Atmospheric Chemistry and Physics Discussions www.atmos-chem-phys-discuss.net 1680-7367 1680-7375 9 2 2009 10.5194/acpd-9-10235-2009 http://www.atmos-chem-phys-discuss.net/9/10235/2009/ http://www.atmos-chem-phys-discuss.net/9/10235/2009/acpd-9-10235-2009.html http://www.atmos-chem-phys-discuss.net/9/10235/2009/acpd-9-10235-2009.pdf 10235 10269 2009-04-23 In-situ ambient quantification of monoterpenes, sesquiterpenes, and related oxygenated compounds during BEARPEX 2007 – implications for gas- and particle-phase chemistry N. C. Bouvier-Brown nbouvier@nature.berkeley.edu A. H. Goldstein J. B. Gilman W. C. Kuster J. A. de Gouw Department of Environmental Science, Policy, and Management, University of California at Berkeley, Berkeley, CA, USA NOAA Earth System Research Laboratory, Boulder, CO, USA Cooperative Institute for Research in Environmental Sciences, University of Colorado at Boulder, Boulder, CO, USA We quantified ambient mixing ratios of 9 monoterpenes, 6 sesquiterpenes, methyl chavicol, the oxygenated terpene linalool, and nopinone using an in-situ gas chromatograph with a quadrupole mass spectrometer (GC-MS). These measurements were a part of the 2007 Biosphere Effects on AeRosols and Photochemistry EXperiment (BEARPEX) at Blodgett Forest, a ponderosa pine forest in the Sierra Nevada Mountains of California. To our knowledge, these observations represent the first direct in-situ ambient quantification of the sesquiterpenes α-bergamotene, longifolene, α-farnesene, and β-farnesene. From average diurnal mixing ratio profiles, we show that α-farnesene emissions are dependent mainly on temperature whereas α-bergamotene and β-farnesene emissions are temperature- and light-dependent. The amount of sesquiterpene mass quantified above the canopy was small (averaging a total of 3.3 ppt during the day), but nevertheless these compounds contributed 8.5% to the overall ozone reactivity above the canopy. Assuming that the monoterpene-to-sesquiterpene emission rate in the canopy is similar to that observed in branch enclosure studies at the site during comparable weather conditions, and the average yield of aerosol mass from these sesquiterpenes is 10–50%, the amount of sesquiterpene mass reacted within the Blodgett Forest canopy alone accounts for 8–38% of the total organic aerosol mass measured during BEARPEX. The oxygenated monoterpene linalool was also quantified for the first time at Blodgett Forest. The linalool mass contribution was small (9.9 ppt and 0.74 ppt within and above the canopy, respectively), but it contributed 1.2% to the total ozone reactivity above the canopy. Reactive and semi-volatile compounds, especially sesquiterpenes, significantly impact the gas- and particle-phase chemistry of the atmosphere at Blodgett Forest and should be included in both biogenic volatile organic carbon emission and atmospheric chemistry models. Andreae, M. O. and Crutzen P. J.: Atmospheric aerosols: Biogeochemical sources and role in atmospheric chemistry, Science, 276, 1052–1058, 1997. Atkinson, R.: Atmospheric chemistry of VOCs and NO_x, Atmos. Environ., 34, 2063–2101, 2000. Atkinson, R. and Arey, J.: Gas-phase tropospheric chemistry of biogenic volatile organic compounds: A review, Atmos. Environ., 37, S197–S219, 2003. Bauer, M. R., Hultman, N. E., Panek, J. A., and Goldstein, A. H.: Ozone deposition to a ponderosa pine plantation in the Sierra Nevada Mountains (CA): A comparison of two different climatic years, J. Geophys. Res., 105, 22123–22136, 2000. Bonn, B., Hirsikko, A., Hakola, H., Kurtén, T., Laakso, L., Boy, M., Dal Maso, M., Mäkelä, J. M., and Kulmala, M.: Ambient sesquiterpene concentration and its link to air ion measurements, Atmos. Chem. Phys., 7, 2893–2916, 2007. Bouvier-Brown, N. C., Holzinger, R., Palitzsch, K., and Goldstein, A. H.: Quantifying sesquiterpene and oxygenated terpene emissions from live vegetation using solid-phase microextraction fibers, J. Chromatogr. A, 1161, 113–120, 2007. Bouvier-Brown, N. C., Holzinger, R., Palitzsch, K., and Goldstein, A. H.: Large emissions of sesquiterpenes and methyl chavicol quantified from branch enclosure measurements, Atmos. Environ., 43, 389–401, 2009a. Bouvier-Brown, N. C., Goldstein, A. H, Worton, D. R., Matross, D. M., Gilman, J. B., Kuster, W. C., Welsh-Bon, D., Warneke, C., de