References

ACPD

Atmospheric Chemistry and Physics Discussions

ACPD

1680-7375

Copernicus GmbH

Göttingen, Germany

10.5194/acpd-7-18179-2007

The Comparative Reactivity Method – a new tool to measure total OH reactivity in ambient air

Sinha

¹ Williams

¹ Crowley

J. N.

¹ Lelieveld

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

19 12 2007

7 6 18179 18220

This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.

This article is available from http://www.atmos-chem-phys-discuss.net/7/18179/2007/acpd-7-18179-2007.html

The full text article is available as a PDF file from http://www.atmos-chem-phys-discuss.net/7/18179/2007/acpd-7-18179-2007.pdf

Hydroxyl (OH) radicals play a vital role in maintaining the oxidizing capacity of the atmosphere. To understand variations in OH radicals both source and sink terms must be understood. Currently the overall sink term, or the total atmospheric reactivity to OH, is poorly constrained. Here, we present a new on-line method to directly measure the total OH reactivity (i.e.~total loss rate of OH radicals) in a sampled air mass. In this method, a reactive molecule (X), not normally present in air, is passed through a glass reactor and its concentration is monitored with a suitable detector. OH radicals are then introduced in the glass reactor at a constant rate to react with X, first in the presence of zero air and then in the presence of ambient air containing VOCs and other OH reactive species. Comparing the amount of X exiting the reactor with and without the ambient air allows the air reactivity to be determined. In our existing set up, X is pyrrole and the detector used is a proton transfer reaction mass spectrometer. The present dynamic range for ambient air reactivity is about 6 to 300 s−1. The system has been tested and calibrated with different single and mixed hydrocarbon standards showing excellent linearity and accountability with the reactivity of the standards. Field tests in the tropical rainforest of Suriname (~53 s−1) and the urban atmosphere of Mainz (~10 s−1) Germany, show the promise of the new method and indicate that a significant fraction of OH reactive species in the tropical forests is likely missed by current measurements. Suggestions for improvements to the technique and future applications are discussed.

References 1

Ammann, C., Brunner, A., Spirig, C., and Neftel, A.: Technical note: Water vapour concentration and flux measurements with PTR-MS, Atmos. Chem. Phys., 6, 4643–4651, 2006.

Atkinson, R., Aschmann, S. M., Winer, A. M., and Carter, W. P. L., Rate Constants for the Gas-Phase Reactions of OH Radicals and O3 with Pyrrole at 295+/-1k and Atmospheric-Pressure, Atmos. Environ., 18, 2105–2107, 1984.

Atkinson, R., Baulch, D. L., Cox, R. A., Crowley, J. N., Hampson, R. F., Hynes, R. G., Jenkin, M. E., Kerr, J. A., Rossi, M. J. and Troe, J. "IUPAC Subcommittee for gas kinetic data evaluation, Evaluated kinetic data, http://www.iupac-kinetic.ch.cam.ac.uk/, 2007

Bavia, M., Bertinelli, F., Taliani, C., and Zauli, C.: Electronic-Spectrum of Pyrrole in Vapor and Crystal, Mol. Phys., 31, 479–489, 1976.

Carslaw, N., Creasey, D. J., Heard, D. E., Jacobs, P. J., Lee, J. D., Lewis, A. C., McQuaid, J. B., Pilling, M. J., Bauguitte, S., Penkett, S. A., Monks, P. S., and Salisbury, G.: Eastern Atlantic Spring Experiment 1997 (EASE97) – 2. Comparisons of model concentrations of OH, HO2, and RO2 with measurements, J. Geophys. Res.-Atmos., 107, 2002.

Cronin, B., Nix, M. G. D., Qadiri, R. H., and Ashfold, M. N. R.: High resolution photofragment translational spectroscopy studies of the near ultraviolet photolysis of pyrrole, Phys. Chem. Chem. Phys., 6, 5031–5041, 2004.

Curtis, A. R. and Sweetenham, W. P.: Facsimile/Chekmat Users Manual, AERE Report R-12805, Her Majesty's Stationary Office, England.

de Gouw, J. and Warneke, C.: Measurements of volatile organic compounds in the earths atmosphere using proton-transfer-reaction mass spectrometry, Mass Spectrom. Rev., 26, 223–257, 2007.

Di Carlo, P., Brune, W. H., Martinez, M., Harder, H., Lesher, R., Ren, X. R., 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.

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.

Hasson, A. S., Chung, M. Y., Kuwata, K. T., Converse, A. D., Krohn, D., and Paulson, S. E.: Reaction of Criegee intermediates with water vapor - An additional source of OH radicals in alkene ozonolysis?, J. Phys. Chem. A, 107, 6176–6182, 2003.

Hasson, A. S., Tyndall, G. S., and Orlando, J. J.: A product yield study of the reaction of HO2 radicals with ethyl peroxy (C2H5O2), acetyl peroxy (CH3C(O)O-2), and acetonyl peroxy (CH3C(O)CH2O2) radicals, J. Phys. Chem. A, 108, 5979–5989, 2004.

