Atmospheric Chemistry and Physics
www.atmos-chem-phys.net
1680-7316
1680-7324
9
4
2009
10.5194/acp-9-1479-2009
http://www.atmos-chem-phys.net/9/1479/2009/
http://www.atmos-chem-phys.net/9/1479/2009/acp-9-1479-2009.html
http://www.atmos-chem-phys.net/9/1479/2009/acp-9-1479-2009.pdf
1479
1501
2009-02-23
Isoprene photooxidation: new insights into the production of acids and organic nitrates
F. Paulot
paulot@caltech.edu
J. D. Crounse
H. G. Kjaergaard
J. H. Kroll
J. H. Seinfeld
P. O. Wennberg
Department of Environmental Science and Engineering, California Institute of Technology, Pasadena, CA, USA
Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA, USA
Department of Chemistry, University of Otago, Dunedin, New Zealand
Center for Aerosol and Cloud Chemistry, Aerodyne Inc., Billerica, MA, USA
Division of Geophysical and Planetary Sciences, California Institute of Technology, Pasadena, CA, USA
We describe a nearly explicit chemical mechanism for isoprene photooxidation
guided by chamber studies that include time-resolved observation of an
extensive suite of volatile compounds. We provide new constraints on the
chemistry of the poorly-understood isoprene δ-hydroxy channels, which
account for more than one third of the total isoprene carbon flux and a
larger fraction of the nitrate yields. We show that the <i>cis</i> branch
dominates the chemistry of the δ-hydroxy channel with less than 5% of
the carbon following the <i>trans</i> branch. The modelled yield of
isoprene nitrates is 12±3% with a large difference between the
δ and β branches. The oxidation of these nitrates releases about
50% of the NO<sub>x</sub>. Methacrolein nitrates (modelled yield
<u>~</u>15±3% from methacrolein) and methylvinylketone nitrates
(modelled yield <u>~</u>11±3% yield from methylvinylketone) are also
observed. Propanone nitrate, produced with a yield of 1% from isoprene,
appears to be the longest-lived nitrate formed in the total oxidation of
isoprene. We find a large molar yield of formic acid and suggest a novel
mechanism leading to its formation from the organic nitrates. Finally, the
most important features of this mechanism are summarized in a condensed
scheme appropriate for use in global chemical transport models.
Amelynck, C., Schoon, N., and Arijs, E.: Gas phase reactions of $\mathrmCF_3O^-$ and $\mathrmCF_3O^- H_2O$ with nitric, formic, and acetic acid, Int. J. Mass Spectrom., 203, 165–175, 2000.
Andreae, M O., Andreae, T W., Talbot, R W., and Harriss, R C.: Formic and acetic acid over the central Amazon region, Brazil. I-Dry season, J. Geophys. Res., 93, 1616–1624, 1988.
Apponi, A J., Hoy, J J., Halfen, D T., Ziurys, L M., and Brewster, M A.: Hydroxyacetone ($\mathrmCH_3COCH_2OH$): a combined microwave and millimeter-wave laboratory study and associated astronomical search, The Astrophysical Journal, 652, 1787–1795, 2006.
Arey, J., Aschmann, S M., Kwok, E. S C., and Atkinson, R.: Alkyl nitrate, hydroxyalkyl nitrate, and hydroxycarbonyl formation from the $\mathrmNO_x$-air photooxidations of $\mathrmC_5−\mathrmC_8$ n-alkanes, J. Phys. Chem. A., 105, 1020–1027, 2001.
Atkinson, R.: Gas-phase tropospheric chemistry of volatile organic compounds: 1. Alkanes and Alkenes, Journal of Physical and Chemical Reference Data, 26, 215–290, 1997.
Atkinson, R., Aschmann, S M., Tuazon, E C., Arey, J., and Zielinska, B.: Formation of 3-Methylfuran from the gas-phase reaction of OH radicals with isoprene and the rate constant for its reaction with the OH radical, Int. J. Chem. Kin., 21, 593–604, 1989.
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 O<sub>x</sub>, HO<sub>x</sub>, NO<sub>x</sub> and SO<sub>x</sub> species, Atmos. Chem. Phys., 4, 1461–1738, 2004.
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 II–gas phase reactions of organic species, Atmos. Chem. Phys., 6, 3625–4055, 2006.
Atkinson, R., Arey, J., and Aschmann, S.: Atmospheric chemistry of alkanes: Review and recent developments, Atmos. Environ., 42, 5859–5871, 2008.
