References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-10-8761-2010

Observations of elevated formaldehyde over a forest canopy suggest missing sources from rapid oxidation of arboreal hydrocarbons

Choi

¹ Faloona

I. C.

¹ Bouvier-Brown

N. C.

² ¹⁰ McKay

² ¹¹ Goldstein

A. H.

² Mao

³ ¹² Brune

W. H.

³ LaFranchi

B. W.

⁴ ¹³ Cohen

R. C.

⁴ ⁵ Wolfe

G. M.

⁶ Thornton

J. A.

⁷ Sonnenfroh

D. M.

⁸ Millet

D. B.

⁹

University of California, Davis, Dept. of Land, Air, and Water Resources, Davis, California, USA

University of California, Berkeley, Dept. of Environmental Science, Policy & Management, Berkeley, California, USA

Pennsylvania State University, Dept. of Meteorology, University Park, Pennsylvania, USA

University of California, Berkeley, Dept. of Chemistry, Berkeley, California, USA

University of California, Berkeley, Dept. of Earth and Planetary Science, Berkeley, California, USA

University of Washington, Dept. of Chemistry, Seattle, Washington, USA

University of Washington, Dept. of Atmospheric Sciences, Seattle, Washington, USA

Physical Sciences Inc., Atmospheric Sciences group, Andover, Massachusetts, USA

University of Minnesota, Dept. of Soil, Water, and Climate, St. Paul, Minnesota, USA

now at: Loyola Marymount University, Dept. of Chemistry and Biochemistry, Los Angeles, California, USA

now at: California Air Resources Board, Sacramento, California, USA

now at: Harvard University, School of Engineering and Applied Sciences, Cambridge, Massachustte, USA

now at: Lawrence Livermore National Lab, Center for Accelerator Mass Spectrometry, Livermore, California, USA

17 09 2010

10 18 8761 8781

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.net/10/8761/2010/acp-10-8761-2010.html

The full text article is available as a PDF file from http://www.atmos-chem-phys.net/10/8761/2010/acp-10-8761-2010.pdf

To better understand the processing of biogenic VOCs (BVOCs) in the pine forests of the US Sierra Nevada, we measured HCHO at Blodgett Research Station using Quantum Cascade Laser Spectroscopy (QCLS) during the Biosphere Effects on Aerosols and Photochemistry Experiment (BEARPEX) of late summer 2007. Four days of the experiment exhibited particularly copious HCHO, with midday peaks between 15–20 ppbv, while the other days developed delayed maxima between 8–14 ppbv in the early evening. From the expansive photochemical data set, we attempt to explain the observed HCHO concentrations by quantifying the various known photochemical production and loss terms in its chemical budget. Overall, known chemistry predicts a factor of 3–5 times less HCHO than observed. By examining diurnal patterns of the various budget terms we conclude that, during the high HCHO period, local, highly reactive oxidation chemistry produces an abundance of formaldehyde at the site. The results support the hypothesis of previous work at Blodgett Forest suggesting that large quantities of oxidation products, observed directly above the ponderosa pine canopy, are evidence of profuse emissions of very reactive volatile organic compounds (VR-VOCs) from the forest. However, on the majority of days, under generally cooler and more moist conditions, lower levels of HCHO develop primarily influenced by the influx of precursors transported into the region along with the Sacramento plume.

References 1

Alvarado, A., Tuazon, E. C., Aschmann, S. M., Arey, J., and Atkinson, R.: Products and mechanisms of the gas-phase reactions of OH radicals and O-3 with 2-methyl-3-buten-2-ol, Atmos. Environ., 33, 2893–2905, 1999.

Atkinson, R.: Gas-phase tropospheric chemistry of volatile organic compounds 1. Alkanes and alkenes, J. Phys. Chem. Ref. Data, 26, 215–290, 1997.

Atkinson, R., Baulch, D. L., Cox, R. A., Hampson, R. F., Kerr, J. A., Rossi, M. J., and Troe, J.: Evaluated kinetic and photochemical data for atmospheric chemistry, organic species: Supplement VII, J. Phys. Chem. Ref. Data, 28, 191–393, 1999.

Atkinson, R. and Arey, J.: Gas-phase tropospheric chemistry of biogenic volatile organic compounds: a review, Atmos. Environ., 37, S197–S219, doi:10.1016/s1352-2310(03)00391-1, 2003.

