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

G. M. Wolfe; T. F. Hanisco; H. L. Arkinson; D. R. Blake; A. Wisthaler; A. Wisthaler; T. Mikoviny; T. B. Ryerson; T. B. Ryerson; T. B. Ryerson; I. Pollack; I. Pollack; J. Peischl; P. O. Wennberg; P. O. Wennberg; J. D. Crounse; J. M. St. Clair; J. M. St. Clair; A. Teng; A. Teng; L. G. Huey; X. Liu; X. Liu; A. Fried; P. Weibring; D. Richter; J. Walega; S. R. Hall; K. Ullmann; J. L. Jimenez; J. L. Jimenez; P. Campuzano-Jost; P. Campuzano-Jost; T. P. Bui; G. Diskin; J. R. Podolske; G. Sachse; G. Sachse; R. C. Cohen; R. C. Cohen

doi:10.5194/acp-22-4253-2022

Atmospheric Chemistry and Physics (Apr 2022)

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

G. M. Wolfe,
T. F. Hanisco,
H. L. Arkinson,
D. R. Blake,
A. Wisthaler,
A. Wisthaler,
T. Mikoviny,
T. B. Ryerson,
T. B. Ryerson,
T. B. Ryerson,
I. Pollack,
I. Pollack,
J. Peischl,
P. O. Wennberg,
P. O. Wennberg,
J. D. Crounse,
J. M. St. Clair,
J. M. St. Clair,
A. Teng,
A. Teng,
L. G. Huey,
X. Liu,
X. Liu,
A. Fried,
P. Weibring,
D. Richter,
J. Walega,
S. R. Hall,
K. Ullmann,
J. L. Jimenez,
J. L. Jimenez,
P. Campuzano-Jost,
P. Campuzano-Jost,
T. P. Bui,
G. Diskin,
J. R. Podolske,
G. Sachse,
G. Sachse,
R. C. Cohen,
R. C. Cohen

Affiliations

G. M. Wolfe: Atmospheric Chemistry and Dynamics Laboratory, NASA Goddard Space Flight Center, Greenbelt, MD, USA
T. F. Hanisco: Atmospheric Chemistry and Dynamics Laboratory, NASA Goddard Space Flight Center, Greenbelt, MD, USA
H. L. Arkinson: Department of Oceanic and Atmospheric Science, University of Maryland, College Park, MD, USA
D. R. Blake: Department of Chemistry, University of California Irvine, Irvine, CA, USA
A. Wisthaler: Institute for Ion Physics and Applied Physics, University of Innsbruck, Innsbruck, Austria
A. Wisthaler: Department of Chemistry, University of Oslo, Oslo, Norway
T. Mikoviny: Department of Chemistry, University of Oslo, Oslo, Norway
T. B. Ryerson: Chemical Sciences Laboratory, NOAA, Boulder, CO, USA
T. B. Ryerson: Cooperative Institute for Research in Environmental Sciences, University of Colorado Boulder, Boulder, CO, USA
T. B. Ryerson: now at: Scientific Aviation, Boulder, CO, USA
I. Pollack: Cooperative Institute for Research in Environmental Sciences, University of Colorado Boulder, Boulder, CO, USA
I. Pollack: now at: Department of Atmospheric Science, Colorado State University, Fort Collins, CO, USA
J. Peischl: Cooperative Institute for Research in Environmental Sciences, University of Colorado Boulder, Boulder, CO, USA
P. O. Wennberg: Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA, USA
P. O. Wennberg: Division of Engineering and Applied Science, California Institute of Technology, Pasadena, CA, USA
J. D. Crounse: Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA, USA
J. M. St. Clair: Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA, USA
J. M. St. Clair: now at: Joint Center for Earth Systems Technology, University of Maryland Baltimore County, Baltimore, MD, USA
A. Teng: Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA, USA
A. Teng: now at: Fifty Years, San Francisco, CA, USA
L. G. Huey: School of Earth and Atmospheric Sciences, Georgia Institute of Technology, Atlanta, GA, USA
X. Liu: School of Earth and Atmospheric Sciences, Georgia Institute of Technology, Atlanta, GA, USA
X. Liu: now at: Monitoring and Laboratory Division, California Air Resources Board, Los Angeles, CA, USA
A. Fried: Institute of Arctic and Alpine Research, University of Colorado, Boulder, CO, USA
P. Weibring: Institute of Arctic and Alpine Research, University of Colorado, Boulder, CO, USA
D. Richter: Institute of Arctic and Alpine Research, University of Colorado, Boulder, CO, USA
J. Walega: Institute of Arctic and Alpine Research, University of Colorado, Boulder, CO, USA
S. R. Hall: Atmospheric Chemistry Observations and Modeling Laboratory, National Center for Atmospheric Research, Boulder, CO, USA
K. Ullmann: Atmospheric Chemistry Observations and Modeling Laboratory, National Center for Atmospheric Research, Boulder, CO, USA
J. L. Jimenez: Cooperative Institute for Research in Environmental Sciences, University of Colorado Boulder, Boulder, CO, USA
J. L. Jimenez: Department of Chemistry, University of Colorado Boulder, Boulder, CO, USA
P. Campuzano-Jost: Cooperative Institute for Research in Environmental Sciences, University of Colorado Boulder, Boulder, CO, USA
P. Campuzano-Jost: Department of Chemistry, University of Colorado Boulder, Boulder, CO, USA
T. P. Bui: Atmospheric Sciences Branch, NASA Ames Research Center, Moffett Field, CA, USA
G. Diskin: Chemistry and Dynamics Branch, NASA Langley Research Center, Hampton, VA, USA
J. R. Podolske: Atmospheric Sciences Branch, NASA Ames Research Center, Moffett Field, CA, USA
G. Sachse: Chemistry and Dynamics Branch, NASA Langley Research Center, Hampton, VA, USA
G. Sachse: National Institute of Aerospace, Hampton, VA, USA
R. C. Cohen: Department of Earth and Planetary Sciences, University of California, Berkeley, Berkeley, CA, USA
R. C. Cohen: College of Chemistry, University of California, Berkeley, Berkeley, CA, USA

DOI: https://doi.org/10.5194/acp-22-4253-2022
Journal volume & issue: Vol. 22
pp. 4253 – 4275

Abstract

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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.

Published in Atmospheric Chemistry and Physics

ISSN: 1680-7316 (Print); 1680-7324 (Online)
Publisher: Copernicus Publications
Country of publisher: Germany
LCC subjects: Science: Physics; Science: Chemistry
Website: http://www.atmospheric-chemistry-and-physics.net/

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