Gouw, J. A., Cahill, T. M., and Holzinger, R.: Methyl chavicol: characterization of its biogenic emission rate, abundance, and oxidation products in the atmosphere, Atmos. Chem. Phys., 9, 2061–2074, 2009b. Boy, M., Karl, T., Turnipseed, A., Mauldin, R. L., Kosciuch, E., Greenberg, J., Rathbone, J., Smith, J., Held, A., Barsanti, K., Wehner, B., Bauer, S., Wiedensohler, A., Bonn, B., Kulmala, M., and Guenther, A.: New particle formation in the Front Range of the Colorado Rocky Mountains, Atmos. Chem. Phys., 8, 1577–1590, 2008. Calogirou, A., Jensen, N. R., Nielsen, C. J., Kotzias, D., and Hjorth, J.: Gas-phase reactions of nopinone, 3-isopropenyl-6-oxo-heptanal, and 5-methyl-5-vinyltetrahydrofuran-2-ol with OH, NO₃, and ozone, Environ. Sci. Technol., 33, 453–460, 1999. Ciccioli, P., Brancaleoni, E., Frattoni, M., Di Palo, V., Valentini, R., Tirone, G., Seufert, G., Bertin, N., Hansen, U., Csiky, O., Lenz, R., and Sharma, M.: Emission of reactive terpene compounds from orange orchards and their removal by within-canopy processes, J. Geophys. Res., 104 (D7), 8077–8094, 1999. Di Carlo, P., Brune, W. H., Martinez, M., Harder, H., Lesher, R., Ren, X., Thornberry, T., Carroll, M.A., Young, V., Shepson, P. B., Riemer, D., Apel, E., and Campbell, C.: Missing OH reactivity in a forest: Evidence for unknown reactive biogenic VOCs, Science, 304, 722–725, 2004. Duhl, T. R., Helmig, D., and Guenther, A.: Sesquiterpene emissions from vegetation: A review, Biogeosciences, 5, 761–777, 2008. Farmer, D. K. and Cohen, R. C.: Observations of HNO₃, $§igma$AN, $§igma$PN, and NO₂ fluxes: evidence for rapid HO_x chemistry within a pine forest canopy, Atmos. Chem. Phys., 8, 3899–3917, 2008. Fuentes, J. D., Lerdau, M., Atkinson, R., Baldocchi, D., Bottenheim, J. W., Ciccioli, P., Lamb, B., Geron, C., Gu, L., Guenther, A., Sharkey, T. D., and Stockwell, W.: Biogenic hydrocarbons in the atmospheric boundary layer: A review, B. Am. Meteorol. Soc., 81, 1537–1575, 2000. Goldan, P. D., Kuster, W. C., Williams, E., Murphy, P. C., Fehsenfeld, F. C., and Meagher, J.: Nonmethane hydrocarbon and oxy hydrocarbon measurements during the 2002 New England Air Quality Study, J. Geophys. Res., 109, D21309, doi:10.1029/2003JD004455, 2004. Goldstein, A. H., Hultman, N. E., Fracheboud, J. M., Bauer, M. R., Panek, J. A., Xu, M., Qi, Y., Guenther, A. B., and Baugh, W.: Effects of climate variability on the carbon dioxide, water, and sensible heat fluxes above a ponderosa pine plantation in the Sierra Nevada (CA), Agr. Forest Meteorol., 101, 113–129, 2000. Goldstein, A. H., McKay, M., Kurpius, M. R., Schade, G. W., Lee, A., Holzinger, R., and Rasmussen, R. A.: Forest thinning experiment confirms ozone deposition to forest canopy is dominated by reaction with biogenic VOCs, Geophys. Res. Lett., 31, L22106, doi:10.1029/2004GL021259, 2004. Goldstein, A. H. and Galbally, I. E.: Known and unexplored organic constituents in the earth's atmosphere, Environ. Sci. Technol., 41, 1514–1521, 2007. Griffin, R. J., Cocker III, D. R., Flagan, R. C., and Seinfeld, J. H.: Organic aerosol formation from the oxidation of biogenic hydrocarbons, J. Geophys. Res., 104(D3), 3555–3567, 1999. Guenther, A. B., Zimmerman, P. R., Harley, P. C., Monson, R. K., and Fall, R.: Isoprene and monoterpene emission rate variability – Model evaluations and sensitivity analyses, J. Geophys. Res., 98, 12609–12617, 1993. Hansen, U. and Seufert, G.: Temperature and light dependence of $\beta $-caryophyllene emission rates, J. Geophys. Res., 108(D24), 4801, doi:10.1029/2003JD003853, 2003. Heald, C. L., Henze, D. K., Horowitz, L. W., Feddema, J., Lamarque, J.