Atkinson, R., Baulch, D. L., Cox, R. A., Crowley, J. N., Hampson, R. F., Hynes, R. G., Jenkin, M. E., Rossi, M. J., and Troe, J.: Evaluated kinetic and photochemical data for atmospheric chemistry: Volume I – gas phase reactions of Ox, HOx, NOx and SOx species, Atmos. Chem. Phys., 4, 1461–1738, doi:10.5194/acp-4-1461-2004, 2004.

Atkinson, R., Baulch, D. L., Cox, R. A., Crowley, J. N., Hampson, R. F., Hynes, R. G., Jenkin, M. E., Rossi, M. J., Troe, J., and IUPAC Subcommittee: Evaluated kinetic and photochemical data for atmospheric chemistry: Volume II – gas phase reactions of organic species, Atmos. Chem. Phys., 6, 3625–4055, doi:10.5194/acp-6-3625-2006, 2006.

Bacher, C., Tyndall, G. S., and Orlando, J. J.: The atmospheric chemistry of glycolaldehyde, J. Atmos. Chem., 39, 171–189, 2001.

Baeza-Romero, M. T., Glowacki, D. R., Blitz, M. A., Heard, D. E., Pilling, M. J., Rickard, A. R., and Seakins, P. W.: A combined experimental and theoretical study of the reaction between methylglyoxal and OH/OD radical: OH regeneration, Phys. Chem. Chem. Phys., 9, 4114–4128, 2007.

Bouvier-Brown, N. C., Goldstein, A. H., Gilman, J. B., Kuster, W. C., and de Gouw, J. A.: In-situ ambient quantification of monoterpenes, sesquiterpenes, and related oxygenated compounds during BEARPEX 2007: implications for gas- and particle-phase chemistry, Atmos. Chem. Phys., 9, 5505–5518, doi:10.5194/acp-9-5505-2009, 2009a.

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, doi:10.1016/j.atmosenv.2008.08.039, 2009b.

Bowman, F. M., Pilinis, C., and Seinfeld, J. H.: Ozone and aerosol productivity of reactive organics, Atmos. Environ., 29, 579–589, 1995.

Butkovskaya, N. I., Pouvesle, N., Kukui, A., and Le Bra, G.: Mechanism of the OH-initiated oxidation of glycolaldehyde over the temperature range 233–296 K, J. Phys. Chem., 110, 13492–13499, 2006.

Calogirou, A., Kotzias, D., and Kettrup, A.: Product analysis of the gas-phase reaction of beta-caryophyllene with ozone, Atmos. Environ., 31, 283–285, 1997.

Choi, W., Faloona, I. C., McKay, M., Goldstein, A. H., and Baker, B.: Estimating the atmospheric boundary layer height over sloped, forested terrain from surface spectral analysis during BEARPEX, Atmos. Chem. Phys. Discuss., in review, 2010.

Day, D. A., Farmer, D. K., Goldstein, A. H., Wooldridge, P. J., Minejima, C., and Cohen, R. C.: Observations of NOx, $§igma$PNs, $§igma$ANs, and HNO3 at a Rural Site in the California Sierra Nevada Mountains: summertime diurnal cycles, Atmos. Chem. Phys., 9, 4879–4896, doi:10.5194/acp-9-4879-2009, 2009.

Dillon, T. J. and Crowley, J. N.: Direct detection of OH formation in the reactions of HO2 with CH3C(O)O2 and other substituted peroxy radicals, Atmos. Chem. Phys., 8, 4877–4889, doi:10.5194/acp-8-4877-2008, 2008.

Dillon, M. B., Lamanna, M. S., Schade, G. W., Goldstein, A. H., and Cohen, R. C.: Chemical evolution of the Sacramento urban plume: Transport and oxidation, J. Geophys. Res.-Atmos., 107, 4045, doi:10.1029/2001jd000969, 2002.

Dreyfus, G. B., Schade, G. W., and Goldstein, A. H.: Observational constraints on the contribution of isoprene oxidation to ozone production on the western slope of the Sierra Nevada, California, J. Geophys. Res.-Atmos., 107, 4365, doi:10.1029/2001jd001490, 2002.