Baker, J., Arey, J., and Atkinson, R.: Formation and reaction of hydroxycarbonyls from the reaction of OH radicals with 1,3-butadiene and isoprene, Environ. Sci. Technol., 39, 4091–4099, 2005.
Bethel, H L., Atkinson, R., and Arey, J.: Kinetics and products of the reactions of selected diols with the OH radical, Int. J. Chem. Kin., 33, 310–316, 2001.
Bierbach, A., Barnes, I., and Becker, K H.: Product and kinetic study of the OH-initiated gas-phase oxidation of furan, 2-methylfuran and furanaldehydes at ≃300 K, Atmos. Environ., 29, 2651–2660, 1995.
Butkovskaya, N I., Pouvesle, N., Kukui, A., and Bras, G L.: Mechanism of the OH-initiated oxidation of glycolaldehyde over the temperature range 233-296 K., J. Phys. Chem. A., 110, 13 492–13 499, 2006a.
Butkovskaya, N I., Pouvesle, N., Kukui, A., Mu, Y., and Le~Bras, G.: Mechanism of the OH-initiated oxidation of hydroxyacetone over the temperature range 236-298 K, J. Phys. Chem. A., 110, 6833–6843, 2006b.
Cameron, M., Sivakumaran, V., Dillon, T J., and Crowley, J N.: Reaction between OH and CH3CHO Part 1. Primary product yields of $\mathrmCH_3$ (296 K), $\mathrmCH_3CO$ (296 K), and $\mathrmH$ (237–296 K), Phys. Chem. Chem. Phys., 4, 3628–3638, 2002.
Carlton, A G., Turpin, B J., Lim, H J., Altieri, K E., and Seitzinger, S.: Link between isoprene and secondary organic aerosol (SOA): Pyruvic acid oxidation yields low volatility organic acids in clouds, Geophys. Res. Lett, 33, L06822, \doi10.1029/2005GL025374, 2006.
Carter, W. P L. and Atkinson, R.: Alkyl nitrate formation from the atmospheric photoxidation of alkanes; a revised estimation method, J. Amos. Chem., 8, 165–173, 1989.
Chameides, W L., Lindsay, R W., Richardson, J., and Kiang, C S.: The role of biogenic hydrocarbons in urban photochemical smog: Atlanta as a case study, Science, 241, 1473, \doi10.1126/science.3420404, 1988.
Chebbi, A. and Carlier, P.: Carboxylic acids in the troposphere, occurrence, sources, and sinks: A review, Atmos. Environ., 30, 4233–4249, 1996.
Chen, X., Hulbert, D., and Shepson, P B.: Measurement of the organic nitrate yield from OH reaction with isoprene, J. Geophys. Res., 103, 25 563–25 568, 1998.
Chuong, B. and Stevens, P S.: Measurements of the kinetics of the OH-initiated oxidation of isoprene, J. Geophys. Res, 107, 4162, \doi10.1029/2001JD000865, 2002.
Chuong, B. and Stevens, P S.: Measurements of the kinetics of the OH-initiated oxidation of methyl vinyl ketone and methacrolein, Int. J. Chem. Kin., 36, 12–25, 2004.
Claeys, M., Graham, B., Vas, G., Wang, W., Vermeylen, R., Pashynska, V., Cafmeyer, J., Guyon, P., Andreae, M O., Artaxo, P., et~al.: Formation of secondary organic aerosols through photooxidation of isoprene, Science, 303, 1173–1176, 2004.
Cox, A P., Brittain, A H., and Finnigan, D J.: Microwave spectrum, structure, dipole moment and quadrupole coupling constants of cis and trans nitrous acids, Trans. Faraday Soc., 67, 2179–2194, 1971.
Crounse, J D., McKinney, K A., Kwan, A J., and Wennberg, P O.: Measurement of gas-phase hydroperoxides by chemical ionization mass spectrometry, Anal. Chem., 78, 6726–6732, 2006.
Dibble, T.: Cyclization of 1, 4-hydroxycarbonyls is not a homogenous gas phase process, Chem. Phys. Lett., 447, 5–9, 2007.
Dibble, T S.: Isomerization of OH-isoprene adducts and hydroxyalkoxy isoprene radicals, J. Phys. Chem. A., 106, 6643–6650, 2002.
Dibble, T S.: Intramolecular hydrogen bonding and double H-atom transfer in peroxy and alkoxy radicals from isoprene, J. Phys. Chem. A., 108, 2199–2207, 2004a.
Dibble, T S.: Prompt chemistry of alkenoxy radical products of the double H-atom transfer of alkoxy radicals from isoprene, J. Phys. Chem. A., 108, 2208–2215, 2004b.
