References

ACPD

Atmospheric Chemistry and Physics Discussions

ACPD

1680-7375

Copernicus GmbH

Göttingen, Germany

10.5194/acpd-7-8755-2007

The tropical forest and fire emissions experiment: method evaluation of volatile organic compound emissions measured by PTR-MS, FTIR, and GC from tropical biomass burning

Karl

T. G.

¹ Christian

T. J.

² Yokelson

R. J.

² Artaxo

³ Min Hao

² Guenther

National Center for Atmospheric Research, Boulder, USA

University of Montana, Department of Chemistry, Missoula, USA

University of Sao Paulo, Department of Physics, Sao Paulo, Brazil

25 06 2007

7 3 8755 8793

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/7/8755/2007/acpd-7-8755-2007.html

The full text article is available as a PDF file from http://www.atmos-chem-phys-discuss.net/7/8755/2007/acpd-7-8755-2007.pdf

Volatile Organic Compound (VOC) emissions from fires in tropical forest fuels were quantified using Proton-Transfer-Reaction Mass Spectrometry (PTRMS), Fourier Transformation Infrared Spectroscopy (FTIR) and gas chromatography (GC) coupled to PTRMS (GC-PTR-MS). We investigated VOC emissions from 19 controlled laboratory fires at the USFS Fire Sciences Laboratory and 16 fires during an intensive airborne field campaign during the peak of the burning season in Brazil in 2004. The VOC emissions were dominated by oxygenated VOCs (OVOC) (OVOC/NMHC ~4:1, NMHC: non-methane hydrocarbons) The specificity of the PTR-MS instrument, which measures the mass to charge ratio of VOCs ionized by H3O+ ions, was validated by gas chromatography and by intercomparing in-situ measurements with those obtained from an open path FTIR instrument. Emission ratios for methyl vinyl ketone, methacrolein, crotonaldehyde, acrylonitrile and pyrrole were measured in the field for the first time. Our measurements show a higher contribution of OVOCs than previously assumed for modeling purposes. Comparison of fresh (<15 min) and aged (>1hour-1day) smoke suggests altered emission ratios due to gas phase chemistry for acetone but not for acetaldehyde and methanol. Emission ratios for numerous, important, reactive VOCs with respect to acetonitrile (a biomass burning tracer) are presented.

References 1

Andreae, M., Talbot, R., Andreae, T. and Harris, R.: Formic and acetic acid over the central Amazon region, Brazil. 1. Dry season, J. Geophys. Res., 93, 1616–1624, 1988.

Andreae, M. O., Artaxo, P., Fischer, H., Freitas, S. R., Gregoire, J. M., Hansel, A., Hoor, P., Kormann, R., Krejci, R., Lange, L., Lelieveld, J., Lindinger, W., Longo, K., Peters, W., de Reus, M., Scheeren, B., Dias, M. A. F. S., Strom, J., van Velthoven, P. F. J. and Williams, J.: Transport of biomass burning smoke to the upper troposphere by deep convection in the equatorial region, Geophys. Res. Lett., 28, 951–954, 2001a.

Andreae, M. O. and Merlet, P.: Emission of trace gases and aerosols from biomass burning, Global Biogeochem. Cycles, 15, 955–966, 2001b.

Bertschi, I. T., Yokelson, R. J., Ward, D. E., Christian, T. J., and Hao, W. M.: Trace gas emissions from the production and use of domestic biofuels in Zambia measured by open-path Fourier transform infrared spectroscopy, J. Geophys. Res., 108, doi:10.1029/2002JD002158, 2003.

Blake, N. J., Blake, D. R., Sive, B. C., Chen, T. Y., Rowland, F. S., Collins, J. E., Sachse, G. W., and Anderson, B. E.: Biomass burning emissions and vertical distribution of atmospheric methyl halides and other reduced carbon gases in the South Atlantic region, J. Geophys. Res.-Atmos., 101, 24 151–24 164, 1996.

Carvalho, J. A., Costa, F. S., Veras, C. A. G., Sandberg, E. C., Alvarado, E. C., Gielow, R., Serra, A. M., and Santos, J. C.: Biomass fire consuption and carbon release rates of rainforest-clearing experiments conducted in northern Mato Grosso, Brazil, J. Geophys. Res., 106, 17 877–17 887, 2001.

Christian, T. J., Kleiss, B., Yokelson, R. J., Holzinger, R., Crutzen, P. J., Hao, W. M., Saharjo, B. H., and Ward, D. E.: Comprehensive laboratory measurements of biomass-burning emissions: 1. Emissions from Indonesian, African, and other fuels, J. Geophys. Res.-Atmos., 108, 4719, doi:10.1029/2003JD003704, 2003.