Facchini, M. C., Fuzzi, S., Lind, J. A., Fierlingeroberlinninger, H., Kalina, M., Puxbaum, H., Winiwarter, W., Arends, B. G., Wobrock, W., Jaeschke, W., Berner, A., and Kruisz, C.: Phase-partitioning and chemical-reactions of low-molecular-weight organic-compounds in fog, Tellus B, 44, 533–544, 1992.

Faloona, I., Tan, D., Brune, W., Hurst, J., Barket, D., Couch, T. L., Shepson, P., Apel, E., Riemer, D., Thornberry, T., Carroll, M. A., Sillman, S., Keeler, G. J., Sagady, J., Hooper, D., and Paterson, K.: Nighttime observations of anomalously high levels of hydroxyl radicals above a deciduous forest canopy, J. Geophys. Res.-Atmos., 106, 24315–24333, 2001.

Fantechi, G., Jensen, N. R., Hjorth, J., and Peeters, J.: Mechanistic studies of the atmospheric oxidation of methyl butenol by OH radicals, ozone and NO3 radicals, Atmos. Environ., 32, 3547–3556, 1998.

Farmer, D. K. and Cohen, R. C.: Observations of HNO3, $§igma$AN, $§igma$PN and NO2 fluxes: evidence for rapid HOx chemistry within a pine forest canopy, Atmos. Chem. Phys., 8, 3899–3917, doi:10.5194/acp-8-3899-2008, 2008.

Ferronato, C., Orlando, J. J., and Tyndall, G. S.: Rate and mechanism of the reactions of OH and Cl with 2-methyl-3-buten-2-ol, J. Geophys. Res., 103, D19, 25579–25586, 1998.

Fried, A., McKeen, S., Sewell, S., Harder, J., Henry, B., Goldan, P., Kuster, W., Williams, E., Baumann, K., Shetter, R., and Cantrell, C.: Photochemistry of formaldehyde during the 1993 Tropospheric OH Photochemistry Experiment, J. Geophys. Res.-Atmos., 102, 6283–6296, 1997.

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), Agric. For. Meteorol., 101, 113–129, 2000.

Gratien, A., Picquet-Varrault, B., Orphal, J., Perraudin, E., Doussin, J. F., and Flaud, J. M.: Laboratory intercomparison of the formaldehyde absorption cross sections in the infrared (1660–1820 cm(-1)) and ultraviolet (300–360 nm) spectral regions, J. Geophys. Res.-Atmos., 112, D05305, doi:10.1029/2006jd007201, 2007.

Griffin, R. J., Cocker, D. R., and Seinfeld, J. H.: Incremental aerosol reactivity: application to aromatic and biogenic hydrocarbons, Environ. Sci. Technol., 33, 2403–2408, 1999.

Grosjean, D.: Formaldehyde and other carbonyls in Los-Angeles ambient air, Environ. Sci. Technol., 16, 254–262, 1982.

Grosjean, D., Miguel, A. H., and Tavares, T. M.: Urban air-pollution in Brazil – acetaldehyde and other carbonyls, Atmos. Environ., 24, 101–106, 1990.

Grosjean, D., Williams, E. L., and Grosjean, E.: Atmospheric chemistry of isoprene and of its carbonyl products, Environ. Sci. Technol., 27, 830–840, 1993a.

Grosjean, D., Williams, E. L., Grosjean, E., Andino, J. M., and Seinfeld, J. H.: Atmospheric oxidation of biogenic hydrocarbons – reaction of ozone with beta-pinene, d-limonene and trans-caryophyllene, Environ. Sci. Technol., 27, 2754–2758, 1993b.

Grosjean, D. and Grosjean, E.: Carbonyl products of the ozone-unsaturated alcohol reaction, J. Geophys. Res., 100, D11, 22815–22820, 1995.

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, doi:10.1021/jp048873t, 2004.

Hauglustaine, D. A. and Ehhalt, D. H.: A three-dimensional model of molecular hydrogen in the troposphere, J. Geophys. Res.-Atmos., 107, 4330, doi:10.1029/2001jd001156, 2002.

Hermans, I., Muller, J. F., Nguyen, T. L., Jacobs, P. A., and Peeters, J.: Kinetics of alpha-hydroxy-alkylperoxyl radicals in oxidation processes. HO2 center dot-initiated oxidation of ketones/aldehydes near the tropopause, J. Phys. Chem. A, 109, 4303–4311, doi:10.1021/jp044080v, 2005.