Heard, D. E. and Pilling, M. J.: Measurement of OH and HO2 in the troposphere, Chem. Rev., 103, 5163–5198, 2003.

Hofzumahaus, A., Aschmutat, U., Hessling, M., Holland, F., and Ehhalt, D. H.: The measurement of tropospheric OH radicals by laser-induced fluorescence spectroscopy during the POPCORN field campaign, Geophys. Res. Lett., 23, 2541–2544, 1996.

Holland, F., Hofzumahaus, A., Schafer, R., Kraus, A., and Patz, H. W.: Measurements of OH and HO2 radical concentrations and photolysis frequencies during BERLIOZ, J. Geophys. Res.-Atmos., 108(D4), 8246, doi:10.1029/2001JD001393, 2003.

Holzinger, R., Lee, A., Paw, K. T., and Goldstein, A. H.: Observations of oxidation products above a forest imply biogenic emissions of very reactive compounds, Atmos. Chem. Phys., 5, 67–75, 2005.

Jeanneret, F., Kirchner, F., Clappier, A., van den Bergh, H., and Calpini, B.: Total VOC reactivity in the planetary boundary layer 1. Estimation by a pump and probe OH experiment, J. Geophys. Res.-Atmos., 106, 3083–3093, 2001.

Karl, T., Potosnak, M., Guenther, A., Clark, D., Walker, J., Herrick, J. D., and Geron, C.: Exchange processes of volatile organic compounds above a tropical rain forest: Implications for modeling tropospheric chemistry above dense vegetation, J. Geophys. Res.-Atmos., 109, D18306, doi:10.1029/2004JD004738, 2004.

Kovacs, T. A. and Brune, W. H.: Total OH loss rate measurement: J. Atmos. Chem., 39, 105–122, 2001.

Kovacs, T. A., Brune, W. H., Harder, H., Martinez, M., Simpas, J. B., Frost, G. J., Williams, E., Jobson, T., Stroud, C., Young, V., Fried, A., and Wert, B.: Direct measurements of urban OH reactivity during Nashville SOS in summer 1999, J. Environ. Monit., 5, 68–74, 2003.

Lelieveld, J., Dentener, F. J., Peters, W., and Krol, M. C.: On the role of hydroxyl radicals in the self-cleansing capacity of the troposphere, Atmos. Chem. Phys., 4, 2337–2344, 2004.

Lewis, A. C., Carslaw, N., Marriott, P. J., Kinghorn, R. M., Morrison, P., 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.

Lindinger, W., Hansel, A., and Jordan, A.: On-line monitoring of volatile organic compounds at pptv levels by means of proton-transfer-reaction mass spectrometry (PTR-MS) – Medical applications, food control and environmental research, Int. J. Mass Spectrom., 173, 191–241, 1998a.

Lindinger, W., Hansel, A., and Jordan, A.: Proton-transfer-reaction mass spectrometry (PTR-MS): on-line monitoring of volatile organic compounds at pptv levels, Chem. Soc. Rev., 27, 347–354, 1998b.

Maris, C., Chung, M. Y., Lueb, R., Krischke, U., Meller, R., Fox, M. J., and Paulson, S. E.: Development of instrumentation for simultaneous analysis of total non-methane organic carbon and volatile organic compounds in ambient air, Atmos. Environ., 37, S149–S158, 2003.

Martinez, M., Harder, H., Kovacs, T. A., et al.: OH and HO2 concentrations, sources, and loss rates during the Southern Oxidants Study in Nashville, Tennessee, summer 1999, J. Geophys. Res.-Atmos., 108(D19), 4617, doi:10.1029/2003JD003551, 2003.

Olson, J. R., Crawford, J. H., Chen, G., et al.: Testing fast photochemical theory during TRACE-P based on measurements of OH, HO2, and CH2O, J. Geophys. Res.-Atmos., 109, D15S10, doi:10.1029/2003JD004278, 2004.

Paulson, S. E., Chung, M. Y., and Hasson, A. S., OH radical formation from the gas-phase reaction of ozone with terminal alkenes and the relationship between structure and mechanism: J. Phys. Chem. A, 103, 8125-8138, 1999.

Poppe, D., Zimmermann, J., Bauer, R., et al.: Comparison Of Measured Oh Concentrations With Model-Calculations: J. Geophys. Res.-Atmos., 99, 16 633–16 642, 1994.

Ren, X. R., Brune, W. H., Cantrell, C. A., Edwards, G. D., Shirley, T., Metcalf, A. R., and Lesher, R. L.: Hydroxyl and peroxy radical chemistry in a rural area of Central Pennsylvania: Observations and model comparisons, J. Atmos. Chem., 52, 231–257, 2005.

