title: Potential role of stabilized Criegee radicals in sulfuric acid production in a high biogenic VOC environment.
abstract: We present field observations made in June 2011 downwind of Dallas-Fort Worth, TX, and evaluate the role of stabilized Criegee radicals (sCIs) in gaseous sulfuric acid (H2SO4) production. Zero-dimensional model calculations show that sCI from biogenic volatile organic compounds composed the majority of the sCIs. The main uncertainty associated with an evaluation of H2SO4 production from the sCI reaction channel is the lack of experimentally determined reaction rates for sCIs formed from isoprene ozonolysis with SO2 along with systematic discrepancies in experimentally derived reaction rates between other sCIs and SO2 and water vapor. In general, the maximum of H2SO4 production from the sCI channel is found in the late afternoon as ozone increases toward the late afternoon. The sCI channel, however, contributes minor H2SO4 production compared with the conventional OH channel in the mid-day. Finally, the production and the loss rates of H2SO4 are compared. The application of the recommended mass accommodation coefficient causes significant overestimation of H2SO4 loss rates compared with H2SO4 production rates. However, the application of a lower experimental value for the mass accommodation coefficient provides good agreement between the loss and production rates of H2SO4. The results suggest that the recommended coefficient for the H2O surface may not be suitable for this relatively dry environment.
authors.affiliation: †Department of Earth System Science, University of California-Irvine, Irvine, California 92697, United States.
authors.forename: Saewung
authors.initials: S
authors.lastname: Kim
authors.affiliation: ‡Atmospheric Sciences and Global Change Division, Pacific Northwest National Laboratory, Richland, Washington 99354, United States.|§Department of Civil and Environmental Engineering, Washington State University, Pullman, Washington 99164, United States.
authors.forename: Alex
authors.initials: A
authors.lastname: Guenther
authors.affiliation: ∥Department of Earth and Atmospheric Sciences, University of Houston, Houston, Texas 77004, United States.
authors.forename: Barry
authors.initials: B
authors.lastname: Lefer
authors.affiliation: ∥Department of Earth and Atmospheric Sciences, University of Houston, Houston, Texas 77004, United States.
authors.forename: James
authors.initials: J
authors.lastname: Flynn
authors.affiliation: ⊥Department of Civil and Environmental Engineering, Rice University, Houston, Texas 77005, United States.
authors.forename: Robert
authors.initials: R
authors.lastname: Griffin
authors.affiliation: ⊥Department of Civil and Environmental Engineering, Rice University, Houston, Texas 77005, United States.
authors.forename: Andrew P
authors.initials: AP
authors.lastname: Rutter
authors.affiliation: ⊥Department of Civil and Environmental Engineering, Rice University, Houston, Texas 77005, United States.|▽California Air Resource Board, Monitoring and Laboratory Division, Sacramento California 95811, United States.
authors.forename: Longwen
authors.initials: L
authors.lastname: Gong
authors.affiliation: ⊥Department of Civil and Environmental Engineering, Rice University, Houston, Texas 77005, United States.
authors.forename: Basak Karakurt
authors.initials: BK
authors.lastname: Cevik
mesh_terms: D004784:Environmental Monitoring / Q000379:methods; D008962:Models, Theoretical; D010126:Ozone / Q000737:chemistry*; D013458:Sulfur Dioxide / Q000737:chemistry; D013464:Sulfuric Acids / Q000737:chemistry*; D013781:Texas; D055549:Volatile Organic Compounds / Q000737:chemistry*
chemical_list: D013464:Sulfuric Acids; D055549:Volatile Organic Compounds; D013458:Sulfur Dioxide; D010126:Ozone; C033158:sulfuric acid