Monoterpene Photooxidation in a Continuous-Flow Chamber: SOA Yields and Impacts of Oxidants, NOx, and VOC Precursors
Abstract
We report monoterpene photooxidation plays an important role in secondary organic aerosol (SOA) formation in the atmosphere. The low-volatility products can enhance new particle formation and particle growth, and thus have influences on climate feedbacks. Here, we present the results of α-pinene and Δ-3-carene photooxidation experiments conducted in continuous-flow mode in an environmental chamber under several reaction conditions. The roles of oxidants, addition of NO, and VOC molecular structure in influencing SOA yield are illustrated. SOA yield from α-pinene photooxidation shows a weak dependence on H2O2 concentration, which is a proxy for HO2 concentration. The high O/C ratios observed in the a-pinene photooxidation products suggest the production of highly oxygenated organic molecules (HOM). Addition of ozone to the chamber during low-NOx photooxidation experiments leads to higher SOA yield. With the addition of NO, the production of N-containing HOMs is enhanced and the SOA yield shows a modest, non-linear dependence on input NO concentration. Carene photooxidation leads to higher SOA yield than α-pinene under similar reaction conditions, which agrees with the lower volatility retrieved from evaporation kinetics experiments. These results improve the understanding of SOA formation from monoterpene photooxidation and could be applied to refine the representation of biogenic SOA formationmore »
- Authors:
-
[1];
[2];
[2];
[3];
[3];
[2]
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Harbin Institute of Technology (China)
- University of Washington, Seattle, WA (United States)
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Department of Chemistry, University of Washington, Seattle, Washington 98195, United States
- Publication Date:
- Research Org.:
- Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Biological and Environmental Research (BER); NOAA Climate and Global Change
- OSTI Identifier:
- 1888285
- Report Number(s):
- PNNL-SA-176021
Journal ID: ISSN 0013-936X
- Grant/Contract Number:
- AC05-76RL01830; SC0006867; SC0011791
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Environmental Science and Technology
- Additional Journal Information:
- Journal Volume: 56; Journal Issue: 17; Journal ID: ISSN 0013-936X
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 54 ENVIRONMENTAL SCIENCES; secondary organic aerosol; chamber; monoterpene; photooxidation; NOx effect
Citation Formats
Liu, Jiumeng, D’Ambro, Emma L., Lee, Ben Hwan, Schobesberger, Siegfried, Bell, David M., Zaveri, Rahul A., Zelenyuk, Alla, Thornton, Joel A., and Shilling, John E. Monoterpene Photooxidation in a Continuous-Flow Chamber: SOA Yields and Impacts of Oxidants, NOx, and VOC Precursors. United States: N. p., 2022.
Web. doi:10.1021/acs.est.2c02630.
Liu, Jiumeng, D’Ambro, Emma L., Lee, Ben Hwan, Schobesberger, Siegfried, Bell, David M., Zaveri, Rahul A., Zelenyuk, Alla, Thornton, Joel A., & Shilling, John E. Monoterpene Photooxidation in a Continuous-Flow Chamber: SOA Yields and Impacts of Oxidants, NOx, and VOC Precursors. United States. https://doi.org/10.1021/acs.est.2c02630
Liu, Jiumeng, D’Ambro, Emma L., Lee, Ben Hwan, Schobesberger, Siegfried, Bell, David M., Zaveri, Rahul A., Zelenyuk, Alla, Thornton, Joel A., and Shilling, John E. Wed .
"Monoterpene Photooxidation in a Continuous-Flow Chamber: SOA Yields and Impacts of Oxidants, NOx, and VOC Precursors". United States. https://doi.org/10.1021/acs.est.2c02630. https://www.osti.gov/servlets/purl/1888285.