Hobbs, P. C. D.: Ultrasensitive laser measurements without tears, Appl. Opt., 36, 903–920, 1997.

Hoffmann, T., Odum, J. R., Bowman, F., Collins, D., Klockow, D., Flagan, R. C., and Seinfeld, J. H.: Formation of organic aerosols from the oxidation of biogenic hydrocarbons, J. Atmos. Chem., 26, 189–222, 1997.

Hofzumahaus, A., Rohrer, F., Lu, K. D., Bohn, B., Brauers, T., Chang, C. C., Fuchs, H., Holland, F., Kita, K., Kondo, Y., Li, X., Lou, S. R., Shao, M., Zeng, L. M., Wahner, A., and Zhang, Y. H.: Amplified Trace Gas Removal in the Troposphere, Science, 324, 1702–1704, doi:10.1126/science.1164566, 2009.

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, doi:10.5194/acp-5-67-2005, 2005.

Hurst, J. M., Barket, D. J., Herrera-Gomez, O., Couch, T. L., Shepson, P. B., Faloona, I., Tan, D., Brune, W., Westberg, H., Lamb, B., Biesenthal, T., Young, V., Goldstein, A., Munger, J. W., Thornberry, T., and Carroll, M. A.: Investigation of the nighttime decay of isoprene, J. Geophys. Res.-Atmos., 106, 24335–24346, 2001.

IPCC: Climate Change 2007: The Physical Science Basis, Intergovernmental Panel on Climate Change, Chapter 2, 140–143, 2007.

Jenkin, M. E., Boyd, A. A., and Lesclaux, R.: Peroxy radical kinetics resulting from the OH-Initiated oxidation of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene and isoprene, J. Atmos. Chem., 29, 267–298, 1998.

Jenkin, M. E., Hurley, M. D., and Wallington, T. J.: Investigation of the radical product channel of the CH3C(O)O-2 + HO2 reaction in the gas phase, Phys. Chem. Chem. Phys., 9, 3149–3162, doi:10.1039/b702757e, 2007.

Kamat, P. C., Roller, C. B., Namjou, K., Jeffers, J. D., Faramarzalian, A., Salas, R., and McCann, P. J.: Measurement of acetaldehyde in exhaled breath using a laser absorption spectrometer, Appl. Opt., 46(19), 3969–3975, 2007.

Karl, M., Dorn, H.-P., Holland, F., Koppmann, R., Poppe, D., Rupp, L., Schaub, A., and Wahner, A.: Product study of the reaction of OH radicals with isoprene in the atmosphere simulation chamber SAPHIR, J. Atmos. Chem., 55, 167–187, 2006.

Kegley-Owen, C. S., Tyndall, G. S., Orlando, J. J., and Fried, A.: Tunable diode laser studies of the reaction of Cl atoms with CH3CHO, Int. J. Chem. Kinet., 31, 766–775, 1999.

Klotz, B., Graedler, F., Sorensen, S., Barnes, I., and Becker, K. H.: A kinetic study of the atmospheric photolysis of alpha-dicarbonyls, Int. J. Chem. Kinet., 33, 9–20, 2001.

Koch, G. and Moortgat, G. K.: Photochemistry of methylglyoxal in the vapor phase, J. Phys. Chem. A, 102, 9142–9153, 1998.

Krinke, S. M. and Wahner, A.: Formaldehyde and ozone deposition velocities determined above a deciduous forest during summer, Eos Trans AGU, 80(46), Fall Meet. Suppl., F158, 1999.

Kurpius, M. R. and Goldstein, A. H.: Gas-phase chemistry dominates O-3 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.

LaFranchi, B. W., Wolfe, G. M., Thornton, J. A., Harrold, S. A., Browne, E. C., Min, K. E., Wooldridge, P. J., Gilman, J. B., Kuster, W. C., Goldan, P. D., de Gouw, J. A., McKay, M., Goldstein, A. H., Ren, X., Mao, J., and Cohen, R. C.: Closing the peroxy acetyl nitrate budget: observations of acyl peroxy nitrates (PAN, PPN, and MPAN) during BEARPEX 2007, Atmos. Chem. Phys., 9, 7623–7641, doi:10.5194/acp-9-7623-2009, 2009.

