[Beck2011] "The gas-phase ozonolysis of ?-humulene.",
Phys Chem Chem Phys
, vol. 13, no. 23: Max Planck Institute for Chemistry, Atmospheric Chemistry Department, Mainz, Germany. email@example.com, pp. 10970–11001, Jun, 2011.
?-Humulene contains three double bonds (DB), and after ozonolysis of the first DB the first-generation products are still reactive towards O(3) and produce second- and third-generation products. The primary aim of this study consisted of identifying the products of the three generations, focusing on the carboxylic acids, which are known to have a high aerosol formation potential. The experiments were performed in a 570 litre spherical glass reactor at 295 K and 730 Torr. Initial mixing ratios were 260-2090 ppb for O(3) and 250-600 ppb for ?-humulene in synthetic air. Reactants and gas-phase products were measured by in situ FTIR spectroscopy. Particulate products were sampled on Teflon filters, extracted with methanol and analyzed by LC-MS/MS-TOF. Using cyclohexane (10-100 ppm) as an OH-radical scavenger and by monitoring the yield of cyclohexanone by PTR-MS, an OH-yield of (10.5 Â± 0.7)% was determined for the ozonolysis of the first DB, and (12.9 Â± 0.7)% of the first-generation products. The rate constant of the reaction of O(3) with ?-humulene is known as k(0) = 1.17 Â± 10(-14) cm(3) molecule(-1) s(-1) [Y. Shu and R. Atkinson, Int. J. Chem. Kinet., 1994, 26, 1193-1205]. The reaction rate constants of O(3) with the first-generation products and the second-generation products were, respectively, determined as k(1) = (3.6 Â± 0.9) x 10(-16) and k(2) = (3.0 Â± 0.7) x 10(-17) cm(3) molecule(-1) s(-1) by Facsimile-simulation of the observed ozone decay by FTIR. A total of 37 compounds in the aerosol phase and 5 products in the gas phase were tentatively identified: 25 compounds of the first-generation products contained C13-C15 species, 9 compounds of the second-generation products contained C8-C11 species, whereas 8 compounds of the third-generation products contained C4-C6 species. The products of all three generations consisted of a variety of dicarboxylic-, hydroxy-oxocarboxylic- and oxo-carboxylic acids. The formation mechanisms of some of the products are discussed. The residual FTIR spectra indicate the formation of secondary ozonides (SOZ) in the gas phase, which are formed by the intramolecular reaction of the Criegee moiety with the carbonyl endgroup. These SOZ revealed to be stable over several hours and its formation was shown not to be affected by the addition of Criegee-radical scavengers such as HCOOH or H(2)O. This suggests that in the ozonolysis of ?-humulene at atmospheric pressures the POZ will decompose rapidly, and that a large fraction of the formed exited Criegee Intermediate will be stabilized to form stable SOZ, while the formation of OH-radicals via the hydroperoxide channel will be a minor process.
 "Ground-level ozone influenced by circadian control of isoprene emissions",
, vol. 4, pp. 671–674, 2011.
<p>The volatile organic compound isoprene is produced by many plant species, and provides protection against biotic and abiotic stresses1. Globally, isoprene emissions from plants are estimated to far exceed anthropogenic emissions of volatile organic compounds2. Once in the atmosphere, isoprene reacts rapidly with hydroxyl radicals3 to form peroxy radicals, which can react with nitrogen oxides to form ground-level ozone4. Here, we use canopy-scale measurements of isoprene fluxes from two tropical ecosystems in Malaysia—a rainforest and an oil palm plantation—and three models of atmospheric chemistry to explore the effects of isoprene fluxes on ground-level ozone. We show that isoprene emissions in these ecosystems are under circadian control on the canopy scale, particularly in the oil palm plantation. As a result, these ecosystems emit less isoprene than present emissions models predict. Using local-, regional- and global-scale models of atmospheric chemistry and transport, we show that accounting for circadian control of isoprene emissions brings model predictions of ground-level ozone into better agreement with measurements, especially in isoprene-sensitive regions of the world.</p>