References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-7-1-2007

In-situ measurement of reactive hydrocarbons at Hohenpeissenberg with comprehensive two-dimensional gas chromatography (GC×GC-FID): use in estimating HO and NO3

Bartenbach

¹ Williams

¹ Plass-Dülmer

² Berresheim

² Lelieveld

Max-Planck-Institute for Chemistry, J. J. Becher Weg 27, 55128 Mainz, Germany

Deutscher Wetterdienst, Meteorologisches Observatorium Hohenpeissenberg, Albin-Schwaiger-Weg 10, 82382 Hohenpeissenberg, Germany

02 01 2007

7 1 1 14

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During a field campaign at the Meteorological Observatory Hohenpeissenberg (MOHp) in July 2004, volatile organic compounds (VOCs) were measured using comprehensive two-dimensional gas chromatography (GC×GC). Comparison to routinely made gas chromatography mass spectrometry (GC-MS) measurements showed good agreement for a variety of anthropogenic and biogenic ambient VOCs ranging in concentration from below the detection limit (0.1 pmol mol−1) to 180 pmol mol−1. Pronounced diurnal cycles were found for both the biogenic and anthropogenic compounds, driven for the most part by the daily rise and fall of the boundary layer over the station. For the reactive compounds (lifetimes <2 days), a significant, non-zero dependency of the variability on lifetime was found, indicating that chemistry (as opposed to transport alone) was playing a role in determining the ambient VOC concentrations. The relationship was exploited using a single-variate analysis to derive a daytime mean value of HO (5.3±1.4×106molecules cm−3), which compares well to that measured at the site, 3.2±2.3×106molecules cm−3. The analysis was extended to the night time data to estimate concentrations for NO3 (1.47±0.2×108molecules cm−3), which is not measured at the site. The feasibility of this approach for environments dominated by emissions of short-lived VOCs to estimate ambient levels of radical species is discussed.

References 1

Acker, K., Möller, D., Wieprecht, W., Meixner, F. X., Bohn, B., Gilge, S., Plass-Dülmer, C., and Berresheim, H.: Strong daytime production of OH from HNO2 at a rural mountain site, Geophys. Res. Lett., L02809, doi:10.1029/2005GL024643, 2006.

Atkinson, R.: Gas-phase tropospheric chemistry of organic compounds, J. Phys. Chem. Ref. Data, 26, 215–290, 1997.

Atkinson, R., Aschmann, S. M., and Arey, J.: Rate constants for the gas-phase reactions of OH and NO3 radicals and O3 with sabinene and camphene at 296+/−2 K, Atmos. Environ., 24, 2647–2656,1990.

Atkinson, R., Aschmann, S. M., and Pitts, J. N.: Rate constants for the gas-phase reactions of the OH radical with a series of monoterpenes at 294 K, Int. J. Chem. Kinet., 18, 287–299, 1986.

Beens, J., Blomberg, J., and Schoenmakers, P. J.: Proper tuning of comprehensive two-dimensional gas chromatography (GC×GC) to optimize the separation of complex oil fractions, J. High Resol. Chromatogr., 23, 182–188, 2000.

Beens, J., Adahchour, M., Vreuls, R. J. J., van Altena, K., and Brinkman, U. A. Th.: Simple, non-moving modulation interface for comprehensive two-dimensional gas chromatography, J. Chromatogr. A, 919, 127–132, 2001.

Berresheim, H., Elste, T., Plass-Dülmer, C., Eisele, F. L., and Tanner, T. J.: Chemical ionization mass spectrometer for long-term measurements of atmospheric OH and H2SO4, Int. J. Mass. Spect., 202, 91–109, 2000.

Bertin, N., Staudt, M., Hansen, U., Seufert, G., Ciccioli, P., Foster P., Fugit, J.-L., and Torres, L.: Diurnal and seasonal course of monoterpene emissions from \textitQuercus ilex (L.) under natural conditions – Application of light and temperature algorithms, Atmos. Environ., 31, 135–144, 1997.

Birmili, W., Berresheim, H., Plass-Dülmer, C., Elste, T., Gilge, S., Wiedensohler, A., and Uhrner, U.: The Hohenpeissenberg aerosol formation experiment (HAFEX): a long-term study including size-resolved aerosol, H2SO4, OH, and monoterpene measurements, Atmos. Chem. Phys., 3, 361–376, 2002.

Birmili, W., Wiedensohler, A., Plass-Dülmer, C., and Berresheim, H.: Evolution of newly formed aerosol particles in the continental boundary layer, J. Geophys. Res., 27, 2205–2208, 2000.

Blake, R. S., Whyte, C., Hughes, C. O., Ellis, A. M., and Monks, P. S.: Demonstration of Proton-Transfer Reaction Time-of-Flight Mass Spectrometry for real-time analysis of trace volatile organic compounds, Anal. Chem., 76, 3841–3845, 2004.

