Stable carbon kinetic isotope effects for the production of methacrolein and methyl vinyl ketone from the gas-phase reactions of isoprene with ozone and hydroxyl radicals

摘要

The stable-carbon kinetic isotope effects (KIEs) associated with the production of methacrolein (MACR) and methyl vinyl ketone (MVK) from the reactions of isoprene with ozone and OH radicals were studied in a 25 L reaction chamber at (298±2) K and ambient pressure. The time dependence of both the stable-carbon isotope ratios and the concentrations was determined using a gas chromatography combustion isotope ratio mass spectrometry (GCC-IRMS) system. The average yields of ~(13)C-containing MACR and MVK generated from the ozone reaction of ~(13)C-containing isoprene differed by -3.6‰, and -4.5‰,, respectively, from the yields for MACR and MVK containing only ~(12)C. For MACR and MVK generated from the OH-radical oxidation of isoprene the corresponding values were -3.8‰, and -2.2‰, respectively. These values indicate a significant depletion in the ~(13)C abundance of MACR and MVK upon their formation relative to isoprene's pre-reaction ~(13)C/~(12)C ratio, which is supported by theoretical interpretations of the oxidation mechanism of isoprene and its ~(13)C-substituted isotopomers. Numerical model calculations of the isoprene + O_3 reaction predicted a similar depletion in ~(13)C for both reaction products upon production. Furthermore, the model predicts mixing ratios and stable carbon delta values for isoprene, MACR, and MVK that were in agreement with the experimental results. The combined knowledge of isotope enrichment values with KIEs will reduce uncertainties in determinations of the photochemical histories of isoprene, MACR, and MVK in the troposphere. The studies presented here were conducted with using isoprene without any artificial isotope enrichment or depletion and it is therefore very likely that these results are directly applicable to the interpretation of studies of isoprene oxidation using stable carbon isotope ratio measurements.