organic aerosols via factor analysis of aerosol mass spectrometry: a review
journal, October 2011
- Zhang, Qi; Jimenez, Jose L.; Canagaratna, Manjula R.
- Analytical and Bioanalytical Chemistry, Vol. 401, Issue 10
Molecular formulas of organic compounds: the nitrogen rule and degree of unsaturation
journal, August 1983
- Pellegrin, Valdo
- Journal of Chemical Education, Vol. 60, Issue 8
Chemistry of fog waters in California's Central Valley: 1. In situ photoformation of hydroxyl radical and singlet molecular oxygen
journal, January 2001
- Anastasio, Cort; McGregor, Keith G.
- Atmospheric Environment, Vol. 35, Issue 6
Primary and secondary organic aerosols in Fresno, California during wintertime: Results from high resolution aerosol mass spectrometry: POA AND SOA IN FRESNO IN WINTER
journal, October 2012
- Ge, Xinlei; Setyan, Ari; Sun, Yele
- Journal of Geophysical Research: Atmospheres, Vol. 117, Issue D19