Centre for Atmospheric Chemistry
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Browsing Centre for Atmospheric Chemistry by Author "Anderson, R.S."
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Item Open Access The carbon kinetic isotope effects of ozone-alkene reactions in the gas-phase and the impact of ozone reactions on the stable carbon isotope ratios of alkenes in the atmosphere(AGU, 2003) Iannone, R.; Anderson, R.S.; Rudolph, J.; Huang, L.; Ernst, D.The kinetic isotope effects (KIEs) for several ozone-alkene reactions in the gas phase were studied in a 30 L PTFE reaction chamber. The time dependence of the stable carbon isotope ratios and the concentrations were determined using a gas chromatography combustion isotope ratio mass spectrometry (GCC-IRMS) system. The following average KIE values were obtained: 18.9 ± 2.8 (ethene), 9.5 ± 2.5 (propene), 8.7 ± 1 (1-butene), 8.1 ± 0.4 (E-2-butene), 7.9 ± 0.4 (1,3-butadiene), 6.7 ± 0.9 (1-pentene), 7.3 ± 0.2 (Z-2-pentene), 6.7 ± 0.7 (cyclopentene), 6.1 ± 1 (isoprene), 5.0 ± 0.7 (1-hexene), 5.6 ± 0.5 (cyclohexene), and 4.3 ± 0.7 (1-heptene). These data are the first of their kind to be reported in the literature. The ozone-alkene KIE values show a systematic inverse dependence from alkene carbon number. Based on the observed KIEs, the contribution of ozone-alkene reactions to the isotopic fractionation of alkenes in the atmosphere can be estimated. On average this contribution is generally small compared to the impact of reaction with OH radicals. However, when OH-concentrations are very low, e.g. during nighttime and at high latitudes in winter, the contribution of the ozone reaction dominates and under these conditions the ozone-alkene reaction will have a clearly visible impact on the stable carbon isotope ratio of atmospheric alkenes.Item Open Access The Hydrogen Kinetic Isotope Effects of the Reactions of n-Alkanes with Chlorine Atoms in the Gas Phase(Springer Netherlands, 2005) Iannone, R.; Anderson, R.S.; Vogel, A.; Eby, P.; Whiticar, M.J.; Rudolph, J.The stable-hydrogen kinetic isotope effects (KIEs) for a series of n-alkanes in reaction with chlorine atoms in the gas phase were studied in a 25-L PTFE reaction chamber at 298 K. The time dependence of both the stable hydrogen isotope ratios and the concentrations was determined using a gas chromatography pyrolysis isotope ratio mass spectrometry (GC-P-IRMS) system. The following KIE values, in per mil (‰), were obtained: 39.6 ± 2.7 (n-butane), 28.2 ± 0.9 (n-pentane), 24.6 ± 1.0 (n-hexane), 24.0 ± 1.2 (n-heptane), 17.9 ± 3.3 (n-octane), 15.1 ± 0.7 (n-nonane), and 14.9 ± 1.8 (n-decane). The errors given are the ±1σ standard errors. These measured values were used to derive structure–reactivity relationship (SRRs), which allow for the calculation of the KIEs for the reaction of n-alkanes with Cl atoms. The results of the calculations agree with the measurements within few per mil or better. The site specific stable hydrogen isotope fractionation effects for methyl groups are approximately a factor of 3 larger than those for methylene group, a finding which is qualitatively similar to site-specific stable hydrogen isotope effects reported in literature for reactions of alkanes with the OH radical. Because n-alkanes with close to natural isotope ratios (i.e. neither artificially labeled, nor enriched or depleted) were used, the KIE data are directly applicable to atmospheric studies. Based on these KIE values, the impact of Cl-atom reactions of the stable hydrogen isotope ratio on alkanes are estimated for different levels of Cl-atom concentrations. On average in the troposphere, the impact of Cl-atom reactions of the stable hydrogen isotope ratio of n-alkanes will be small. However, in regions of the troposphere with high concentrations of Cl atoms, such as the tropospheric ozone depletion episodes during polar sunrise, the impact of Cl-atom reactions is substantial.Item Open Access Laboratory Studies of the Hydrogen Kinetic Isotope Effects (KIES) of the Reaction of Non-Methane Hydrocarbons with the OH Radical in the Gas Phase(Springer Netherlands, 2004) Iannone, R.; Anderson, R.S.; Vogel, A.; Rudolph, J.; Eby, P.; Whiticar, M.J.The hydrogen kinetic isotope effects (KIEs) of the reactions of 15 non-methane hydrocarbons (NMHCs) with the OH radical were measured at 298 ± 2 K. The measurements were made using NMHCs without artificial isotopic labeling or enrichment. The following average hydrogen KIE values, in per mil (), were obtained: 29.8 ± 2.1 (toluene),51.6 ± 2.1 (n-butane), 97.3± 12.5 (i-butane), 63.2 ± 5.9 (cyclopentane), 10.5 (p-xylene), 26.8 ± 3.5 (ethylbenzene), 65.9± 7.0 (n-pentane), 79.5 ± 9.6 (cyclohexane), 52.8 ± 5.0(n-hexane), 38.9 ± 7.8 (n-heptane), 33.4 ± 3.1 (n-octane), 29.6 ± 1.6(n-nonane), and 29.0 ± 5.3 (n-decane). The KIEs for reactions of two alkenes (cyclohexene and 1-heptene) could not be determined accurately due to interference from reaction with ozone, but nevertheless the results clearly show that the KIEs for reaction of alkenes with OH are