@article{osti_1888285,
title = {Monoterpene Photooxidation in a Continuous-Flow Chamber: SOA Yields and Impacts of Oxidants, NOx, and VOC Precursors},
author = {Liu, Jiumeng and D’Ambro, Emma L. and Lee, Ben Hwan and Schobesberger, Siegfried and Bell, David M. and Zaveri, Rahul A. and Zelenyuk, Alla and Thornton, Joel A. and Shilling, John E.},
abstractNote = {We report monoterpene photooxidation plays an important role in secondary organic aerosol (SOA) formation in the atmosphere. The low-volatility products can enhance new particle formation and particle growth, and thus have influences on climate feedbacks. Here, we present the results of α-pinene and Δ-3-carene photooxidation experiments conducted in continuous-flow mode in an environmental chamber under several reaction conditions. The roles of oxidants, addition of NO, and VOC molecular structure in influencing SOA yield are illustrated. SOA yield from α-pinene photooxidation shows a weak dependence on H2O2 concentration, which is a proxy for HO2 concentration. The high O/C ratios observed in the a-pinene photooxidation products suggest the production of highly oxygenated organic molecules (HOM). Addition of ozone to the chamber during low-NOx photooxidation experiments leads to higher SOA yield. With the addition of NO, the production of N-containing HOMs is enhanced and the SOA yield shows a modest, non-linear dependence on input NO concentration. Carene photooxidation leads to higher SOA yield than α-pinene under similar reaction conditions, which agrees with the lower volatility retrieved from evaporation kinetics experiments. These results improve the understanding of SOA formation from monoterpene photooxidation and could be applied to refine the representation of biogenic SOA formation in models.},
doi = {10.1021/acs.est.2c02630},
journal = {Environmental Science and Technology},
number = 17,
volume = 56,
place = {United States},
year = {Wed Aug 17 00:00:00 EDT 2022},
month = {Wed Aug 17 00:00:00 EDT 2022}
}
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Works referenced in this record:
Aging of biogenic secondary organic aerosol via gas-phase OH radical reactions
journal, August 2012
- Donahue, N. M.; Henry, K. M.; Mentel, T. F.
- Proceedings of the National Academy of Sciences, Vol. 109, Issue 34
Kinetics, products, and mechanisms of secondary organic aerosol formation
journal, January 2012
- Ziemann, Paul J.; Atkinson, Roger
- Chemical Society Reviews, Vol. 41, Issue 19
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
Formation and evolution of molecular products in α-pinene secondary organic aerosol
journal, November 2015
- Zhang, Xuan; McVay, Renee C.; Huang, Dan D.
- Proceedings of the National Academy of Sciences, Vol. 112, Issue 46
Highly Oxygenated Organic Molecules (HOM) from Gas-Phase Autoxidation Involving Peroxy Radicals: A Key Contributor to Atmospheric Aerosol
journal, January 2019
- Bianchi, Federico; Kurtén, Theo; Riva, Matthieu
- Chemical Reviews, Vol. 119, Issue 6
The effect of particle acidity on secondary organic aerosol formation from <i>α</i>-pinene photooxidation under atmospherically relevant conditions
journal, November 2016
- Han, Yuemei; Stroud, Craig A.; Liggio, John
- Atmospheric Chemistry and Physics, Vol. 16, Issue 21
Secondary Organic Aerosol Production from Terpene Ozonolysis. 1. Effect of UV Radiation
journal, September 2005
- Presto, Albert A.; Huff Hartz, Kara E.; Donahue, Neil M.
- Environmental Science & Technology, Vol. 39, Issue 18
The effect of water on gas–particle partitioning of secondary organic aerosol. Part I: α-pinene/ozone system
journal, December 2001
- Cocker III, David R.; Clegg, Simon L.; Flagan, Richard C.
- Atmospheric Environment, Vol. 35, Issue 35
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
Elemental Analysis of Organic Species with Electron Ionization High-Resolution Mass Spectrometry
journal, November 2007
- Aiken, Allison C.; DeCarlo, Peter F.; Jimenez, Jose L.
- Analytical Chemistry, Vol. 79, Issue 21
Effect of the OH Radical Scavenger Hydrogen Peroxide on Secondary Organic Aerosol Formation from α-Pinene Ozonolysis
journal, April 2011
- Henry, Kaytlin M.; Donahue, Neil M.
- Aerosol Science and Technology, Vol. 45, Issue 6
Development of an Aerosol Mass Spectrometer for Size and Composition Analysis of Submicron Particles
journal, July 2000
- Jayne, John T.; Leard, Danna C.; Zhang, Xuefeng
- Aerosol Science and Technology, Vol. 33, Issue 1-2
The Model of Emissions of Gases and Aerosols from Nature version 2.1 (MEGAN2.1): an extended and updated framework for modeling biogenic emissions
journal, January 2012
- Guenther, A. B.; Jiang, X.; Heald, C. L.
- Geoscientific Model Development, Vol. 5, Issue 6
Efficient Isoprene Secondary Organic Aerosol Formation from a Non-IEPOX Pathway
journal, September 2016
- Liu, Jiumeng; D’Ambro, Emma L.; Lee, Ben H.
