Variability and Time of Day Dependence of Ozone Photochemistry in Western Wildfire Plumes.

Understanding the efficiency and variability of photochemical ozone (O3) production from western wildfire plumes is important to accurately estimate their influence on North American air quality. A set of photochemical measurements were made from the NOAA Twin Otter research aircraft as a part of the Fire Influence on Regional to Global Environments and Air Quality (FIREX-AQ) experiment. We use a zero-dimensional (0-D) box model to investigate the chemistry driving O3 production in modeled plumes. Modeled afternoon plumes reached a maximum O3 mixing ratio of 140 ± 50 ppbv (average ± standard deviation) within 20 ± 10 min of emission compared to 76 ± 12 ppbv in 60 ± 30 min in evening plumes. Afternoon and evening maximum O3 isopleths indicate that plumes were near their peak in NOx efficiency. A radical budget describes the NOx volatile - organic compound (VOC) sensitivities of these plumes. Afternoon plumes displayed a rapid transition from VOC-sensitive to NOx-sensitive chemistry, driven by HOx (=OH + HO2) production from photolysis of nitrous acid (HONO) (48 ± 20% of primary HOx) and formaldehyde (HCHO) (26 ± 9%) emitted directly from the fire. Evening plumes exhibit a slower transition from peak NOx efficiency to VOC-sensitive O3 production caused by a reduction in photolysis rates and fire emissions. HOx production in evening plumes is controlled by HONO photolysis (53 ± 7%), HCHO photolysis (18 ± 9%), and alkene ozonolysis (17 ± 9%).

[1]  J. D. de Gouw,et al.  The nitrogen budget of laboratory-simulated western US wildfires during the FIREX 2016 Fire Lab study , 2020, Atmospheric Chemistry and Physics.

[2]  J. Thornton,et al.  HONO Emissions from Western U.S. Wildfires Provide Dominant Radical Source in Fresh Wildfire Smoke. , 2020, Environmental science & technology.

[3]  J. Thornton,et al.  Performance of a new coaxial ion–molecule reaction region for low-pressure chemical ionization mass spectrometry with reduced instrument wall interactions , 2019, Atmospheric Measurement Techniques.

[4]  Kei Sato,et al.  Relative and Absolute Sensitivity Analysis on Ozone Production in Tsukuba, a City in Japan. , 2019, Environmental science & technology.

[5]  A. Hofzumahaus,et al.  Fast photochemistry in wintertime haze: Consequences for pollution mitigation strategies. , 2019, Environmental science & technology.

[6]  A. Goldstein,et al.  Highly speciated measurements of terpenoids emitted from laboratory and mixed-conifer forest prescribed fires. , 2019, Environmental science & technology.

[7]  M. Andreae.  Emission of trace gases and aerosols from biomass burning – an updated assessment , 2019, Atmospheric Chemistry and Physics.

[8]  J. D. de Gouw,et al.  OH chemistry of non-methane organic gases (NMOGs) emitted from laboratory and ambient biomass burning smoke: evaluating the influence of furans and oxygenated aromatics on ozone and secondary NMOG formation , 2019, Atmospheric Chemistry and Physics.

[9]  J. Peischl,et al.  Nighttime Chemical Transformation in Biomass Burning Plumes: A Box Model Analysis Initialized with Aircraft Observations. , 2019, Environmental science & technology.

[10]  J. D. de Gouw,et al.  Secondary organic aerosol (SOA) yields from NO3 radical + isoprene based on nighttime aircraft power plant plume transects , 2018, Atmospheric Chemistry and Physics.

[11]  Robert J. Yokelson,et al.  High- and low-temperature pyrolysis profiles describe volatile organic compound emissions from western US wildfire fuels , 2018, Atmospheric Chemistry and Physics.

[12]  J. D. de Gouw,et al.  Identification and Quantification of 4-Nitrocatechol Formed from OH and NO3 Radical-Initiated Reactions of Catechol in Air in the Presence of NOx: Implications for Secondary Organic Aerosol Formation from Biomass Burning. , 2018, Environmental science & technology.

