References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-9-615-2009

Eddy covariance fluxes of acyl peroxy nitrates (PAN, PPN and MPAN) above a Ponderosa pine forest

Wolfe

G. M.

¹ Thornton

J. A.

² Yatavelli

R. L. N.

² McKay

³ Goldstein

A. H.

³ LaFranchi

⁴ Min

K.-E.

⁴ Cohen

R. C.

⁴

Department of Chemistry, University of Washington, Seattle, WA, USA

Department of Atmospheric Sciences, University of Washington, Seattle, WA, USA

Department of Environmental Science, Policy, and Management, University of California, Berkeley, CA, USA

Department of Chemistry, University of California, Berkeley, CA, USA

27 01 2009

9 2 615 634

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During the Biosphere Effects on AeRosols and Photochemistry EXperiment 2007 (BEARPEX-2007), we observed eddy covariance (EC) fluxes of speciated acyl peroxy nitrates (APNs), including peroxyacetyl nitrate (PAN), peroxypropionyl nitrate (PPN) and peroxymethacryloyl nitrate (MPAN), above a Ponderosa pine forest in the western Sierra Nevada. All APN fluxes are net downward during the day, with a median midday PAN exchange velocity of −0.3 cm s−1; nighttime storage-corrected APN EC fluxes are smaller than daytime fluxes but still downward. Analysis with a standard resistance model shows that loss of PAN to the canopy is not controlled by turbulent or molecular diffusion. Stomatal uptake can account for 25 to 50% of the observed downward PAN flux. Vertical gradients in the PAN thermal decomposition (TD) rate explain a similar fraction of the flux, suggesting that a significant portion of the PAN flux into the forest results from chemical processes in the canopy. The remaining "unidentified" portion of the net PAN flux (~15%) is ascribed to deposition or reactive uptake on non-stomatal surfaces (e.g. leaf cuticles or soil). Shifts in temperature, moisture and ecosystem activity during the summer – fall transition alter the relative contribution of stomatal uptake, non-stomatal uptake and thermochemical gradients to the net PAN flux. Daytime PAN and MPAN exchange velocities are a factor of 3 smaller than those of PPN during the first two weeks of the measurement period, consistent with strong intra-canopy chemical production of PAN and MPAN during this period. Depositional loss of APNs can be 3–21% of the gross gas-phase TD loss depending on temperature. As a source of nitrogen to the biosphere, PAN deposition represents approximately 4–19% of that due to dry deposition of nitric acid at this site.

References 1

Arya, S. P.: Introduction to Micrometeorology, Academic Press, San Diego, CA, USA, 1988.

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.

Brown, S. S., Dibb, J. E., Stark, H., Aldener, M., Vozella, M., Whitlow, S., Williams, E. J., Lerner, B. M., Jakoubek, R., Middlebrook, A. M., DeGouw, J. A., Warneke, C., Goldan, P. D., Kuster, W. C., Angevine, W. M., Sueper, D. T., Quinn, P. K., Bates, T. S., Meagher, J. F., Fehsenfeld, F. C., and Ravishankara, A. R.: Nighttime removal of NOx in the summer marine boundary layer, Geophys. Res. Lett., 31, L07108, doi:10.1029/2004GL019412, 2004.

Bytnerowicz, A. and Fenn, M. E.: Nitrogen deposition in California forests: a review, Environ. Pollut., 92(2), 127–146, 1996.

California Department of Forestry and Fire Protection (CDF): 2007 Fire Incidents, online http://cdfdata.fire.ca.gov, last access: 14 April 2008, 2008.

Cleary, P. A., Wooldridge, P. J., Millet, D. B., McKay, M., Goldstein, A. H., and Cohen, R. C.: Observations of total peroxy nitrates and aldehydes: measurement interpretation and inference of OH radical concentrations, Atmos. Chem. Phys., 7, 1947–1960, 2007.

Day, D. A., Wooldridge, P. J., and Cohen, R. C.: Observations of the effects of temperature on atmospheric HNO3, $\sum$ANs, $\sum$PNs, and NOx: evidence for a temperature-dependent HOx source, Atmos. Chem. Phys., 8, 1867–1879, 2008.

Dillon, M. B., Lamanna, M. S., Schade, G. W., Goldstein, A., and Cohen, R. C.: Chemical evolution of the Sacramento urban plume: Transport and oxidation, J. Geophys. Res., 107(D5), 4045, doi:10.1029/2001JD000969, 2002.