- Environmental Science & Technology, Vol. 50, Issue 18
Formation of Highly Oxidized Molecules from NO 3 Radical Initiated Oxidation of Δ-3-Carene: A Mechanistic Study
journal, May 2019
- Draper, Danielle C.; Myllys, Nanna; Hyttinen, Noora
- ACS Earth and Space Chemistry, Vol. 3, Issue 8
Phase partitioning and volatility of secondary organic aerosol components formed from α-pinene ozonolysis and OH oxidation: the importance of accretion products and other low volatility compounds
journal, January 2015
- Lopez-Hilfiker, F. D.; Mohr, C.; Ehn, M.
- Atmospheric Chemistry and Physics, Vol. 15, Issue 14
Influence of vapor wall loss in laboratory chambers on yields of secondary organic aerosol
journal, April 2014
- Zhang, X.; Cappa, C. D.; Jathar, S. H.
- Proceedings of the National Academy of Sciences, Vol. 111, Issue 16
Gas-phase tropospheric chemistry of biogenic volatile organic compounds: a review
journal, January 2003
- Atkinson, Roger; Arey, Janet
- Atmospheric Environment, Vol. 37
Particle Phase Acidity and Oligomer Formation in Secondary Organic Aerosol
journal, December 2004
- Gao, Song; Ng, Nga L.; Keywood, Melita
- Environmental Science & Technology, Vol. 38, Issue 24
Impact of NOx on secondary organic aerosol (SOA) formation from α-pinene and β-pinene photooxidation: the role of highly oxygenated organic nitrates
journal, January 2020
- Pullinen, Iida; Schmitt, Sebastian; Kang, Sungah
- Atmospheric Chemistry and Physics, Vol. 20, Issue 17
A robust clustering algorithm for analysis of composition-dependent organic aerosol thermal desorption measurements
journal, January 2020
- Li, Ziyue; D'Ambro, Emma L.; Schobesberger, Siegfried
- Atmospheric Chemistry and Physics, Vol. 20, Issue 4
Double Bonds Are Key to Fast Unimolecular Reactivity in First-Generation Monoterpene Hydroxy Peroxy Radicals
journal, March 2020
- Møller, Kristian H.; Otkjær, Rasmus V.; Chen, Jing
- The Journal of Physical Chemistry A, Vol. 124, Issue 14
Investigation of α-Pinene + Ozone Secondary Organic Aerosol Formation at Low Total Aerosol Mass
journal, June 2006
- Presto, Albert A.; Donahue, Neil M.
- Environmental Science & Technology, Vol. 40, Issue 11
Inter-comparison of laboratory smog chamber and flow reactor systems on organic aerosol yield and composition
journal, January 2015
- Bruns, E. A.; El Haddad, I.; Keller, A.
- Atmospheric Measurement Techniques, Vol. 8, Issue 6
Direct Observations of Atmospheric Aerosol Nucleation
journal, February 2013
- Kulmala, M.; Kontkanen, J.; Junninen, H.
- Science, Vol. 339, Issue 6122
Hydroxyl radical-induced formation of highly oxidized organic compounds
journal, December 2016
- Berndt, Torsten; Richters, Stefanie; Jokinen, Tuija
- Nature Communications, Vol. 7, Issue 1
Growth Kinetics and Size Distribution Dynamics of Viscous Secondary Organic Aerosol
journal, January 2018
- Zaveri, Rahul A.; Shilling, John E.; Zelenyuk, Alla
- Environmental Science & Technology, Vol. 52, Issue 3
Gas-phase products and secondary aerosol yields from the ozonolysis of ten different terpenes
journal, January 2006
- Lee, Anita; Goldstein, Allen H.; Keywood, Melita D.
- Journal of Geophysical Research, Vol. 111, Issue D7
α-pinene photooxidation under controlled chemical conditions – Part 2: SOA yield and composition in low- and high-NO x environments
journal, January 2012
- Eddingsaas, N. C.; Loza, C. L.; Yee, L. D.
- Atmospheric Chemistry and Physics, Vol. 12, Issue 16
Organic Aerosol Yields from α-Pinene Oxidation: Bridging the Gap between First-Generation Yields and Aging Chemistry
journal, October 2012
- Henry, Kaytlin M.; Lohaus, Theresa; Donahue, Neil M.
- Environmental Science & Technology, Vol. 46, Issue 22
OH radical formation yields from the gas-phase reactions of O 3 with alkenes and monoterpenes
journal, December 1996
- Chew, Andrew A.; Atkinson, Roger
- Journal of Geophysical Research: Atmospheres, Vol. 101, Issue D22
Evolution of Organic Aerosols in the Atmosphere
journal, December 2009
- Jimenez, J. L.; Canagaratna, M. R.; Donahue, N. M.