Dillon, T J., Horowitz, A., Hölscher, D., Crowley, J N., Vereecken, L., Peeters, J., and Matter, S.: Reaction of HO with hydroxyacetone ($\mathrmHOCH_2C(O)CH_3$): rate coefficients (233–363 K) and mechanism, Phys. Chem. Chem. Phys., 8, 236–246, 2006.
Duce, R A., LaRoche, J., Altieri, K., Arrigo, K R., Baker, A R., Capone, D G., Cornell, S., Dentener, F., Galloway, J., Ganeshram, R S., et~al.: Impacts of atmospheric anthropogenic nitrogen on the open ocean, Science, 320, 893–897, \doi10.1126/science.1150369, 2008.
Fan, J. and Zhang, R.: Atmospheric Oxidation Mechanism of Isoprene, Environ. Chem., 1, 140–149, 2004.
Fiore, A M., Horowitz, L W., Purves, D W., II, H L., Evans, M J., Wang, Y., Li, Q., and Yantosca, R M.: Evaluating the contribution of changes in isoprene emissions to surface ozone trends over the eastern United States, J. Geophys. Res., 110, D12303, \doi10.1029/2004JD005485, 2005.
Francisco-Marquez, M., Alvarez-Idaboy, J R., Galano, A., and Vivier-Bunge, A.: A possible mechanism for furan formation in the tropospheric oxidation of dienes, Environ. Sci. Technol., 39, 8797–8802, 2005.
Giacopelli, P., Ford, K., Espada, C., and Shepson, P B.: Comparison of the measured and simulated isoprene nitrate distributions above a forest canopy, J. Geophys. Res., 110, D01304, \doi10.1029/2004JD005123, 2005.
Greenwald, E., North, S., Georgievskii, Y., and Klippenstein, S.: A two transition state model for radical-molecule reactions: applications to isomeric branching in the OH-isoprene reaction, J. Phys. Chem. A., 111, 5582–5592, 2007.
Guenther, A., Karl, T., Harley, P., Wiedinmyer, C., Palmer, P I., and Geron, C.: Estimates of global terrestrial isoprene emissions using MEGAN (Model of Emissions of Gases and Aerosols from Nature), Atmos. Chem. Phys., 6, 3181–3210, 2006.
Harley, P., Vasconcellos, P., Vierling, L., Pinheiro, C C., Greenberg, J., Guenther, A., Klinger, L., Almeida, S S., Neill, D., Baker, T., et~al.: Variation in potential for isoprene emissions among neotropical forest sites, Glob. Change Biol., 10, 630–650, 2004.
Harley, P C., Monson, R K., and Lerdau, M T.: Ecological and evolutionary aspects of isoprene emission from plants, Oecologia, 118, 109–123, 1999.
Hasson, A S., Tyndall, G S., and Orlando, J J.: A product yield study of the reaction of $\mathrmHO_2$ radicals with ethyl peroxy ($\mathrmC_2H_5O_2$), acetyl peroxy ($\mathrmCH_3 C(O)O_2$), and acetonyl peroxy ($\mathrmCH_3C(O)CH_2O_2$) radicals, J. Phys. Chem., 108, 5979–5989, 2004.
Henze, D K. and Seinfeld, J H.: Global secondary organic aerosol from isoprene oxidation, Geophys. Res. Lett., 33, L09812, \doi10.1029/2006GL025976, 2006.
Hermans, I., Müller, J F., Nguyen, T L., Jacobs, P., and Peeters, J.: Kinetics of α-hydroxy-alkylperoxyl radicals in oxidation processes. $\mathrmHO_2$ initiated oxidation of ketones/aldehydes near the tropopause, J. Phys. Chem. A., 109, 4303–4311, 2005.
Horowitz, L W., Liang, J., Gardner, G M., and Jacob, D J.: Export of reactive nitrogen from North America during summertime- Sensitivity to hydrocarbon chemistry, J. Geophys. Res., 103, 13 451–13 476, 1998.
Horowitz, L W., Fiore, A M., Milly, G P., Cohen, R C., Perring, A., Wooldridge, P J., Hess, P G., Emmons, L K., and Lamarque, J.: Observational constraints on the chemistry of isoprene nitrates over the eastern United States, J. Geophys. Res., 112(12), D12S08, \doi10.1029/2006JD007747, 2007.
Huey, L G., Villalta, P W., Dunlea, E J., Hanson, D R., and Howard, C J.: Reactions of $\mathrmCF_3O^-$ with atmospheric trace gases, J. Phys. Chem., 100, 190–194, 1996.
