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Potential Role of Stabilized Criegee Radicals in Sulfuric Acid Production in a High Biogenic VOC Environment
Journal article   Open access   Peer reviewed

Potential Role of Stabilized Criegee Radicals in Sulfuric Acid Production in a High Biogenic VOC Environment

Saewung Kim, Alex Guenther, Barry Lefer, James Flynn, Robert Griffin, Andrew P. Rutter, Longwen Gong and Basak Karakurt Cevik
Environmental science & technology, Vol.49(6), pp.3383-3391
03/17/2015
PMID: 25700170

Abstract

Engineering Engineering, Environmental Environmental Sciences Environmental Sciences & Ecology Life Sciences & Biomedicine Science & Technology Technology
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 502 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.
url
https://doi.org/10.1021/es505793tView
Published (Version of record) Open

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