- Science, Vol. 326, Issue 5959
Secondary organic aerosol formation from isoprene photooxidation under high-NO x conditions : SOA FORMATION FROM ISOPRENE OXIDATION
journal, September 2005
- Kroll, Jesse H.; Ng, Nga L.; Murphy, Shane M.
- Geophysical Research Letters, Vol. 32, Issue 18
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
Carbon oxidation state as a metric for describing the chemistry of atmospheric organic aerosol
journal, January 2011
- Kroll, Jesse H.; Donahue, Neil M.; Jimenez, Jose L.
- Nature Chemistry, Vol. 3, Issue 2
Potential dual effect of anthropogenic emissions on the formation of biogenic secondary organic aerosol (BSOA)
journal, January 2019
- Kari, Eetu; Hao, Liqing; Ylisirniö, Arttu
- Atmospheric Chemistry and Physics, Vol. 19, Issue 24
SOA and gas phase organic acid yields from the sequential photooxidation of seven monoterpenes
journal, August 2018
- Friedman, Beth; Farmer, Delphine K.
- Atmospheric Environment, Vol. 187
Solar eclipse demonstrating the importance of photochemistry in new particle formation
journal, April 2017
- Jokinen, Tuija; Kontkanen, Jenni; Lehtipalo, Katrianne
- Scientific Reports, Vol. 7, Issue 1
High-resolution biogenic global emission inventory for the time period 2000–2019 for air quality modelling
journal, January 2022
- Sindelarova, Katerina; Markova, Jana; Simpson, David
- Earth System Science Data, Vol. 14, Issue 1
The properties and behavior of α-pinene secondary organic aerosol particles exposed to ammonia under dry conditions
journal, January 2017
- Bell, David M.; Imre, Dan; T. Martin, Scot
- Physical Chemistry Chemical Physics, Vol. 19, Issue 9
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
The link between organic aerosol mass loading and degree of oxygenation: an α-pinene photooxidation study
journal, January 2013
- Pfaffenberger, L.; Barmet, P.; Slowik, J. G.
- Atmospheric Chemistry and Physics, Vol. 13, Issue 13
A large source of low-volatility secondary organic aerosol
journal, February 2014
- Ehn, Mikael; Thornton, Joel A.; Kleist, Einhard
- Nature, Vol. 506, Issue 7489
Airborne Single Particle Mass Spectrometers (SPLAT II & miniSPLAT) and New Software for Data Visualization and Analysis in a Geo-Spatial Context
journal, January 2015
- Zelenyuk, Alla; Imre, Dan; Wilson, Jacqueline
- Journal of The American Society for Mass Spectrometry, Vol. 26, Issue 2
Effect of NO<sub>x</sub> level on secondary organic aerosol (SOA) formation from the photooxidation of terpenes
journal, January 2007
- Ng, N. L.; Chhabra, P. S.; Chan, A. W. H.
- Atmospheric Chemistry and Physics, Vol. 7, Issue 19
Recent advances in understanding secondary organic aerosol: Implications for global climate forcing: Advances in Secondary Organic Aerosol
journal, June 2017
- Shrivastava, Manish; Cappa, Christopher D.; Fan, Jiwen
- Reviews of Geophysics, Vol. 55, Issue 2
Ozonolysis of α -pinene at atmospherically relevant concentrations: Temperature dependence of aerosol mass fractions (yields)
journal, January 2007
- Pathak, Ravi K.; Stanier, Charles O.; Donahue, Neil M.
- Journal of Geophysical Research, Vol. 112, Issue D3
Effect of oxidant concentration, exposure time, and seed particles on secondary organic aerosol chemical composition and yield
journal, January 2015
- Lambe, A. T.; Chhabra, P. S.; Onasch, T. B.
- Atmospheric Chemistry and Physics, Vol. 15, Issue 6
Anthropogenic enhancements to production of highly oxygenated molecules from autoxidation
journal, March 2019
- Pye, Havala O. T.; D’Ambro, Emma L.; Lee, Ben H.