Dollard, G. J., Jones, B. M. R., and Davies, T. J.: Dry deposition of HNO3 and PAN, A.E.R.E. Rep. R13780, Harwell Lab., Oxfordshire, UK, 1990.

Doskey, P. V., Kotamarthi, R. V., Fukui, Y., Cook, D. R., Breitbeil III, F. W., and Wesely, M. L.: Air-surface exchange of peroxyacetyl nitrate at a grassland site, J. Geophys. Res., 109, D10310, doi:10.1029/2004JD004533, 2004.

Dyer, A. J.: A review of flux-profile relationships, Bound.-Lay. Meteorol., 7, 363–372, 1974.

Faloona, I. C., Tan, D., Lesher, R. L., Hazen, N. L., Frame, C. L., Simpas, J. B., Harder, H., Martinez, M., Di Carlo, P., Ren, X. R., and Brune, W. H.: A laser-induced fluorescence instrument for detecting tropospheric OH and HO2: Characteristics and calibration, J. Atmos. Chem., 47, 139–167, 2004.

Farmer, D. K. and Cohen, R. C.: Observations of HNO3, $\sum$AN, $\sum$PN and NO2 fluxes: evidence for rapid HOx chemistry within a pine forest canopy, Atmos. Chem. Phys., 8, 3899–3917, 2008.

Farmer, D. K., Wooldridge, P. J., and Cohen, R. C.: Application of thermal-dissociation laser induced fluorescence (TD-LIF) to measurement of HNO3, Salkyl nitrates, Speroxy nitrates, and NO2 fluxes using eddy covariance, Atmos. Chem. Phys., 6, 3471–3486, 2006.

Foken, T. and Wichura, B.: Tools for quality assessment of surface-based flux measurements, Agr. Forest Meteorol., 78, 83–105, 1996.

Gao, W., Wesely, M. L., and Lee, I. Y.: A numerical study of the effects of air chemistry on fluxes of NO, NO2, and O3 near the surface, J. Geophys. Res., 96(D10), 18761–18769, 1991.

Garland, J. A. and Penkett, S. A.: Absorption of peroxy acetyl nitrate and ozone by natural surfaces, Atmos. Environ., 10, 1127–1131, 1976.

Gerosa, G., Derghi, F., and Cieslik, S.: Comparison of Different Algorithms for Stomatal Ozone Flux Determination from Micrometeorological Measurements, Water Air Soil Pollut., 179, 309–321, 2007.

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.

Goulding, K. W. T., Bailey, N. J., Bradbury, N. J., Hargreaves, P., Howe, M., Murphy, D. V., Poulton, P. R., and Willison, T. W.: Nitrogen deposition and its contribution to nitrogen cycling and associated soil processes, New Phytol., 139, 49–58, 1998.

Grosjean, D., Grosjean, E., and Williams, E. L.: Thermal decomposition of PAN, PPN and vinyl-PAN, Air and Waste, 44(4), 391–396, 1994a.

Grosjean, D., Grosjean, E., and Williams, E. L., II: Thermal decomposition of C3-substituted peroxyacyl nitrates, Res. Chem. Intermed., 20(3–5), 447–461, 1994b.

Hill, A. C.: Vegetation: A Sink for Atmospheric Pollutants, Japca. J. Air. Waste Ma., 21(6), 341–346, 1971.

Højstrup, J.: A statistical data screening procedure, Meas. Sci. Technol., 4, 153–157, 1993.

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.

Horst, T. W.: A simple formula for attenuation of eddy fluxes measured with first-order-response scalar sensors, Bound.-Lay. Meteorol., 82, 219–233, 1997.

Hudman, R. C., Jacob, D. J., Cooper, O. R., Evans, M. J., Heald, C. L., Park, R. J., Fehsenfeld, F., Flocke, F., Holloway, J., Hübler, G., Kita, K., Koike, M., Kondo, Y., Neuman, A., Nowak, J., Oltmans, S., Parrish, D., Roberts, J. M., and Ryerson, T.: Ozone production in transpacific Asian pollution plumes and implications for ozone air quality in California, J. Geophys. Res., 109, D23S10, doi:10.1029/2004JD004974, 2004.