Largiuni, O., Giacomelli, M. C., and Piccardi, G.: Concentration of peroxides and formaldehyde in air and rain and gas-rain partitioning, J. Atmos. Chem., 41, 1–20, 2002.

Lee, A., Goldstein, A. H., Keywood, M. D., Gao, S., Varutbangkul, V., Bahreini, R., Ng, N. L., Flagan, R. C., and Seinfeld, J. H.: Gas-phase products and secondary aerosol yields from the ozonolysis of ten different terpenes, J. Geophys. Res.-Atmos., 111, D07302, doi:10.1029/2005jd006437, 2006a.

Lee, A., Goldstein, A. H., Kroll, J. H., Ng, N. L., Varutbangkul, V., Flagan, R. C., and Seinfeld, J. H.: Gas-phase products and secondary aerosol yields from the photooxidation of 16 different terpenes, J. Geophys. Res.-Atmos., 111, D17305, doi:10.1029/2006jd007050, 2006b.

Lee, Y. N., Zhou, X., Kleinman, L. I., Nunnermacker, L. J., Springston, S. R., Daum, P. H., Newman, L., Keigley, W. G., Holdren, M. W., Spicer, C. W., Young, V., Fu, B., Parrish, D. D., Holloway, J., Williams, J., Roberts, J. M., Ryerson, T. B., and Fehsenfeld, F. C.: Atmospheric chemistry and distribution of formaldehyde and several multioxygenated carbonyl compounds during the 1995 Nashville Middle Tennessee Ozone Study, J. Geophys. Res.-Atmos., 103, 22449–22462, 1998.

Lelieveld, J., Butler, T. M., Crowley, J. N., Dillon, T. J., Fischer, H., Ganzeveld, L., Harder, H., Lawrence, M. G., Martinez, M., Taraborrelli, D., and Williams, J.: Atmospheric oxidation capacity sustained by a tropical forest, Nature, 452, 737–740, doi:10.1038/nature06870, 2008.

Lightfoot, P. D., Roussel, P., Caralp, F., and Lesclaux, R.: Flash-photolysis study of the CH3O2 + CH3O2 and CH3O2 + HO2 reactions between 60-K and 719-K – unimolecular decomposition of methylhydroperoxide, J. Chem. Soc. Faraday Trans., 87, 3213–3220, 1991.

Macdonald, A. M., Makar, P. A., Anlauf, K. G., Hayden, K. L., Bottenheim, J. W., Wang, D., and Dann, T.: Summertime formaldehyde at a high-elevation site in Quebec, J. Geophys. Res.-Atmos., 106, 32361–32374, 2001.

Macoas, E. M. S., Lundell, J., Pettersson, M., Khriachtchev, L., Fausto, R., and Rasanen, M.: Vibrational spectroscopy of cis- and trans-formic acid in solid argon, J. Mol. Spectrosc., 219, 70–80, doi:10.1016/s0022-2852(03)00018-3, 2003.

Magneron, I., Mellouki, A., Le Bras, G., Moortgat, G. K., Horowitz, A., and Wirtz, K.: Photolysis and OH-Initiated oxidation of glycolaldehyde under atmospheric conditions, J. Phys. Chem. A, 109, 4552–4561, doi:10.1021/jp044346y, 2005.

Mao, J., Ren, X., Chen, Z., Brune, W., LaFranchi, B., Cohen, R., Gilman, J., and De Gouw, J.: HO$_\rm $ chemistry in and above a forest canopy in seasonal transition, AGU Fall Meeting, A32C-03, Oral Presentation, San Francisco, USA, 2008.

Martin, R. V., Parrish, D. D., Ryerson, T. B., Nicks, D. K., Chance, K., Kurosu, T. P., Jacob, D. J., Sturges, E. D., Fried, A., and Wert, B. P.: Evaluation of GOME satellite measurements of tropospheric NO2 and HCHO using regional data from aircraft campaigns in the southeastern United States, J. Geophys. Res.-Atmos., 109, D24307, doi:10.1029/2004jd004869, 2004.

Millet, D. B., Jacob, D. J., Boersma, K. F., Fu, T. M., Kurosu, T. P., Chance, K., Heald, C. L., and Guenther, A.: Spatial distribution of isoprene emissions from North America derived from formaldehyde column measurements by the OMI satellite sensor, J. Geophys. Res.-Atmos., 113, D02307, doi:10.1029/2007jd008950, 2008.