Christian, T. J., Kleiss, B., Yokelson, R. J., Holzinger, R., Crutzen, P. J., Hao, W. M., Shirai, T. and Blake, D. R.: Comprehensive laboratory measurements of biomass-burning emissions: 2. First intercomparison of open-path FTIR, PTR-MS, and GC- MS/FID/ECD, J. Geophys. Res.-Atmos., 109, D02311, doi:10.1029/2003JD003874, 2004. %

%Christian, T. J., Karl, T., Yokelson, R. J., Guenther, A., and Hao, W. M.: %The Tropical Forest and Fire Emissions Experiment: Comprehensive laboratory %measurements of the emissions from burning sugar cane, palms, and other %tropical fuels, Atmos. Chem. Phys. Discuss., submitted, %2007a. %

%Christian, T. J., Yokelson, R. J., Carvalho, A., Griffith, D. W. T., %Alvarado, E. C., Santos, J. C., Neto, T. G. S., Veras, C. A. G., and Hao, W. %M.: The Tropical Forest and Fire Emissions Experiment: Trace gases emitted %by smoldering logs and dung on deforestation and pasture fires in Brazil, %Atmos. Chem. Phys. Discuss., submitted, 2007b.

Crutzen, P. J. and Andreae, M. O.: Biomass Burning in the Tropics: impact on atmospheric chemistry and biogeochemical cycles, Science, 250, 1669–1678, 1990.

Crutzen, P. J., Delany, A. C., Greenberg, J., Haagenson, P., Heidt, L. E., Lueb, R., Pollock, W., Seiler, W., Wartburg, A., and Zimmerman, P.: Tropospheric Chemical Composition Measurements in Brazil During the Dry Season, J. Atmos. Chem., 2, 233–256, 1985.

de Gouw, J. A., Warneke, C., Stohl, A., Wollny, A. G., Brock, C. A., Cooper, O. R., Holloway, J. S., Trainer, M., Fehsenfeld, F. C., Atlas, E. L., Donnelly, S. G., Stroud, V., and Lueb, A.: Volatile organic compounds composition of merged and aged forest fire plumes from Alaska and western Canada, J. Geophys. Res.-Atmos., 111, D10303, doi:10.1029/2005JD006175, 2006.

Ferek, R. J., Reid, J. S., Hobbs, P. V., Blake, D. R., and Liousse, C.: Emission factors of hydrocarbons, halocarbons, trace gases and particles from biomass burning in Brazil, J. Geophys. Res.-Atmos., 103, 32 107–32 118, 1998.

Friedli, H. R., Atlas, E., Stroud, V. R., Giovanni, L., Campos, T., and Radke, L. F.: Volatile organic trace gases emitted from North American wildfires, Global Biogeochem. Cycles, 15, 435–452, 2001.

Goode, J. G., Yokelson, R. J., Ward, D. E., Susott, R. A., Babbitt, R. E., Davies, M. A., and Hao, W. M.: Measurements of excess O3, CO2, CO, CH4, C2H2, HCN, NO, NH3, HCOOH, CH3COOH, HCHO, and CH3OH in 1997 Alaskan biomass burning plumes by airborne Fourier transform infrared spctroscopy (AFTIR), J. Geophys. Res., 105, 22 147–22 166, 2000.

Greenberg, J., Lee, B., Helmig, D., and Zimmerman, P.: Fully automated gas chromatograph-flame ionization detector system for the in situ determination of atmospheric non-methane hydrocarbons at low parts per trillion concentration, J.Chromotogr., 676, 389–398, 1994.

Greenberg, J. P., Friedli, H., Guenther, A. B., Hanson, D., Harley, P., and Karl, T.: Volatile organic emissions from the distillation and pyrolysis of vegetation, Atmos. Chem. Phys., 6, 81–91, 2006.

Griffith, D. W. T.: Synthetic calibration and quantitative analysis of gas-phase FT-IR spectra, Appl. Spectroscopy, 50, 59–70, 1996.

Hansel, A., Singer, W., Wisthaler, A., Schwarzmann, M., and Lindinger, W.: Energy dependencies of the proton transfer reactions H3O(+)+CH2O double left right arrow CH2OH++H2O, International Journal of Mass Spectrometry, 167, 697–703, 1997.

Hobbs, P. V., Sinah, P., Yokelson, R. J., Christian, T. J., Blake, D. R., Gao, S., Kirchstetter, T. W., Novakov, T., and Pilewskie, P.: Evolution of gases and particles from a savanna fire in South Africa, J. Geophys. Res., 108, 8485, doi:8410.1029/2002JD002352, 2003.