[13]  J. Jimenez,et al.  Non-methane organic gas emissions from biomass burning: identification, quantification, and emission factors from PTR-ToF during the FIREX 2016 laboratory experiment , 2017 .

[14]  D. Griffith,et al.  Aerosol optical properties and trace gas emissions by PAX and OP-FTIR for laboratory-simulated western US wildfires during FIREX , 2017 .

[15]  D. Blake,et al.  Higher measured than modeled ozone production at increased NO x levels in the Colorado Front Range , 2017 .

[16]  S. Herndon,et al.  Changes in ozone and precursors during two aged wildfire smoke events in the Colorado Front Range in summer 2015 , 2017 .

[17]  Jennifer K. Balch,et al.  Human-started wildfires expand the fire niche across the United States , 2017, Proceedings of the National Academy of Sciences.

[18]  A. Stohl,et al.  Wildfire influences on the variability and trend of summer surface ozone in the mountainous western United States , 2016 .

[19]  R. Dickerson,et al.  Ozone production and its sensitivity to NO x and VOCs: results from the DISCOVER-AQ field experiment, Houston 2013 , 2016 .

[20]  J. Seinfeld,et al.  Formation of highly oxygenated low-volatility products from cresol oxidation , 2016 .

[21]  A. P. Williams,et al.  Impact of anthropogenic climate change on wildfire across western US forests , 2016, Proceedings of the National Academy of Sciences.

[22]  G. Wolfe,et al.  The Framework for 0-D Atmospheric Modeling (F0AM) v3.1 , 2016 .

[23]  Jack J. Lin,et al.  Instrumentation and Measurement Strategy for the NOAA SENEX Aircraft Campaign as Part of the Southeast Atmosphere Study 2013. , 2016, Atmospheric measurement techniques.

[24]  D. Blake,et al.  Multi-instrument comparison and compilation of non-methane organic gas emissions from biomass burning and implications for smoke-derived secondary organic aerosol precursors , 2016 .

[25]  A. Westerling.  Increasing western US forest wildfire activity: sensitivity to changes in the timing of spring , 2016, Philosophical Transactions of the Royal Society B: Biological Sciences.

[26]  Brian D. Drollette,et al.  Oil sands operations as a large source of secondary organic aerosols , 2016, Nature.

[27]  I. R. Burling,et al.  Biomass burning emissions and potential air quality impacts of volatile organic compounds and other trace gases from fuels common in the US , 2015 .

[28]  E. Fischer,et al.  Smoke in the City: How Often and Where Does Smoke Impact Summertime Ozone in the United States? , 2015, Environmental science & technology.

[29]  F. Keutsch,et al.  In situ measurements and modeling of reactive trace gases in a small biomass burning plume , 2015 .

[30]  David W. Fahey,et al.  Challenges of a lowered U.S. ozone standard , 2015, Science.

[31]  D. Jaffe,et al.  Ozone enhancement in western US wildfire plumes at the Mt. Bachelor Observatory: The role of NOx , 2015 .

[32]  Jonathan Williams,et al.  Characterization of biomass burning emissions from cooking fires, peat, crop residue, and other fuels with high-resolution proton-transfer-reaction time-of-flight mass spectrometry , 2015 .

[33]  C. Sweeney,et al.  High winter ozone pollution from carbonyl photolysis in an oil and gas basin , 2014, Nature.

[34]  J. Pankow,et al.  Identification and quantification of gaseous organic compounds emitted from biomass burning using two-dimensional gas chromatography-time-of-flight mass spectrometry , 2014 .

[35]  J. Thornton,et al.  An iodide-adduct high-resolution time-of-flight chemical-ionization mass spectrometer: application to atmospheric inorganic and organic compounds. , 2014, Environmental science & technology.