Misson, L., Tang, J. W., 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, Agric. For. Meteorol., 130, 207–222, doi:10.1016/j.agrformet.2005.04.001, 2005.

Miyoshi, A., Hatakeyama, S., and Washida, N.: OH radical-initiated photooxidation of isoprene – an estimate of global CO production, J. Geophys. Res.-Atmos., 99, 18779–18787, 1994.

Moise, T., Denzer, W., and Rudich, Y.: Direct kinetics study of the reaction of peroxyacetyl radical with NO between 218 and 370 K, J. Phys. Chem. A, 103, 6766–6771, 1999.

Monson, R. K. and Fall, R.: Isoprene emission from Aspen leaves – influence of environment and relation to photosynthesis and photorespiration, J. Plant Physiol., 90, 267–274, 1989.

Muller, K., Pelzing, M., Gnauk, T., Kappe, A., Teichmann, U., Spindler, G., Haferkorn, S., Jahn, Y., and Herrmann, H.: Monoterpene emissions and carbonyl compound air concentrations during the blooming period of rape (Brassica napus), Chemosphere, 49, 1247–1256, 2002.

Munger, J. W., Jacob, D. J., and Hoffmann, M. R.: The occurrence of bisulfite-aldehyde addition-products in fogwater and cloudwater, J. Atmos. Chem., 1, 335–350, 1984.

Murphy, J. G., Day, D. A., Cleary, P. A., Wooldridge, P. J., Millet, D. B., Goldstein, A. H., and Cohen, R. C.: The weekend effect within and downwind of Sacramento – Part 1: Observations of ozone, nitrogen oxides, and VOC reactivity, Atmos. Chem. Phys., 7, 5327–5339, doi:10.5194/acp-7-5327-2007, 2007.

National Center for Atmospheric Research (NCAR): TUV Radiation Model v4.5, online: http://cprm.acd.ucar.edu/Models/TUV/, 2008.

Orlando, J. J., Tyndall, G. S., and Paulson, S. E.: Mechanism of the OH-initiated oxidation of methacrolein, Geophys. Res. Lett., 26, 2191–2194, 1999.

Paulot, F., Crounse, J. D., Kjaergaard, H. G., Kroll, J. H., Seinfeld, J. H., and Wennberg, P. O.: Isoprene photooxidation: new insights into the production of acids and organic nitrates, Atmos. Chem. Phys., 9, 1479–1501, doi:10.5194/acp-9-1479-2009, 2009.

Paulson, S. E., Flagan, R. C., and Seinfeld, J. H.: Atmospheric photooxidation of isoprene, 1. The hydroxyl radical and ground-state atomic oxygen reactions, Int. J. Chem. Kinet., 24, 79–101, 1992.

Perrin, A., Keller, F., and Flaud, J. M.: New analysis of the nu(2), nu(3), nu(4), and nu(6) bands of formaldehyde, (H2CO)-C-12-O-16 line positions and intensities in the 5–10 μ m spectral region, J. Mol. Spectrosc., 221, 192–198, doi:10.1016/s0022-2852(03)00207-8, 2003.

Possanzini, M., Dipalo, V., Petricca, M., Fratarcangeli, R., and Brocco, D.: Measurements of lower carbonyls in Rome ambient air, Atmos. Environ., 30, 3757–3764, 1996.

Ruppert, L. and Becker, K. H.: A product study of the OH radical-initiated oxidation of isoprene: formation of C-5-unsaturated diols, Atmos. Environ., 34, 1529–1542, 2000.

Seinfeld, J. H. and Pandis, S. N.: Atmospheric Chemistry and Physics: from Air Pollution to Climate Change, John Willey & Sons, Inc, 1998.

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, 1121–1124, 1992.

Spaulding, R. S., Schade, G. W., Goldstein, A. H., and Charles, M. J.: Characterization of secondary atmospheric photooxidation products: Evidence for biogenic and anthropogenic sources, J. Geophys. Res.-Atmos., 108, 4247, doi:10.1029/2002jd002478, 2003.

Sprengnether, M., Demerjian, K. L., Donahue, N. M., and Anerson, J. G.: Product analysis of the OH oxidation of isoprene and 1,3-butadiene in the presence of NO, J. Geophys. Res., 107, 4269, doi:10.1029/2001JD000716, 2002.