-F., Guenther, A., Hess, P. G., Vitt, F., Seinfeld, J. H., Goldstein, A. H., and Fung, I.: Predicted change in global secondary organic aerosol concentrations in response to future climate, emissions, and land use change, J. Geophys. Res., 113, D052211, doi:10.1029/2007JD009092, 2008. Helmig, D., Revermann, T., Pollmann, J., Kaltschmidt, O., Hernandez, A. J., Bocquet, F., and David, D.: Calibration system and analytical considerations for quantitative sesquiterpene measurements in air, J. Chromatogr. A, 1002, 193–211, 2003. Hoffmann, T.: Adsorptive preconcentration technique including oxidant scavenging for the measurement of reactive natural hydrocarbons in ambient air, Fresenius' J. Anal. Chem., 351, 41–47, 1995. Hoffmann, T., Odum, J., Bowman, F., Collins, D., Klockow, D., Flagan, R. C., and Seinfeld, J. H.: Aerosol formation potential of biogenic hydrocarbons, J. Aerosol Sci., 27, S233–S234, 1996. Holzinger, R., Lee, A., Paw, K. T., and Goldstein, U. A. H.: Observations of oxidation products above a forest imply biogenic emissions of very reactive compounds, Atmos. Chem. Phys., 5, 67–75, 2005. Jaoui, M. and Kamens, R. M.: Gas and particulate products distribution from the photooxidation of α-humulene in the presence of NO_x, natural atmospheric air and sunlight, J. Atmos. Chem., 46, 29–54, 2003. Jaoui, M., Leungsakul, S., and Kamens, R. M.: Gas and particle products distribution from the reaction of β-caryophyllene with ozone, J. Atmos. Chem., 45, 261–287, 2003. Kurpius, M. R. and Goldstein, A. H.: Gas-phase chemistry dominates O₃ loss to a forest, implying a source of aerosols and hydroxyl radicals to the atmosphere, Geophys. Res. Lett., 30, 1371, doi:10.1029/2002GL016785, 2003. Lamanna, M. S. and Goldstein, A. H.: In situ measurements of C₂-C$_10$ volatile organic compounds above a Sierra Nevada ponderosa pine plantation, J. Geophys. Res., 104, 21247–21262, 1999. Lee, A., Schade, G. W., Holzinger, R., and Goldstein, A. H.: A comparison of new measurements of total monoterpene flux with improved measurements of speciated monoterpene flux, Atmos. Chem. Phys., 5, 505–513, 2005. Levis, S., Wiedinmyer, C., Bonan, G. B., and Guenther, A.: Simulating biogenic volatile organic compound emissions in the Community Climate System Model, J. Geophys. Res., 108, 4659, doi:10.1029/2002JD003203, 2003. Millet, D. B., Donahue, N. M., Pandis, S. N., Polidori, A., Stanier, C. O., Turpin, B. J., and Goldstein, A. H.: Atmospheric volatile organic compound measurements during the Pittsburgh Air Quality Study: Results, interpretation, and quantification of primary and secondary contributions, J. Geophys. Res., 110, D07S07, doi:10.1029/2004JD004601, 2005. Ortega, J. and Helmig, D.: Approaches for quantifying reactive and low-volatility biogenic organic compound emissions by vegetation enclosure techniques – Part A, Chemosphere, 72, 343–364, 2008. Owen, S. M., Boissard, C., and Hewitt, C. N.: Volatile organic compounds (VOCs) emitted from 40 Mediterranean plant species: VOC speciation and extrapolation to habitat scale, Atmos. Environ., 35, 5393–5409, 2001. Pollmann, J., Ortega, J., and Helmig, D.: Analysis of atmospheric sesquiterpenes: Sampling losses and mitigation of ozone interferences, Environ. Sci. Technol., 39, 9620–9629, 2005. Sakulyanontvittaya, T., Duhl, T., Wiedinmyer, C., Helmig, D., Matsunaga, S., Potosnak, M., Milford, J., and Guenther, A.: Monoterpene and sesquiterpene emission estimates for the United States, Environ. Sci. Technol., 42, 1623–1629, 2008. Saxton, J. E., Lewis, A. C., Kettlewell, J. H., Ozel, M. Z., Gogus, F., Boni, Y., Korogone, S. O. U., and Serça, D.: Isoprene and monoterpene measurements in a secondary forest in northern Benin, Atmos. Chem. Phys., 7, 4095–4106, 2007. Schade, G. W., Goldstein, A. H., and Lamanna, M. S.: Are monoterpene emissions influenced by humidity?, Geophys. Res. Lett., 26, 2187, 1999. Schade, G. W., Goldstein, A. H., Gray, D. W., and Lerdau, M. T.: Canopy and leaf level 2-methyl-3-buten-2-ol fluxes from a ponderosa pine plantation, Atmos. Environ., 34, 3535–3544, 2000. Schade, G. W. and Goldstein, A. H.: Increase of monoterpene emissions from a pine plantation as a result of mechanical disturbances, Geophys. Res. Lett., 30, 1380, doi:10.1029/2002GL016138, 2003. Staudt, M., Bertin, N., Hansen, U., Seufert, G., Ciccioli, P., Foster, P., Frenzel, B., and Fugit, J.-L.: Seasonal and diurnal patterns of monoterpene emissions from Pinus pinea (L.) under field conditions, Atmos. Environ., 31, 145–156, 1997. Staudt, M., Bertin, N., Frenzel, B., and Seufert, G.: Seasonal variation in amount and composition of monoterpenes emitted by young \textitPinus pinea trees – Implications for emission modeling, J. Atmos. Chem., 35, 77–99, 2000. US EPA, M.l.: Estimation Programs Interface Suite for Microsoft Windows, AOPWIN v.1.92, United States Environmental Protection Agency, Washington DC, USA, 2000.