[36]  S. K. Akagi,et al.  Pitfalls with the use of enhancement ratios or normalized excess mixing ratios measured in plumes to characterize pollution sources and aging , 2013 .

[37]  J. Thornton,et al.  N2O5 uptake coefficients and nocturnal NO2 removal rates determined from ambient wintertime measurements , 2013 .

[38]  J. D. de Gouw,et al.  Vertically resolved measurements of nighttime radical reservoirs in Los Angeles and their contribution to the urban radical budget. , 2012, Environmental science & technology.

[39]  S. K. Akagi,et al.  Measurements of reactive trace gases and variable O3 formation rates in some South Carolina biomass burning plumes , 2012 .

[40]  D. Blake,et al.  Observations of nonmethane organic compounds during ARCTAS - Part 1: Biomass burning emissions and plume enhancements , 2011 .

[41]  D. Venables,et al.  Near-ultraviolet absorption cross sections of nitrophenols and their potential influence on tropospheric oxidation capacity. , 2011, The journal of physical chemistry. A.

[42]  W. Brune,et al.  Interactive comment on “ Direct measurement of ozone production rates in Houston in 2009 and comparison with two estimation methods ” , 2012 .

[43]  D. M. Brookes,et al.  Ozone production in remote oceanic and industrial areas derived from ship based measurements of peroxy radicals during TexAQS 2006 , 2010 .

[44]  W. Brune,et al.  Atmospheric oxidation capacity in the summer of Houston 2006: Comparison with summer measurements in other metropolitan studies , 2010 .

[45]  Ryan Z. Hinrichs,et al.  Heterogeneous reactions of surface-adsorbed catechol with nitrogen dioxide: substrate effects for tropospheric aerosol surrogates. , 2010, Physical chemistry chemical physics : PCCP.

[46]  Scott C. Herndon,et al.  Atmospheric Chemistry and Physics a Case Study of Ozone Production, Nitrogen Oxides, and the Radical Budget in Mexico City , 2022 .

[47]  E. Crosson,et al.  A cavity ring-down analyzer for measuring atmospheric levels of methane, carbon dioxide, and water vapor , 2008 .

[48]  D. Spracklen,et al.  Influence of fires on O3 concentrations in the western U.S. , 2008, Environmental science & technology.

[49]  Luigi Mondello,et al.  Comprehensive two-dimensional gas chromatography-mass spectrometry: a review. , 2008, Mass spectrometry reviews.

[50]  M. Molina,et al.  Oxidative capacity of the Mexico City atmosphere - Part 1: A radical source perspective , 2007 .

[51]  Katrin Fuhrer,et al.  Field-deployable, high-resolution, time-of-flight aerosol mass spectrometer. , 2006, Analytical chemistry.

[52]  T. Swetnam,et al.  Warming and Earlier Spring Increase Western U.S. Forest Wildfire Activity , 2006, Science.

[53]  R. Derwent,et al.  Atmospheric Chemistry and Physics Protocol for the Development of the Master Chemical Mechanism, Mcm V3 (part B): Tropospheric Degradation of Aromatic Volatile Organic Compounds , 2022 .

[54]  J H Seinfeld,et al.  Urban Air Pollution: State of the Science , 1989, Science.

[55]  W. Chameides,et al.  The role of biogenic hydrocarbons in urban photochemical smog: Atlanta as a case study. , 1988, Science.

[56]  H. Levy.  Normal Atmosphere: Large Radical and Formaldehyde Concentrations Predicted , 1971, Science.

[57]  P. Crutzen.  The influence of nitrogen oxides on the atmospheric ozone content , 1970 .

[58]  B. Duncan,et al.  Vegetation fire emissions and their impact on air pollution and climate , 2009 .

[59]  L. Kleinman.  The dependence of tropospheric ozone production rate on ozone precursors , 2005 .

[60]  R. Olariu,et al.  Nitrated phenols in the atmosphere: a review , 2005 .