Ren, X. R., Brune, W. H., Oliger, A., Metcalf, A. R., Simpas, J. B., Shirley, T., Schwab, J. J., Bai, C. H., Roychowdhury, U., Li, Y. Q., Cai, C. X., Demerjian, K. L., He, Y., Zhou, X. L., Gao, H. L., and Hou, J.: OH, HO2, and OH reactivity during the PMTACS-NY Whiteface Mountain 2002 campaign: Observations and model comparison, J. Geophys. Res.-Atmos., 111, D10S03, doi:10.1029/2005JD006126, 2006.

Ren, X. R., Harder, H., Martinez, M., Lesher, R. L., Oliger, A., Shirley, T., Adams, J., Simpas, J. B., and Brune, W. H.: HOx concentrations and OH reactivity observations in New York City during PMTACS-NY2001, Atmos. Environ., 37, 3627–3637, 2003.

Roberts, J. M., Bertman, S. B., Jobson, T., Niki, H., and Tanner, R.: Measurement of total nonmethane organic carbon (C-y): Development and application at Chebogue Point, Nova Scotia, during the 1993 North Atlantic Regional Experiment campaign, J. Geophys. Res.-Atmos., 103, 13 581–13 592, 1998.

Sadanaga, Y., Yoshino, A., Kato, S., and Kajii, Y.: Measurements of OH reactivity and photochemical ozone production in the urban atmosphere, Environ. Sci. Technol., 39, 8847–8852, 2005.

Sadanaga, Y., Yoshino, A., Kato, S., Yoshioka, A., Watanabe, K., Miyakawa, Y., Hayashi, I., Ichikawa, M., Matsumoto, J., Nishiyama, A., Akiyama, N., Kanaya, Y., and Kajii, Y.: The importance of NO2 and volatile organic compounds in the urban air from the viewpoint of the OH reactivity, Geophys. Res. Lett., 31, D10S03, doi:10.1029/2005JD006126, 2004a.

Sadanaga, Y., Yoshino, A., Watanabe, K., Yoshioka, A., Wakazono, Y., Kanaya, Y., and Kajii, Y.: Development of a measurement system of OH reactivity in the atmosphere by using a laser-induced pump and probe technique, Rev. Sci. Instrum., 75, 2648–2655, 2004b.

Salisbury, G., Williams, J., Holzinger, R., Gros, V., Mihalopoulos, N., Vrekoussis, M., Sarda-Esteve, R., Berresheim, H., von Kuhlmann, R., Lawrence, M., and Lelieveld, J.: Ground-based PTR-MS measurements of reactive organic compounds during the MINOS campaign in Crete, July–August 2001, Atmos. Chem. Phys., 3, 925–940, 2003.

Shirley, T. R., Brune, W. H., Ren, X., Mao, J., Lesher, R., Cardenas, B., Volkamer, R., Molina, L. T., Molina, M. J., Lamb, B., Velasco, E., Jobson, T., and Alexander, M.: Atmospheric oxidation in the Mexico City Metropolitan Area (MCMA) during April 2003, Atmos. Chem. Phys., 6, 2753–2765, 2006.

Sickles, J. E., Eaton, W. C., Ripperton, L. A., and Wright, R.S., US Environmental Protection Agency, EPA-60017-77-104, 1977.

Sinha, V., Williams, J., Meyerhofer, M., Riebesell, U., Paulino, A. I., and Larsen, A.: Air-sea fluxes of methanol, acetone, acetaldehyde, isoprene and DMS from a Norwegian fjord following a phytoplankton bloom in a mesocosm experiment, Atmos. Chem. Phys., 7, 739–755, 2007a.

Sinha, V., Williams, J., Crutzen P., and Lelieveld J.: Methane emissions from boreal and tropical forest ecosystems derived from in-situ measurements, Atmos. Chem. Phys. Discuss., 7, 14 011–14 039, 2007b.

Smith, S. C., Lee, J. D., Bloss, W. J., Johnson, G. P., Ingham, T., and Heard, D. E.: Concentrations of OH and HO2 radicals during NAMBLEX: measurements and steady state analysis, Atmos. Chem. Phys., 6, 1435–1453, 2006.

Williams, J., Poschl, U., Crutzen, P. J., Hansel, A., Holzinger, R., Warneke, C., Lindinger, W., and Lelieveld, J.: An atmospheric chemistry interpretation of mass scans obtained from a proton transfer mass spectrometer flown over the tropical rainforest of Surinam, J. Atmos. Chem., 38, 133–166, 2001.

Williams, J., Yassaa, N., Bartenbach, S., and Lelieveld, J.: Mirror image hydrocarbons from Tropical and Boreal forests, Atmos. Chem. Phys., 7, 973–980, 2007.

Yoshino, A., Sadanaga, Y., Watanabe, K., Kato, S., Miyakawa, Y., Matsumoto, J., and Kajii, Y.: Measurement of total OH reactivity by laser-induced pump and probe technique – comprehensive observations in the urban atmosphere of Tokyo, Atmos. Environ., 40, 7869–7881, 2006.