Holzinger, R., Warneke, C., Hansel, A., Jordan, A., Lindinger, W., Scharffe, D. H., Schade, G., and Crutzen, P. J.: Biomass burning as a source of formaldehyde, acetaldehyde, methanol, acetone, acetonitrile, and hydrogen cyanide, Geophys. Res. Lett., 26, 1161–1164, 1999.

Holzinger, R., Williams, J., Salisbury, G., Klupfel, T., de Reus, M., Traub, M., Crutzen, P. J., and Lelieveld, J.: Oxygenated compounds in aged biomass burning plumes over the Eastern Mediterranean: evidence for strong secondary production of methanol and acetone, Atmos. Chem. Phys., 5, 39–46, 2005.

Jost, C., Trentmann, J., Sprung, D., Andreae, M. O., McQuaid, J. B., and Barjat, H.: Trace gas chemistry in a young biomass burning plume over Namibia: Observations and model simulations, J. Geophys. Res., 108, 8482, doi: 8410.1029/2002JD002431, 2003.

Karl, T., Guenther, A., Spirig, C., Hansel, A., and Fall, R.: Seasonal variation of biogenic VOC emissions above a mixed hardwood forest in northern Michigan (vol 30, pg 2186, 2003), Geophys. Res. Lett., 31, 2186, doi:10.1029/2003GL018432, 2004.

Karl, T., Hansel, A., Mark, T., Lindinger, W., and Hoffmann, D.: Trace gas monitoring at the Mauna Loa Baseline observatory using proton-transfer reaction mass spectrometry, Int. J. Mass Spectrometry, 223, 527–538, 2003.

Kaufman, Y. J., Hobbs, P. V., Kirchhoff, V. W. J. H., Artaxo, P., Remer, L. A., Holben, B. N., King, M. D., Ward, D. E., Prins, E. M., Longo, K. M., Mattos, L. F., Nobre, C. A., Spinhirne, J. D., Ji, Q., Thompson, A. M., Gleason, J. F., Christopher, S. A., and Tsay, S. C.: Smoke, Clouds, and Radiation - Brazil (SCAR-B) experiment, J. Geophys. Res.-Atmos., 103, 31 783–31 808, 1998.

Koppmann, R., Khedim, A., Rudolph, J., Poppe, D., Andreae, M. O., Helas, G., Welling, M., and Zenker, T.: Emissions of organic trace gases from savanna fires in southern Africa during the 1992 Southern African Fire Atmosphere Research Initiative and their impact on the formation of tropospheric ozone, J. Geophys. Res.-Atmos., 102, 18 879–18 888, 1997.

Lindinger, W., Jordan, A., and Hansel, A.: Proton-transfer-reaction mass spectroscopy (PTR-MS): on-line monitoring of volatile organic compounds at pptv levels, Chem. Soc. Rev., 27, 347–534, 1998.

Lobert, J. M., Scharffe, D. H., Hao, W. M., and Crutzen, P. J.: Importance of biomass burning in the atmospheric budgets of nitrogen-containing gases, Nature, 346, 552–554, 1990.

Mason, S. A., Field, R. J., Yokelson, R. J., Kochivar, M. A., Tinsley, M. R., Ward, D. E., and Hao, W. M.: Complex effects arising in smoke plume simulations due to inclusion of direct emissions of oxygenated organic species from biomass combustion, J.f Geophys. Res., 106, 12 527–12 537, 2001.

Mauzerall, D. L., Logan, J. A., Jacob, D. J., Anderson, B. E., Blake, D. R., Bradshaw, J. D., Heikes, B., Sachse, G. W., Singh, H., and Talbot, B.: Photochemistry in biomass burning plumes and implications for tropospheric ozone over the tropical South Atlantic, J. Geophys. Res.-Atmos., 103, 8401–8423, 1998.

McKeen, S. A., Mount, G., Eisele, F., Williams, E., Harder, J., Goldan, P., Kuster, W., Liu, S. C., Baumann, K., Tanner, D., Fried, A., Sewell, S., Cantrell, C., and Shetter, R.: Photochemical modeling of hydroxyl and its relationship to other species during the Tropospheric OH Photochemistry Experiment, J. Geophys. Res.-Atmos., 102, 6467–6493, 1997.

Norman, M., Wisthaler, A., and Hansel, A.: O2+ as primary reagent ion in the PTR-MS instrument: detection of gas-phase ammonia, 3rd International Conference on Proton Transfer Reaction Mass Spectrometry and Its Applications, 2007.