- Proceedings of the National Academy of Sciences, Vol. 116, Issue 14
Formation of OH radicals in the gas phase reactions of O 3 with a series of terpenes
journal, January 1992
- Atkinson, Roger; Aschmann, Sara M.; Arey, Janet
- Journal of Geophysical Research, Vol. 97, Issue D5
Photodegradation of α-Pinene Secondary Organic Aerosol Dominated by Moderately Oxidized Molecules
journal, May 2021
- Pospisilova, Veronika; Bell, David M.; Lamkaddam, Houssni
- Environmental Science & Technology, Vol. 55, Issue 10
Online analysis of secondary organic aerosols from OH-initiated photooxidation and ozonolysis of α-pinene, β-pinene, Δ3-carene and d-limonene by thermal desorption–photoionisation aerosol mass spectrometry
journal, January 2017
- Fang, Wenzheng; Gong, Lei; Sheng, Liusi
- Environmental Chemistry, Vol. 14, Issue 2
Source characterization of highly oxidized multifunctional compounds in a boreal forest environment using positive matrix factorization
journal, January 2016
- Yan, Chao; Nie, Wei; Äijälä, Mikko
- Atmospheric Chemistry and Physics, Vol. 16, Issue 19
Loading-dependent elemental composition of α-pinene SOA particles
journal, January 2009
- Shilling, J. E.; Chen, Q.; King, S. M.
- Atmospheric Chemistry and Physics, Vol. 9, Issue 3
Chamber-based insights into the factors controlling epoxydiol (IEPOX) secondary organic aerosol (SOA) yield, composition, and volatility
journal, January 2019
- D'Ambro, Emma L.; Schobesberger, Siegfried; Gaston, Cassandra J.
- Atmospheric Chemistry and Physics, Vol. 19, Issue 17
A novel method for online analysis of gas and particle composition: description and evaluation of a Filter Inlet for Gases and AEROsols (FIGAERO)
journal, January 2014
- Lopez-Hilfiker, F. D.; Mohr, C.; Ehn, M.
- Atmospheric Measurement Techniques, Vol. 7, Issue 4
Particle-Phase Diffusion Modulates Partitioning of Semivolatile Organic Compounds to Aged Secondary Organic Aerosol
journal, January 2020
- Zaveri, Rahul A.; Shilling, John E.; Zelenyuk, Alla
- Environmental Science & Technology, Vol. 54, Issue 5
Elemental ratio measurements of organic compounds using aerosol mass spectrometry: characterization, improved calibration, and implications
journal, January 2015
- Canagaratna, M. R.; Jimenez, J. L.; Kroll, J. H.
- Atmospheric Chemistry and Physics, Vol. 15, Issue 1
Modeling aerosol formation in alpha-pinene photo-oxidation experiments
journal, January 2008
- Capouet, M.; Müller, J. -F.; Ceulemans, K.
- Journal of Geophysical Research, Vol. 113, Issue D2
Pathways to Highly Oxidized Products in the Δ3-Carene + OH System
journal, February 2022
- D’Ambro, Emma L.; Hyttinen, Noora; Møller, Kristian H.
- Environmental Science & Technology, Vol. 56, Issue 4
Ambient aerosol sampling using the Aerodyne Aerosol Mass Spectrometer
journal, January 2003
- Jimenez, Jose L.
- Journal of Geophysical Research, Vol. 108, Issue D7
Photolysis Controls Atmospheric Budgets of Biogenic Secondary Organic Aerosol
journal, March 2020
- Zawadowicz, Maria A.; Lee, Ben H.; Shrivastava, Manish
- Environmental Science & Technology, Vol. 54, Issue 7
SOA formation from the photooxidation of α -pinene: systematic exploration of the simulation of chamber data
journal, January 2016
- McVay, Renee C.; Zhang, Xuan; Aumont, Bernard
- Atmospheric Chemistry and Physics, Vol. 16, Issue 5
Chemistry of secondary organic aerosol: Formation and evolution of low-volatility organics in the atmosphere
journal, May 2008
- Kroll, Jesse H.; Seinfeld, John H.
- Atmospheric Environment, Vol. 42, Issue 16
An Iodide-Adduct High-Resolution Time-of-Flight Chemical-Ionization Mass Spectrometer: Application to Atmospheric Inorganic and Organic Compounds
journal, May 2014
- Lee, Ben H.; Lopez-Hilfiker, Felipe D.; Mohr, Claudia
- Environmental Science & Technology, Vol. 48, Issue 11
Production of extremely low volatile organic compounds from biogenic emissions: Measured yields and atmospheric implications
journal, May 2015
- Jokinen, Tuija; Berndt, Torsten; Makkonen, Risto
- Proceedings of the National Academy of Sciences, Vol. 112, Issue 23