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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

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Abstract

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 (δ 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‰/(μ mol of photons m−2 s−1) for the studied range from 400 to 1700 μ 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.

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References

  • Atkinson, R., 1997: Gas-phase tropospheric chemistry of volatile organic compounds: 1. Alkanes and alkenes, J. Phys. Chem. Ref. Data 26, 215-290.

    Google Scholar 

  • Brenninkmeijer, C. A. M., Lowe, D. C., Manning, M. R., Sparks, R. J., and Velthoven, P. F. J., 1995: The 13C, 14C, and 18O isotopic composition of CO, CH4, and CO2 in the higher southern latitudes lower stratosphere, J. Geophys. Res. 100, 26,163-26,172.

    Google Scholar 

  • Ehhalt, D. H., Rohrer, F., Wahner, A., Prather, M. J., and Blake, D. R., 1998: On the use of hydrocarbons for the determination of tropospheric OH concentrations, J. Geophys. Res. 103, 18,981-18,997.

    Google Scholar 

  • Guenther, A., Hewitt, C. N., Erickson, D., Fall, R., Geron, C., Graedel, T., Harley, P., Klingerm, L., Lerdau, M., McKay, W. A., Pierce, T., Scholes, B., Steinbrecher, R., Tallamraju, R., Taylor, J., and Zimmerman, P., 1995: A global model of natural volatile organic compound emissions, J. Geophys. Res. 100, 8873-8892.

    Google Scholar 

  • Jobson, B. T., Wu, Z., Niki, H., and Barrie, L. A., 1994: Seasonal trend of isoprene, C2-C5 alkanes and acetylene at a remote boreal site in Canada, J. Geophys. Res. 99, 1589-1599.

    Google Scholar 

  • Jobson, B. T., Parrish, D. D., Goldan, P., Kuster, W., Fehsenfeld, F. C., Blake, D. R., Blake, N. J., and Niki, H., 1998: Spatial and temporal variability of nonmethane hydrocarbon mixing ratios and their relation to photochemical lifetime, J. Geophys. Res. 103, 13,557-13,567.

    Google Scholar 

  • Jobson, B. T., McKeen, S. A., Parrish, D. D., Fehsenfeld, F. C., Blake, D. R., Goldstein, A. H., Schauffler, S. M., and Elkins, J. W., 1999: Trace gas mixing ratio variability versus lifetime in the troposphere and stratosphere: Observations, J. Geophys. Res. 104, 16,091-16,113.

    Google Scholar 

  • Lowe, D. C., Brenninkmeijer, C. A. M., Brailsford, G. W., Lassey, K. R., Gomez, A. J., and Nisbet, E. G., 1994: Concentration and 13C records of atmospheric methane in New Zealand and Antarctica: Evidence for changes in methane sources, J. Geophys. Res. 99, 16,913-16,925.

    Google Scholar 

  • Martin, R. S., Westberg, H., Allwine, E., Ashman, L., Farmer, J. C., and Lamb, B., 1991: Measurement of isoprene and its atmospheric oxidation product in a Central Pennsylvania deciduous forest, J. Atmos. Chem. 13, 1-32.

    Google Scholar 

  • Matthews, D. E. and Hayes, A. J., 1978: Isotope ratio monitoring gas chromatography-mass spectrometry, Anal. Chem. 50, 1465-1473.

    Google Scholar 

  • McKeen, S. A., Trainer, M., Hsie, E.-Y., Tallamraju, R. K., and Liu, S. C., 1990: On the indirect determination of atmospheric OH-radical concentrations from reactive hydrocarbon measurements, J. Geophys. Res. 95, 7493-7500.

    Google Scholar 

  • McKeen, S. A., Liu, S. C., Hsie, E.-Y., Lin, X., Bradshaw, J. D., Smyth, S., Gregory, G. L., and Blake, D. R., 1996: Hydrocarbon ratios during PEM-WEST A: A model perspective, J. Geophys. Res. 101, 2087-2109.

    Google Scholar 

  • McKenna, D. S., Hord, C. J., and Kent, J. M., 1995: Hydroxyl radical concentrations and Kuwait oil fire emission rates for March 1991, J. Geophys. Res. 100, 26,005-26,026.

    Google Scholar 

  • McKenna, D. S., 1997: Analytic solution of reaction diffusion equations and implications for the concept of an air parcel, J. Geophys. Res. 102, 19,719-13,725.

    Google Scholar 

  • McLaren, R. and Singleton, D. L., 1996: Analysis of motor vehicle sources and their contribution to ambient hydrocarbon distributions at urban sites in Toronto during the Southern Ontario Oxidants Study, Atmos. Environ. 30, 2219-2232.

    Google Scholar 

  • Montzka, S. A., Trainer, M., Goldan, P. D., Kuster, W. C., and Fehsenfeld, F. C., 1993: Isoprene and its oxidation products methyl vinyl ketone and methacrolein in the rural troposphere, J. Geophys. Res. 98, 1101-1111.