Roberts, J. Williams, J., Baumann, K., Buhr, M. P., Goldan, P. D., Holloway, J., Huebler, G., Kuster, W.C., McKeen, S. A., Ryerson, T. B., Trainer, M., Williams, E. J., Fehsenfeld, F. C., Bertman, S.B., Nouaime, G., Seaver, C., Grodzinsky, G., Rodgers, M., and Young, V. L: Measurements of PAN, PPN, MPAN made during the 1994 and 1995 Nashville intensives of the Southern Oxidant Study: Implications for regional ozone production from biogenic hydrocarbons, J. Geophys. Res., 103, 22 473–22 490, 1998.

Singh, H. B., Salas, L. J., Chatfield, R. B., Czech, E., Fried, A., Walega, J., Evans, M. J., Field, B. D., Jacob, D. J., Blake, D., Heikes, B., Talbot, R., Sachse, G., Crawford, J. H., Avery, M. A., Sandholm, S., and Fuelberg, H.: Analysis of the atmospheric distribution, sources, and sinksof oxygenated volatile organic chemicals based on measurements over the Pacific during TRACE-P, J. Geophys. Res., 109, D15S07, doi:10.1029/2003JD003883, 2004.

Sinha, P., Hobbs, P. V., Yokelson, R. J., Bertschi, I. T., Blake, D. R., Simpson, I. J., Gao, S., Kirchstetter, T. W., and Novakov, T.: Emissions of trace gases and particles from savanna fires in southern Africa, J. Geophys. Res., 108, 8487 doi:10.1029/2002JD002325, 2003.

Trentmann, J., Yokelson, R. J., Hobbs, P. V., Winterrath, T., Christian, T. J., Andreae, M. O. and Mason, S. A.: An analysis of the chemical processes in the smoke plume from a savanna fire, J. Geophys. Res.-Atmos., 110, D12301, doi:10.1029/2004JD005628, 2005.

Ward, D. E., Hao, W. M., Susott, R. A., Babbitt, R. E., Shea, R. W., Kauffman, J. B., and Justice, C. O.: Effect of fuel composition on combustion efficiency and emission factors for African savanna ecosystems, J. Geophys. Res.-Atmos., 101, 23 569–23 576, 1996.

Warneke, C., de Gouw, J. A., Goldan, P. D., Kuster, W. C., and Fall, R.: Validation of atmospheric measurements by proton-transfer-reaction mass spectrometry using a gas-chromatographic pre-separation method, Environ. Sci. Technol., 37, 2494–2501, 2003a.

Warneke, C., De Gouw, J. A., Kuster, W. C., Goldan, P. D., and Fall, R.: Validation of atmospheric VOC measurements by proton-transfer-reaction mass spectrometry using a gas-chromatographic preseparation method, Environ. Sci. Technol., 37, 2494–2501, 2003b.

Warneke, C., van der Veen, C., Luxembourg, S., de Gouw, J. A., and Kok, A.: Measurements of benzene and toluene in ambient air using proton-transfer-reaction mass spectrometry: calibration, humidity dependence, and field intercomparison, Int. J. Mass Spectrometry, 207, 167–182, 2001.

Yokelson, R. J., Bertschi, I. T., Christian, T. J., Hobbs, P. V., Ward, D. E. and Hao, W. M.: Trace gas measurements in nascent, aged, and cloud-processed smoke from African savanna fires by airborne Fourier transfrom infrared spectroscopy (AFTIR), J. Geophys. Res., 108, 8478, doi:8410.1029/2002JD002322, 2003a.

Yokelson, R. J., Christian, T. J., Bertschi, I. T., and Hao, W. M.: Evaluation of adsorption effects on measurements of ammonia, acetic acid, and methanol, J. Geophys. Res.-Atmos., 108, 4649, doi:10.1029/2003JD003549, 2003b.

Yokelson, R. J., Karl, T., Artaxo, P., Blake, D., Christian, T. J., Griffith, D. W. T., Guenther, A., and Hao, W. M.: The Tropical Forest and Fire Emissions Experiment: Overview and airborne fire emission factor measurements, Atmos. Chem. Phys. Discuss., 7, 6903–6958, 2007.

Yokelson, R. J., Susott, R., Ward, D. E., Reardon, J. and Griffith, D. W. T.: Emissions from smoldering combustion of biomass measured by open-path Fourier transform infrared spectroscopy, J. Geophys. Res.-Atmos., 102, 18 865–18 877, 1996.