Jensen, N. O. and Hummelshøj, P.: Derivation of canopy resistance for water vapour fluxes over a spruce forest, using a new technique for the viscous sublayer resistance, Agr. Forest Meteorol., 73, 339–352, 1995.

Jensen, N. O. and Hummelshøj, P.: Erratum to "Derivation of canopy resistance for water vapor fluxes over a spruce forest, using a new technique for the viscous sublayer resistance", Agr. Forest Meteorol., 85, p 289, 1997.

Kaimal, J. C. and Finnigan, J. J.: Atmospheric Boundary Layer Flows: Their Structure and Measurement, Oxford University Press, Inc., New York, NY, USA, 1994.

Kames, J. and Schurath, U.: Henry's Law and Hydrolysis-Rate Constants for Peroxyacyl Nitrates (PANs) Using a Homogeneous Gas-Phase Source, J. Atmos. Chem., 21, 151–164, 1995.

Kotchenruther, R. A., Jaffe, D. A., and Jaeglé, L.: Ozone photochemistry and the role of peroxyacetyl nitrate in the springtime northeastern Pacific troposphere: Results from the Photochemical Ozone Budget of the Eastern North Pacific Atmosphere (PHOBEA) campaign, J. Geophys. Res., 106(D22), 28731–28742, 2001.

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(7), 1371–1374, doi:10.1029/2002GL016785, 2003.

Kurpius, M. R., Panek, J. A., Nikolov, N. T., McKay, M., and Goldstein, A. H.: Partitioning of water flux in a Sierra Nevada ponderosa pine plantation, Agr. Forest Meteorol., 117, 173–192, doi:10.1016/S0168-1923(03)00062-5, 2003.

LaFranchi, B. W., Wolfe, G. M., Thornton, J. A., et al.: Observations of acyl peroxy nitrates (PAN, PPN, and MPAN) during BEARPEX 2007: Constraints on temperature dependent sources of peroxy acetyl and hydroxyl (OH) radicals, Atmos. Chem. Phys, accepted, 2008.

Lee, X., Massman, W., and Law, B.: Handbook of Micrometeorology: A Guide for Surface Flux Measurement and Analysis, Kluwer Academic Publishers, Dordrecht, The Netherlands, 2004.

Lenschow, D. H. and Kristensen, L.: Uncorrelated noise in turbulence measurements, J. Ocean. Atmos. Technol., 2, 68–81, 1985.

Lenschow, D. H. and Raupach, M. R.: The attenuation of fluctuations in scalar concentrations through sampling tubes, J. Geophys. Res., 96, 5259–5268, 1991.

Magnani, F., Mencuccini, M., Borghetti, M., Berbigier, P., Berninger, F., Delzon, S., Grelle, A., Hari, P., Jarvis, P. G., Kolari, P., Kowalski, A. S., Lankreijer, H., Law, B. E., Lindroth, A., Loustau, D., Manca, G., Moncrieff, J. B., Rayment, M., Tedeschi, V., Valentini, R., and Grace, J.: The human footprint in the carbon cycle of temperate and boreal forests, Nature, 447, 7146, 849–851, 2007.

Massman, W.: The Attenuation of Concentration Fluctuations in Turbulent Flow Through a Tube, J. Geophys. Res., 96(D8), 15269–15273, 1991.

McFadyen, G. G. and Cape, J. N.: Physical and chemical influences on PAN concentrations at a rural site, Atmos. Environ., 33(18), 2929–2940, 1999.

McMillen, R. T.: An eddy correlation technique with extended applicability to non-simple terrain, Bound.-Lay. Meteorol., 43, 231–245, 1988.

Mihelcic, D., Holland, F., Hofzumahaus, A., Hoppe, L., Konrad, S., Müsgen, P., Pätz, H.-W., Schäfer, H. J., Schmitz, T., Volz-Thomas, A., Bächmann, K., Schlomski, S., Platt, U., Geyer, A., Alicke, B., and Moortgat, G. K.: Peroxy radicals during BERLIOZ at Pabstthum: Measurements, radical budgets and ozone production, J. Geophys. Res., 108, 8254, doi:10.1029/2001JD001014, 2003.

Misson, L., Tang, J., Xu, M., McKay, M., and Goldstein, A.: Influences of recovery from clear-cut, climate variability, and thinning on the carbon balance of a young ponderosa pine plantation, Agr. Forest Meteorol., 130, 207–222, 2005.