Blomberg, J., Schoenmakers, P. J., Beens, J., and Tijssen, R.: Comprehensive two-dimensional gas chromatography (GC×GC) and its applicability to the characterization of complex (petrochemical) mixtures, J. High Resol. Chromatogr., 20, 539–544, 1997.

Calogirou, A., Larsen, B. R., Brussol, C., Duana, M., and Kotzias, D.: Decomposition of terpenes by ozone during sampling on Tenax, Anal. Chem., 68, 1499–1506, 1996.

Corchnoy, S. B. and Atkinson, R.: Kinetics of the gas-phase reactions of OH and NO3 radicals with 2-carene, 1,8-cineole, p-cymene, and terpinolene, Environ. Sci. Technol., 24, 1497–1502, 1990.

Dallüge, J., Beens, J., and Brinkman, U. A.Th.: Comprehensive two-dimensional gas chromatography: A powerful and versatile analytical tool, J. Chromatogr. A., 1000, 69–108, 2003.

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

Fenger, J.: Urban air quality, Atmos. Environ., 33, 4877–4900, 1999.

Finlayson-Pitts, B. J. and Pitts Jr., J. N.: Chemistry of the upper and lower atmosphere, Academic Press, 2000.

Fuentes, J. D., Lerdau, M., Atkinson, R., Baldocchi, D., Bottenheim, J. W., Ciccioli, P., Lamb, B., Geron, C., Gu, L., Guenther, A., Shaerkey, T. D., and Stockwell, W.: Biogenic hydrocarbons in the atmospheric boundary layer: A review, Bull. Am. Meteorol. Soc., 81, 1537–1575, 2000.

Fulton, D., Gillespie T., Fuentes, J., and Wang, D.: Volatile organic compound emissions from young black spruce trees, Agric. Forest Met., 90, 247–255, 1998.

Geyer, A., Ackermann, R., Dubois, R., Lohrmann, B., Müller, T., and Platt, U.: Long-term observation of nitrate radicals in the continental boundary layer near Berlin, Atmos. Environ., 38, 4733–4747, 2001.

Hakola, H., Laurila, T., Lindfors, V., Hellén, H., Gaman, A., and Rinne, J.: Variation of the VOC emission rates of birch species during the growing season, Boreal Environ. Res., 6, 237–249, 2001.

Hakola, H., Tervainen, V., Laurila, T., Hiltunen, V., Hellén, H., and Keronen, P.: Seasonal variation of VOC concentrations above a boreal coniferous forest, Atmos. Environ., 37, 1623–1634, 2003.

Handisides, G. M., Plass-Dülmer, C., Gilge, S., Bingemer, H., and Berresheim, H.: Hohenpeissenberg Photochemical Experiment (HOPE 2000): Measurements and photostationary state calculations of OH and peroxy radicals, Atmos. Chem. Phys., 3, 1565–1588, 2003.

Harynuk, J. and Górecki, T.: New liquid nitrogen cryogenic modulator for comprehensive two-dimensional gas chromatography, J. Chromatogr. A, 1019, 53–63, 2003.

Inomata, S., Tanimoto, H., Nobuyuki, A., Hirokawa, J., and Sadanaga, Y.: A novel discharge source of hydronium ions for proton-transfer reaction ionization: design, characterization, and performance, Rapid Comm. Mass Spectr., 20, 1025–1029, 2006.

Jacobson, M. Z.: Atmospheric pollution~: History, science and regulation, Cambridge University Press, 2002.

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.: Trace gas mixing ratio variability versus lifetime in the troposphere and stratosphere: Observations, J. Geophys. Res., 104, 16 091–16 113, 1999.

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

Junge, C. E.: Residence time and variability of tropospheric trace gases, Tellus, 26, 477–488, 1974.

Karl, T., Crutzen, P. J., Mandl, M., Staudinger, M., Guenther, A., Jordan, A., Fall, R., and Lindinger, W.: Variability-lifetime relationship of VOCs observed at the Sonnblick Observatory 1999 – estimation of HO-densities, Atmos. Environ., 35, 5287–5300, 2001.

Kinghorn, R. M. and Marriott, P. J.: Comprehensive two-dimensional gas chromatography using a modulation cryogenic trap, J. High Resol. Chromatogr., 21, 620–622, 1998.

Kirstine, W., Galbally, I., Ye, Y., and Hooper, M.: Emissions of volatile organic compounds (primarily oxygenated species) from pasture, J. Geophys. Res., 103, 10 605–10 619, 1998.

König, G., Brunda, M., Puxbaum, H., Hewitt, C. N., Duckham, S. C., and Rudolph, J.: Relative contribution of oxygenated hydrocarbons to the total biogenic VOC emissions of selected mid-european agricultural and natural plant species, Atmos. Environ., 29, 861–874, 1995.

