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Photochemical evolution of the 2013 California Rim Fire: synergistic impacts of reactive hydrocarbons and enhanced oxidants

Wolfe, Glenn M. and Hanisco, Thomas F. and Arkinson, Heather L. and Blake, Donald R. and Wisthaler, Armin and Mikoviny, Tomas and Ryerson, Thomas B. and Pollack, Ilana and Peischl, Jeff and Wennberg, Paul O. and Crounse, John D. and St. Clair, Jason M. and Teng, Alex and Huey, L. Gregory and Liu, Xiaoxi and Fried, Alan and Weibring, Petter and Richter, Dirk and Walega, James and Hall, Samuel R. and Ullmann, Kirk and Jimenez, Jose L. and Campuzano-Jost, Pedro and Bui, T. Paul and Diskin, Glenn and Podolske, James R. and Sachse, Glen and Cohen, Ronald C. (2022) Photochemical evolution of the 2013 California Rim Fire: synergistic impacts of reactive hydrocarbons and enhanced oxidants. Atmospheric Chemistry and Physics, 22 (6). pp. 4253-4275. ISSN 1680-7324. doi:10.5194/acp-22-4253-2022.

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Large wildfires influence regional atmospheric composition, but chemical complexity challenges model predictions of downwind impacts. Here, we elucidate key connections within gas-phase photochemistry and assess novel chemical processes via a case study of the 2013 California Rim Fire plume. Airborne in situ observations, acquired during the NASA Studies of Emissions, Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys (SEAC⁴RS) mission, illustrate the evolution of volatile organic compounds (VOCs), oxidants, and reactive nitrogen over 12 h of atmospheric aging. Measurements show rapid formation of ozone and peroxyacyl nitrates (PNs), sustained peroxide production, and prolonged enhancements in oxygenated VOCs and nitrogen oxides (NOₓ). Observations and Lagrangian trajectories constrain a 0-D puff model that approximates plume photochemical history and provides a framework for evaluating process interactions. Simulations examine the effects of (1) previously unmeasured reactive VOCs identified in recent laboratory studies and (2) emissions and secondary production of nitrous acid (HONO). Inclusion of estimated unmeasured VOCs leads to a 250 % increase in OH reactivity and a 70 % increase in radical production via oxygenated VOC photolysis. HONO amplifies radical cycling and serves as a downwind NOₓ source, although impacts depend on how HONO is introduced. The addition of initial HONO (representing primary emissions) or particulate nitrate photolysis amplifies ozone production, while heterogeneous conversion of NO₂ suppresses ozone formation. Analysis of radical initiation rates suggests that oxygenated VOC photolysis is a major radical source, exceeding HONO photolysis when averaged over the first 2 h of aging. Ozone production chemistry transitions from VOC sensitive to NOₓ sensitive within the first hour of plume aging, with both peroxide and organic nitrate formation contributing significantly to radical termination. To simulate smoke plume chemistry accurately, models should simultaneously account for the full reactive VOC pool and all relevant oxidant sources.