    Google Scholar 

  • Montzka, S., Trainer, M., Angevine, W. M., and Fehsenfeld, F. C., 1995: Measurements of 3-methyl furan, methyl vinyl ketone, and methacrolein at a rural forested site in the southeastern United States, J. Geophys. Res. 100, 11,393-11,401.

    Google Scholar 

  • Parrish, D. D., Hahn, C. J., Williams, E. J., Norton, R. B., Fehsenfeld, F. C., Singh, H. B., Shetter, J. D., Gandrud, B. W., and Ridley, B. A., 1992: Indications of photochemical histories of pacific air masses from measurements of atmospheric trace species at Point Arena, California, J. Geophys. Res. 97, 15,883-15,901.

    Google Scholar 

  • Pierotti, D., Wofsy, S. C, Jacob, D., Rasmussen, R. A., 1990: Isoprene and its oxidation products: Methacrolein and methyl vinyl ketone, J. Geophys. Res. 95, 1871-1881.

    Google Scholar 

  • Roberts, J. M., Fehsenfeld, F. C., Liu, S. C., Bollinger, M. J., Hahn, C., Albritton, D. L., and Sievers, R. E., 1984: Measurements of aromatic hydrocarbon ratios and NO x concentrations in the rural troposphere: Observation of air mass photochemical aging and NO x removal, Atmos. Environ. 18, 2421-2432.

    Google Scholar 

  • Rudolph, J. and Johnen, F. J., 1990: Measurements of light atmospheric hydrocarbons over the Atlantic in regions of low biological activity, J. Geophys. Res. 95, 20,583-20,591.

    Google Scholar 

  • Rudolph, J., Lowe, D. C., Martin, R. J., and Clarkson, T. S., 1997: A novel method for compound specific determination of d 13C in volatile organic compounds, Geophys. Res. Lett. 24, 659-662.

    Google Scholar 

  • Rudolph, J., 1999: Measurement of nonmethane hydrocarbons in the atmosphere, Proceedings of the workshop on volatile organic compounds in the troposphere held in Juelich (Germany) from 27-31 October, 1997, pp. 11-35.

  • Rudolph, J. and Czuba, E., 2000: On the use of isotopic composition measurements of volatile organic compounds to determine the ‘photochemical age’ of an air mass, Geophys. Res. Lett. 27, 3865-3868.

    Google Scholar 

  • Rudolph, J., Czuba, E., and Huang, L., 2000: The stable carbon isotope fractionation for reactions of selected hydrocarbons with OH-radicals and its relevance for atmospheric chemistry, J. Geophys. Res. 105, 29,329-29,346.

    Google Scholar 

  • Sharkey, T. D., Loreto, F., Delwiche, C. F., and Treichel, I.W., 1991: Fractionation of carbon isotopes during biogenesis of atmospheric isoprene, Plant Psychol. 97, 463-466.

    Google Scholar 

  • Tsunogai, U., Yoshida, N., and Gamo, T., 1999: Carbon isotopic composition of C2-C5 hydrocarbons and methyl chloride in urban, coastal, and maritime atmospheres over the western North Pacific, J. Geophys. Res. 104, 16,033-16,039.

    Google Scholar 

  • Williams, J., Roberts, J. M., Fehsenfeld, F. C., Bertman, S. B., Buhr, M. P., Goldan, P. D., Hubler, G., Kuster, W. C., Ryerson, T. B., Trainer, M., and Young, V., 1997: Regional ozone from biogenic hydrocarbons deduced from airborne measurements of PAN, PPN, and MPAN, Geophys. Res. Lett. 24, 1099-1102.

    Google Scholar 

  • Williams, J., Fischer, H., Harris, G. W., Crutzen, P. J., Hoor, P., Hansel, A., Holzinger, R., Warneke, C., Lindinger, W., Scheeren, B., and Lelieveld, J., 2000: Variability-lifetime relationship for organic trace gases: A novel aid to compound identification and estimation of HO concentrations, J. Geophys. Res. 105, 20,473-20,486.

    Google Scholar 

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Authors and Affiliations

  1. Centre for Atmospheric Chemistry, Rm. 006 Steacie Science Bldg., York University, 4700 Keele Street, Toronto, Ontario, M3J 1P3, Canada

    J. Rudolph, R. S. Anderson, K. V. Czapiewski, E. Czuba & A. E. Thompson

  2. Meteorological Services of Canada, Environment Canada, Toronto, Ontario, Canada

    D. Ernst & L. Huang

  3. University of Guelph, Ontario, Canada

    T. Gillespie & C. Rigby

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  1. J. Rudolph
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  2. R. S. Anderson
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  3. K. V. Czapiewski
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  4. E. Czuba
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  5. D. Ernst
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  6. T. Gillespie
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  7. L. Huang
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  8. C. Rigby
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  9. A. E. Thompson
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Rudolph, J., Anderson, R.S., Czapiewski, K.V. et al. 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. Journal of Atmospheric Chemistry 44, 39–55 (2003). https://doi.org/10.1023/A:1022116304550

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  • DOI: https://doi.org/10.1023/A:1022116304550

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