Ledford, E. B., and Billesbach, C. A.: Jet-cooled thermal modulator for comprehensive multidimensional gas chromatography, J. High. Resol. Chromatogr., 23, 202–204, 2000.

Ledford, E. B., TerMaat, J. R., Billesbach, C. A.: What is loop modulation?, Technical Note KT030606-1, 2004.

Lewis, A. C., Carslaw, N., Marriott, P. J., Kinghorn, R. M., Morrison, P. D., Lee, A. L., Bartle, K. D., and Pilling, M. J.: A larger pool of ozone-forming carbon compounds in urban atmospheres, Nature, 405, 778–781, 2000.

Liu, Z. Y. and Phillips, J. B.: Comprehensive two-dimensional gas-chromatography using an on-column thermal modulator interface, J. Chromatogr. Sci., 29, 227–231, 1991.

Marriott, P. J. and Kinghorn, R. M.: Longitudinally modulated cryogenic system. A generally applicable approach to solute trapping and mobilization in gas chromatography, Anal. Chem., 69, 2582–2588, 1997.

Marriott, P. J., Shellie, R. A., Fergeus, J., Ong, R. C. Y., and Morrison, P. D.: High resolution essential oil analysis by using comprehensive gas chromatographic methology, Flavour Fragr. J., 15, 225–239, 2000.

Phillips, J. B., Gaines, R. B., Blomberg, J, van der Wielen, F. W. M., Dimandja, J. M., Green, V., Granger, J., Patterson, D., Racovalis, L., de Geus, H. J., de Boer, J., Haglund, P., Lipsky, J., Sinha, V., and Ledford, E. B.: A robust thermal modulator for comprehensive two-dimensional gas chromatography, J. High Resol. Chromatogr., 22, 3–10, 1999.

Plass-Dülmer, C., Michl, K., Ruf, R., and Berresheim, H.: C2–C$_8$ hydrocarbon measurement and quality control procedures at the Global Atmosphere Watch Observatory Hohenpeissenberg, J. Chrom. A, 953, 175–197, 2002.

Rohrer, F. and Berresheim, H.: Stability in the self-cleaning of the troposphere observed over five years, Nature, 442, 184–187, doi:10.1038/nature04924, 2006.

Schade G. W., Goldstein, A. H., and Lamanna, M. S.: Are monoterpene emissions influenced by humidity?, Geophys. Res. Lett., 14, 2187–2190, 1999.

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.

Street, R. A., Duckham, S. C., and Hewitt, C. N.: Laboratory and field studies of biogenic volatile organic compound emissions from Sitka spruce (Picea sitchensis Bong) in the United Kingdom, J. Geophys. Res., 101, 22 799–22 806, 1996.

Tollsten, L. and Müller, P. M.: Volatile organic compounds emitted from beech leaves, Phytochemistry, 43, 759–762, 1996.

Venkatramani, C. J. and Phillips, J. B.: Comprehensive 2-dimensional gas-chromatography applied to the analysis of complex mixtures, J. Micro. Sep., 5, 511–516, 1993.

Williams, J., Fischer, H., Harris, G. W., Crutzen, P. J., and Hoor, P.: Variability-lifetime relationship for organic trace gases: A novel aid to compound identification and estimation of HO concentrations, 2000, J. Geophys. Res, 105, 20 473–20 486, 2000.

Williams, J., Gros, V., Bonsang, B., and Kazan, V.: HO cycle in 1997 and 1998 over the southern Indian Ocean derived from CO, radon, and hydrocarbon measurements made at Amsterdam Island, J. Geophys. Res., 106, 12 719–12 725, 2001.

Williams, J.: Organic trace gases: an overview, Environ. Chem., 1, 125–136, 2004.

Xu, X., van Stee, L. L. P., Williams, J., Beens, J., Adahchour, M., Vreuls, R. J. J., Brinkman, U. A. T, and Lelieveld, J.: Comprehensive two-dimensional gas chromatography GC×GC measurements of volatile organic compounds in the atmosphere, Atmos. Chem. Phys., 3, 665–682, 2003a.

Xu, X., Williams, J., Plass-Dülmer, C., Berresheim, H., Salisbury, G., Lange, L., and Lelieveld, J.: GC×GC measurements of C$_7$–C$_11$ aromatic and n-alkane hydrocarbons on Crete, in air from Eastern Europe during the MINOS campaign, Atmos. Chem. Phys., 3, 1461–1475, 2003b.

Yatagai, M., Ohira, M., Ohira, T., and Nagai, S.: Seasonal variations of terpene emission from trees and influence of temperature, light and contact stimulation on terpene emission, Chemosphere, 30, 1137–1149, 1995.