Item Type:Article
Related URLs:
URLURL TypeDescription Information ItemCode
Wolfe, Glenn M.0000-0001-6586-4043
Hanisco, Thomas F.0000-0001-9434-8507
Arkinson, Heather L.0000-0002-0282-4164
Blake, Donald R.0000-0002-8283-5014
Wisthaler, Armin0000-0001-5050-3018
Mikoviny, Tomas0000-0002-8461-0783
Ryerson, Thomas B.0000-0003-2800-7581
Pollack, Ilana0000-0001-7151-9756
Peischl, Jeff0000-0002-9320-7101
Wennberg, Paul O.0000-0002-6126-3854
Crounse, John D.0000-0001-5443-729X
St. Clair, Jason M.0000-0002-9367-5749
Teng, Alex0000-0002-6434-0501
Huey, L. Gregory0000-0002-0518-7690
Liu, Xiaoxi0000-0002-5104-8886
Fried, Alan0000-0002-5230-3527
Weibring, Petter0000-0001-9567-3803
Richter, Dirk0000-0002-2156-031X
Walega, James0000-0001-9167-8121
Hall, Samuel R.0000-0002-2060-7112
Ullmann, Kirk0000-0002-4724-9634
Jimenez, Jose L.0000-0001-6203-1847
Campuzano-Jost, Pedro0000-0003-3930-010X
Bui, T. Paul0000-0001-9189-0405
Diskin, Glenn0000-0002-3617-0269
Podolske, James R.0000-0003-2771-5375
Cohen, Ronald C.0000-0001-6617-7691
Additional Information:© Author(s) 2022. This work is distributed under the Creative Commons Attribution 4.0 License. Received: 04 Nov 2021 – Discussion started: 12 Nov 2021 – Revised: 22 Jan 2022 – Accepted: 15 Feb 2022 – Published: 01 Apr 2022. The SEAC⁴RS mission was supported by the NASA Tropospheric Composition program and grants from the NASA ROSES SEAC⁴RS program (grant nos. NNH10ZDA001N, NNX12AC03G, and NNX12AB82G). We thank the DC-8 pilots, crew, payload operators, and mission scientists, for their hard work and dedication. We thank Luke Ziemba, Lee Thornhill, and the LARGE team, for the LAS data. We thank Anthony Bucholtz, for the BBR data. We are also grateful to NASA ESPO, for the mission logistics. Analysis and modeling were supported by NOAA Climate Program Office's Atmospheric Chemistry, Carbon Cycle, and Climate program (grant no. NA17OAR4310004). The Jimenez group acknowledges support from NASA (grant nos. 80NSSC19k0124 and 80NSSC18K0630). The PTR-MS measurements during SEAC⁴RS were supported by the Austrian Federal Ministry for Transport, Innovation, and Technology (bmvit) through the Austrian Space Applications Programme (ASAP) of the Austrian Research Promotion Agency (FFG). Armin Wisthaler and Tomas Mikoviny received support from the Visiting Scientist Program at the National Institute of Aerospace (NIA). We thank many colleagues for their assistance, insight, and feedback, including Steve Brown, Christine Wiedinmyer, Sarah Strode, Ann Marie Carlton, Matt Coggon, Jim Roberts, Joel Thornton, and Qiaoyun Peng. This research has been supported by the NASA Earth Sciences Division (grant nos. NNH10ZDA001N, NNX12AC03G, NNX12AB82G, 80NSSC19K0124, and 80NSSC18K0630) and the NASA Climate Program Office (grant no. NA17OAR4310004). Author contributions. GMW conceptualized the study, conducted the modeling and analysis, and wrote the paper. All authors contributed to the collection of SEAC⁴RS observations used to constrain and evaluate the model. The supplement related to this article is available online at: Code and data availability. Data used in this study are archived at (SEAC4RS Science Team, 2013). The F0AM box model is available at (last access: 18 May 2021) and (Wolfe, 2021). The model setup code is available from the contact author upon request. This paper was edited by Andreas Hofzumahaus and reviewed by D. A. J. Jaffe and one anonymous referee. Competing interests. At least one of the (co-)authors is a member of the editorial board of Atmospheric Chemistry and Physics. The peer-review process was guided by an independent editor, and the authors also have no other competing interests to declare.
Funding AgencyGrant Number
National Oceanic and Atmospheric Administration (NOAA)NA17OAR4310004
Bundesministerium für Verkehr, Innovation und Technologie (BMVIT)UNSPECIFIED
Österreichische Forschungsförderungsgesellschaft (FFG)UNSPECIFIED
National Institute of Aerospace (NIA)UNSPECIFIED
Issue or Number:6
Record Number:CaltechAUTHORS:20220414-28035000
Persistent URL:
Official Citation:Wolfe, G. M., Hanisco, T. F., Arkinson, H. L., Blake, D. R., Wisthaler, A., Mikoviny, T., Ryerson, T. B., Pollack, I., Peischl, J., Wennberg, P. O., Crounse, J. D., St. Clair, J. M., Teng, A., Huey, L. G., Liu, X., Fried, A., Weibring, P., Richter, D., Walega, J., Hall, S. R., Ullmann, K., Jimenez, J. L., Campuzano-Jost, P., Bui, T. P., Diskin, G., Podolske, J. R., Sachse, G., and Cohen, R. C.: Photochemical evolution of the 2013 California Rim Fire: synergistic impacts of reactive hydrocarbons and enhanced oxidants, Atmos. Chem. Phys., 22, 4253–4275,, 2022.
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:114331
Deposited By: George Porter
Deposited On:15 Apr 2022 15:55
Last Modified:15 Apr 2022 15:55

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