Steiner, A. L., Tonse, S., Cohen, R. C., Goldstein, A. H., and Harley, R. A.: Biogenic 2-methyl-3-buten-2-ol increases regional ozone and HOx sources, Geophys. Res. Lett., 34, L15806, doi:10.1029/2007gl030802, 2007.

Stevens, P., L'Esperance, D., Chuong, B., and Martin, G.: Measurements of the kinetics of the OH-initiated oxidation of isoprene: Radical propagation in the OH + isoprene + O-2 + NO reaction system, Int. J. Chem. Kinet., 31, 637–643, 1999.

Stevens, P. S., Mather, J. H., Brune, W. H., Eisele, F., Tanner, D., Jefferson, A., Cantrell, C., Shetter, R., Sewall, S., Fried, A., Henry, B., Williams, E., Baumann, K., Goldan, P., and Kuster, W.: HO2/OH and RO(2)/HO2 ratios during the Tropospheric OH Photochemistry Experiment: Measurement and theory, J. Geophys. Res.-Atmos., 102, 6379–6391, 1997.

Suh, H. H., Bahadori, T., Vallarino, J., and Spengler, J. D.: Criteria air pollutants and toxic air pollutants, Environ. Health Perspect., 108, 625–633, 2000.

Sumner, A. L., Shepson, P. B., Couch, T. L., Thornberry, T., Carroll, M. A., Sillman, S., Pippin, M., Bertman, S., Tan, D., Faloona, I., Brune, W., Young, V., Cooper, O., Moody, J., and Stockwell, W.: A study of formaldehyde chemistry above a forest canopy, J. Geophys. Res.-Atmos., 106, 24387–24405, 2001.

Tan, D., Faloona, I., Simpas, J. B., Brune, W., Shepson, P. B., Couch, T. L., Sumner, A. L., Carroll, M. A., Thornberry, T., Apel, E., Riemer, D., and Stockwell, W.: HOx budgets in a deciduous forest: results from the PROPHET summer 1998 campaign, J. Geophys. Res.-Atmos., 106, 24407–24427, 2001.

Thornton, J. A., Wooldridge, P. J., Cohen, R. C., Martinez, M., Harder, H., Brune, W. H., Williams, E. J., Roberts, J. M., Fehsenfeld, F. C., Hall, S. R., Shetter, R. E., Wert, B. P., and Fried, A.: Ozone production rates as a function of NOx abundances and HOx production rates in the Nashville urban plume, J. Geophys. Res.-Atmos., 107, 4146, doi:10.1029/2001jd000932, 2002.

Tuazon, E. C. and Atkinson, R.: A product study of the gas-phase reaction of isoprene with the OH radical in the presence of NO$_\rm $, Int. J. Chem. Kinet., 22, 1221–1236, 1990.

Tyndall, G. S., Cox, R. A., Granier, C., Lesclaux, R., Moortgat, G. K., Pilling, M. J., Ravishankara, A. R., and Wallington, T. J.: Atmospheric chemistry of small organic peroxy radicals, J. Geophys. Res.-Atmos., 106, 12157–12182, 2001.

Wolfe, G. M., Thornton, J. A., Bouvier-Brown, N. C., Goldstein, A. H., Park, J.-H., McKay, M., Matross, D. M., Mao, J., Brune, W. H., LaFranchi, B. W., Browne, E. C., Min, K.-E., Wooldridge, P. J., Cohen, R. C., Crounse, J. D., Faloona, I. C., Gilman, J. B., Kuster, W. C., de Gouw, J. A., Huisman, A., and Keutsch, F. N.: The chemistry of Atmosphere-Forest Exchange (CAFE) Model – Part 2: Application to BEARPEX-2007 observations, Atmos. Chem. Phys. Discuss., in press, 2010.

Wolfe, G. M., Thornton, J. A., Yatavelli, R. L. N., McKay, M., Goldstein, A. H., LaFranchi, B., Min, K.-E., and Cohen, R. C.: Eddy covariance fluxes of acyl peroxy nitrates (PAN, PPN and MPAN) above a Ponderosa pine forest, Atmos. Chem. Phys., 9, 615–634, doi:10.5194/acp-9-615-2009, 2009.