significantly lower than those for saturated hydrocarbons. The KIEs for reaction of alkanes are smaller than isotope effects reported in literature for the reactions of NMHCs artificially labeled with deuterium. The main reason for this difference is the reduced probability for reaction at a labeled site for compounds with close to natural deuterium abundance, although some impact of secondary isotope effects cannot be ruled out. Still, the KIEs for NMHCs with natural or close to natural abundance of deuterium are of sufficient magnitude to allow determination of the extent of chemical processing of hydrocarbons in the atmosphere using methods analogous to stable carbon KIE studies. Furthermore, it is shown that combining stable hydrogen and stable carbon isotope ratio data has the potential to also provide valuable information regarding the stable isotope ratios of emissions, and specifically to test one of the key assumptions of the stable isotope hydrocarbon clock, the absence of significant variations of the stable isotope ratio for the emitted NMHCs.Item Open Access The Stable Carbon Isotope Ratio of Biogenic Emissions of Isoprene and the Potential Use of Stable Isotope Ratio Measurements to Study Photochemical Processing of Isoprene in the Atmosphere(Springer Netherlands, 2003) Rudolph, J.; Anderson, R.S.; Czapiewski, K. v.; Czuba, E.; Ernst, D.; Gillispie, T.; Huang, L.; Rigby, C.; Thompson, A.E.A technique was developed that allows the determination of the stable carbon isotope ratio of isoprene in air. The method was used for a limited number of ambient measurements as well as laboratory studies of isoprene emitted from Velvet Bean (Mucana pruriens L. var. utilis), including the light and temperature dependence. The mean stable carbon isotope ratio ( 13C) of isoprene emitted from Velvet Bean (Mucana pruriens L. var. utilis) for all our measurements is –27.7 ± 2.0 (standard deviation for 23 data points). Our results indicate a small dependence of the stable carbon isotope ratios on leaf temperature and photosynthetic photon flux density (PPFD). The light dependence is 0.0026 ± 0.0012/( mol of photons m–2 s–1) for the studied range from 400 to 1700 mol of photons m–2 s–1. The temperature dependence is 0.16 ± 0.09/K. On average, the emitted isoprene is 2.6 ± 0.9 lighter than the leaf carbon. An uncertainty analysis of the possibility to use stable carbon isotope ratio measurements of isoprene for estimates of its mean photochemical age suggests that meaningful results can be obtained. This is supported by the results of a small number of measurements of the stable carbon isotope composition of ambient isoprene at different locations. The results range from approximately –29 to –16. They are consistent with vegetation emissions of isoprene that is slightly depleted in 13C relative to the plant material and enrichment of 13C in the atmosphere due to isotope fractionation associated with the reaction with OH-radicals. The stable carbon isotope ratio of ambient isoprene at locations directly influenced by isoprene emissions is very close to the values we found in our emission studies, whereas at sites located remote from isoprene emitting vegetation we find substantial enrichment of 13C. This suggests that stable carbon isotope ratio measurements will be a valuable, quantitative method to determine the extent of photochemical processing of isoprene in ambient air.Item Open Access Stable carbon isotope signatures of background tropospheric chloromethane and CFC113(Springer Verlag, 2002) Thompson, A.E.; Anderson, R.S.; Rudolph, J.; Huang, L.Samples of background air were collected in thelower troposphere of the Northern (high Arctic,northern Ontario, Vancouver and Houston) andSouthern (Baring Head, New Zealand) Hemispheresover the period July 1999 until March 2001.These samples were analysed for the stablecarbon isotope ratios of1,1,1-trichlorotrifluoroethane (CFC113) andCH3Cl using a gaschromatography-continuous flow on-linecombustion isotope ratio mass spectrometrycombination. For CH3Cl the global averageof the stable carbon isotope ratio is –36.2± 0.3 (error of mean). The average isbased on 78 data points, standard deviation forall measurements is 2.3, and the 90%confidence interval is –35.8 to –36.6.However, the number of data points from theSouthern Hemisphere is rather limited and thusthis observation is not necessarilyrepresentative for the entire SouthernHemisphere. A simple isotopic budget ofCH3Cl shows the most important parametersneeding to be defined are the kinetic isotopeeffect of CH3Cl destruction by OH radicalsand the source composition of CH3Clemitted by the oceans and biomass burning ofC-4 plants. Present budgets of atmosphericCH3Cl show a significant deficit in thesource strength. We estimate that the averagestable carbon isotope ratio of the additionalCH3Cl emissions required to balance thebudget is –41.9 ± 7.8. The averageCFC113 isotopic composition based on 38measurements is –23.3 ± 1.6 (error ofmean), = 9.6 with no significantdifference between the hemispheres.