Monteith, J. L. and Unsworth, M. H.: Principles of Environmental Physics, 2nd ed., Edward Arnold, London, UK, , 1990.

Moore, C. J.: Frequency response correction for eddy correlation, Bound.-Lay. Meteorol., 37, 17–36, 1986.

Moxim, W. J., Levy II, H., and Kasibhatla, P. S.: Simulated global tropospheric PAN: Its transport and impact on NOx, J. Geophys. Res., 101(D7), 12621–12638, 1996.

Murphy, J. G., Day, D. A., Cleary, P. A., Wooldridge, P. J., and Cohen, R. C.: Observations of the diurnal and seasonal trends in nitrogen oxides in the western Sierra Nevada, Atmos. Chem. Phys., 6, 5321–5338, 2006.

National Center for Atmospheric Research (NCAR): TUV Radiation Model v4.4, online: http://cprm.acd.ucar.edu/Models/TUV/, last access: 23 May 2008, 2008.

Okano, K., Tobe, K., and Furukawa, A.: Foliar uptake of peroxyacetyl nitrate (PAN) by herbaceous species varying in susceptibility to this pollutant, New Phytol., 114, 139–145, 1990.

Orlando, J. J., Tyndall, G. S., Bertman, S. B., Chen, W., and Burkholder, J. B.: Rate coefficient for the reaction of OH with CH2=C(CH$_3)$C(O)OONO2 (MPAN), Atmos. Environ., 36, 1895–1900, 2002.

Parrish, D. D., Dunlea, E. J., Atlas, E. L., Schauffler, S., Donnelly, S., Stroud, V., Goldstein, A. H., Millet, D. B., McKay, M., Jaffe, D. A., Price, H. U., Hess, P. G., Flocke, F., and Roberts, J. M.: Changes in the photochemical environment of the temperate North Pacific troposphere in response to increased Asian emissions, J. Geophys. Res., 109, D23S18, doi:10.1029/2004JD004978, 2004.

Pilegaard, K., Jensen, N. O., and Hummelshøj, P.: Seasonal and diurnal variation in the deposition velocity of ozone over a spruce forest in Denmark, Water Air Soil Pollut., 85, 2223–2228, 1995.

Pryor, S. C. and Klemm, O.: Experimentally derived estimates of nitric acid dry deposition velocity and viscous sub-layer resistance at a conifer forest, Atmos. Environ., 38(18), 2769–2777, 2004.

Ritter, J. A., Lenschow, D. H., Barrick, J. D. W., Gregory, G. L., Sachse, G. W., Hill, G. F., and Woerner, M. A.: Airborne flux measurements and budget estimates of trace species over the Amazon Basin during the GTE/ABLE-2B Expedition, J. Geophys. Res., 95(D10), 16875–16886, 1990.

Roberts, J. M.: The Atmospheric Chemistry of Organic Nitrates, Atmos. Environ., 24A(2), 243–287, 1990.

Roberts, J. M. and Bertman, S. B.: The thermal decomposition of peroxyacetic nitric anhydride (PAN) and peroxymethacrylic nitric anhydride (MPAN), Int. J. Chem. Kinet., 24(3), 297–307, 1992.

Roberts, J. M., Flocke, F., Chen, G., de Gouw, J., Holloway, J. S., Hübler, G., Neuman, J. A., Nicks Jr., D. K., Nowak, J. B., Parrish, D. D., Ryerson, T. B., Sueper, D. T., Warneke, C., and Fehsenfeld, F. C.: Measurement of peroxycarboxylic nitric anhydrides (PANs) during the ITCT 2K2 aircraft intensive experiment, J. Geophys. Res., 109, D23S21, doi:10.1029/2004JD004960, 2004.

Rummel, U., Ammann, C., Kirkman, G. A., Moura, M. A. L., Foken, T., Andreae, M. O., and Meixner, F. X.: Seasonal variation of ozone deposition to a tropical rain forest in southwest Amazonia, Atmos. Chem. Phys., 7, 5415–5435, 2007.

Schade, G. W., Goldstein, A. H., and Lamanna, M. S.: Are monoterpene emissions influenced by humidity?, Geophys. Res. Lett., 26, 2187–2190, 1999.