Jacob, D J. and Wofsy, S C.: Photochemistry of biogenic emissions over the Amazon forest, J. Geophys. Res., 93, 1477–1486, 1988.
Jenkin, M E., Hurley, M D., and Wallington, T J.: Investigation of the radical product channel of the $\mathrmCH_3C(O)O_2 + HO_2$ reaction in the gas phase, Phys. Chem. Chem. Phys., 9, 3149–3162, 2007.
Johnson III, R. D.: NIST Computational Chemistry Comparison and Benchmark Database NIST Standard Reference Database Number 101 Release 14, prefixhttp://srdata.nist.gov/cccbdb, 2006.
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. Amos. Chem., 55, 167–187, 2006.
Karunanandan, R., Hölscher, D., Dillon, T J., Horowitz, A., Crowley, J N., Vereecken, L., and Peeters, J.: Reaction of HO with Glycolaldehyde, $\mathrmHOCH_2CHO$: Rate Coefficients (240–362 K) and Mechanism, J. Phys. Chem. A., 111, 897–908, 2007.
Kroll, J H., Ng, N L., Murphy, S M., Flagan, R C., and Seinfeld, J H.: Secondary organic aerosol formation from isoprene photooxidation, Environ. Sci. Technol, 40, 1869–1877, 2006.
Kwok, E. S C. and Atkinson, R.: Estimation of hydroxyl radical reaction rate constants for gas-phase organic compounds using a structure-reactivity relationship: an update, Atmos. Environ., 29, 1685–1695, 1995.
Lei, W., Zhang, R., Sean~McGivern, W., Derecskei-Kovacs, A., and North, S.: Theoretical study of isomeric branching in the isoprene–OH reaction: implications to final product yields in isoprene oxidation, Chem. Phys. Lett., 326, 109–114, 2000.
Lei, W., Zhang, R., McGivern, W S., Derecskei-Kovacs, A., and North, S W.: Theoretical study of $\mathrmOH-O_2$-isoprene peroxy radicals, J. Phys. Chem. A., 105, 471–477, 2001.
Marstokk, K. and Mollendal, H.: Microwave spectra of isotopic glycolaldehydes, substitution structure, intramolecular hydrogen bond and dipole moment, J. Molecular Struct., 16, 259–270, 1973.
Maryott, A A. and Buckley, F.: US National Bureau of Standards Circular No. 537, National Bureau of Standards, Washington, DC, 1953.
Méreau, R., Rayez, M T., Rayez, J C., Caralp, F., and Lesclaux, R.: Theoretical study on the atmospheric fate of carbonyl radicals: kinetics of decomposition reactions, Phys. Chem. Chem. Phys., 3, 4712–4717, 2001.
Neeb, P.: Structure-reactivity based estimation of the rate constants for hydroxyl radical reactions with hydrocarbons, J. Amos. Chem., 35, 295–315, 2000.
Neeb, P., Sauer, F., Horie, O., and Moortgat, G K.: Formation of hydroxymethyl hydroperoxide and formic acid in alkene ozonolysis in the presence of water vapour, Atmos. Environ., 31, 1417–1423, 1997.
Ng, N L., Kwan, A J., Surratt, J D., Chan, A. W H., Chhabra, P S., Sorooshian, A., Pye, H. O T., Crounse, J D., Wennberg, P O., Flagan, R C., and Seinfeld, J H.: Secondary organic aerosol (SOA) formation from reaction of isoprene with nitrate radicals (NO<sub>3</sub>), Atmos. Chem. Phys., 8, 4117–4140, 2008.
O'Brien, J M., Czuba, E., Hastie, D R., Francisco, J S., and Shepson, P B.: Determination of the hydroxy nitrate yields from the reaction of $\mathrmC_2$–$\mathrmC_6$ alkenes with OH in the presence of NO, J. Phys. Chem. A., 102, 8903–8908, 1998.
Okumura, M. and Sander, S P.: Gas-phase formation rates of nitric acid and its isomers under urban conditions, California Environmental Protection Agency, Air Ressources Board, 2005.
Orlando, J J. and Tyndall, G S.: The atmospheric chemistry of the HC (O) CO radical, Int. J. Chem. Kin., 33, 149–156, 2001.
Orlando, J J., Tyndall, G S., Bertman, S B., Chen, W., and Burkholder, J B.: Rate coefficient for the reaction of OH with $\mathrmCH_2 = C (CH_3) C (O) OONO_2$ (MPAN), Atmos. Environ., 36, 1895–1900, 2002.