Schrimpf, W., Lienaerts, K., Mueller, K. P., Rudolph, J., Neubert, R., Schuessler, W., and Levin, I.: Dry deposition of peroxyacetyl nitrate (PAN): Determination of its deposition velocity at night from measurements of the atmospheric PAN and $^222$ Radon concentration gradient, Geophys. Res. Lett., 23(24), 3599–3602, 1996.

Seaman, N. L., Stauffer, D. R., and Lario-Gibbs, A. M.: A multiscale four-dimensional data assimilation system applied in the San Joaquin Valley during SARMAP, I, modeling design and basic performance characteristics, J. Applied Meteorol., 34, 1739–1761, 1995.

Shepson, P. B., Bottenheim, J. W., Hastie, D. R., and Venkatram, A.: Determination of the relative ozone and PAN deposition velocities at night, Geophys. Res. Lett., 19(11), 1121–1124, 1992.

Sievering, H., Kelly, T., McConville, G., Seibold, C., and Turnipseed, A.: Nitric acid dry deposition to conifer forests: Niwot Ridge spruce-fir-pine study, Atmos. Environ., 35(22), 3851–3859, 2001.

Slusher, D. L., Huey, L. G., Tanner, D. J., Flocke, F. M., and Roberts, J. M.: A thermal dissociation-chemical ionization mass spectrometry (TD-CIMS) technique for the simultaneous measurement of peroxyacyl nitrates and dintrogen pentoxide, J. Geophys. Res., 109, D19315, doi:10.1029/2004JD004670, 2004.

Sparks, J. P., Roberts, J. M., and Monson, R. K.: The uptake of gaseous organic nitrogen by leaves: A significant global nitrogen transfer process, Geophys. Res. Lett., 30(23), 2189, doi:10.1029/2003GL018578, 2003.

Talukdar, R. K., Burkholder, J. B., Schmoltner, A. M., Roberts, J. M., Wilson, R. R., and Ravishankara, A. R.: Investigation of the loss processes for peroxyacetyl nitrate in the atmosphere: UV photolysis and reaction with OH, J. Geophys. Res., 100(D7), 14163–14173, 1995.

Taylor, O. C.: Importance of peroxyacetylnitrate (PAN) as a phytotoxic air pollutant, J. Air Pollut. Cont. Assoc., 19, 347–351, 1969.

Thom, A. S.: Momentum, mass and heat exchange of plant communities, in: Vegetation and Atmosphere, edited by: Monteith, J. L., 57–109, Elsevier, New York, NY, USA, 1975.

Turnipseed, A. A., Huey, L. G., Nemitz, E., Stickel, R., Higgs, J., Tanner, D. J., Slusher, D. L., Sparks, J. P., Flocke, F., and Guenther, A.: Eddy covariance fluxes of peroxyacetyl nitrates (PANs) and NOy to a coniferous forest, J. Geophys. Res., 111, D09304, doi:10.1029/2005JD006631, 2006.

Villalta, P. W. and Howard, C. J.: Direct Kinetics Study of the CH3C(O)O2+NO Reaction Using Chemical Ionization Mass Spectrometry, J. Phys. Chem., 100, 13624–13628, 1996.

Warneck, P. and Zerbach, T.: Synthesis of peroxyacetyl nitrate in air by acetone photolysis, Environ. Sci. Technol., 26, 74–79, 1992.

Wesely, M. L.: Parameterization of surface resistances to gaseous dry deposition in regional-scale numerical models, Atmos. Environ., 23(6), 1293–1304, 1989.

Wesely, M. L. and Hicks, B. B.: A review of the current status of knowledge on dry deposition, Atmos. Environ., 34, 2261–2282, 2000.

Wolfe, G. M., Thornton, J. A., McNeill, V. F., Jaffe, D. A., Reidmiller, D., Chand, D., Smith, J., Swartzendruber, P., Flocke, F., and Zheng, W.: Influence of trans-Pacific pollution transport on acyl peroxy nitrate abundances and speciation at Mount Bachelor Observatory during INTEX-B, Atmos. Chem. Phys., 7, 5309–5325, 2007.

Xu, M., DeBiase, T. A., Qi, Y., Goldstein, A., and Liu, Z.: Ecosystem respiration in a young ponderosa pine plantation in the Sierra Nevada Mountains, California, Tree Physiol., 21, 309–318, 2001.