Papagni, C., Arey, J., and Atkinson, R.: Rate constants for the gas-phase reactions of OH radicals with a series of unsaturated alcohols, Int. J. Chem. Kin., 33, 142–147, 2001.
Park, J., Stephens, J C., Zhang, R., and North, S W.: Theoretical study of the alkoxy radicals derived from isoprene: pressure-and temperature-dependent decomposition rates, J. Phys. Chem. A., 107, 6408–6414, 2003.
Park, J., Jongsma, C G., Zhang, R., and North, S W.: OH/OD Initiated Oxidation of Isoprene in the Presence of $\mathrmO_2$ and NO, J. Phys. Chem. A., 108, 10 688–10 697, 2004.
Patchen, A K., Pennino, M J., Kiep, A C., and Elrod, M J.: Direct kinetics study of the product-forming channels of the reaction of isoprene-derived hydroxyperoxy radicals with NO, Int. J. Chem. Kin., 39, 353–361, 2007.
Paulson, S. and Seinfeld, J.: Development and evaluation of a photooxidation mechanism for isoprene, J. Geophys. Res., 97, 20 703–20 715, \doi10.1029/92JD01914, 1992.
Paulson, S E., Flagan, R C., and Seinfeld, J H.: Atmospheric photooxidation of isoprene. I: The hydroxyl radical and ground state atomic oxygen reactions, Int. J. Chem. Kin., 24, 79–101, 1992.
Peeters, J., Vereecken, L., and Fantechi, G.: The detailed mechanism of the OH-initiated atmospheric oxidation of α-pinene: a theoretical study, Phys. Chem. Chem. Phys., 3, 5489–5504, 2001.
Peeters, J., Fantechi, G., and Vereecken, L.: A Generalized Structure-Activity Relationship for the Decomposition of (Substituted) Alkoxy Radicals, J. Amos. Chem., 48, 59–80, 2004.
Pfister, G G., Emmons, L K., Hess, P G., Lamarque, J F., Orlando, J J., Walters, S., Guenther, A., Palmer, P I., and Lawrence, P J.: Contribution of isoprene to chemical budgets: A model tracer study with the NCAR CTM MOZART-4, J. Geophys. Res., 113, D05308, \doi10.1029/2007JD008948, 2008.
Roberts, J M. and Fajer, R W.: UV absorption cross sections of organic nitrates of potential atmospheric importance and estimation of atmospheric lifetimes, Environ. Sci. Technol., 23, 945–951, 1989.
Rosenstiel, T N., Potosnak, M J., Griffin, K L., Fall, R., and Monson, R K.: Increased $\mathrmCO_2$ uncouples growth from isoprene emission in an agriforest ecosystem, Nature, 421, 256–259, 2003.
Sander, S.: Chemical kinetics and photochemical data for use in atmospheric studies evaluation number 15, National Aeronautics and Space Administration, Jet Propulsion Laboratory, California Institute of Technology, 2006.
Sanderson, M G., Jones, C D., Collins, W J., Johnson, C E., and Derwent, R G.: Effect of climate change on isoprene emissions and surface ozone levels, Geophys. Res. Lett., 30, 1936, \doi10.1029/2003GL017642, 2003.
Saunders, S M., Jenkin, M E., Derwent, R G., and Pilling, M J.: Protocol for the development of the Master Chemical Mechanism, MCM v3 (Part A): Tropospheric degradation of non-aromatic volatile organic compounds, Atmos. Chem. Phys., 3, 161–180, 2003.
Shallcross, D E. and Monks, P S.: New Directions: A role for isoprene in biosphere–climate–chemistry feedbacks, Atmos. Env., 34, 1659–1660, 2000.
Sprengnether, M., Demerjian, K L., Donahue, N M., and Anderson, J G.: Product analysis of the OH oxidation of isoprene and 1, 3-butadiene in the presence of NO, J. Geophys. Res., 107, 8–8, 2002.
Su, T. and Chesnavich, W J.: Parametrization of the ion–polar molecule collision rate constant by trajectory calculations, J. Chem. Phys., 76, 5183–5185, \doi10.1063/1.442828, 1982.
Surratt, J D., Murphy, S M., Kroll, J H., Ng, N L., Hildebrandt, L., Sorooshian, A., Szmigielski, R., Vermeylen, R., Maenhaut, W., Claeys, M., et~al.: Chemical composition of secondary organic aerosol formed from the photooxidation of isoprene, J. Phys. Chem. A., 110, 9665–9690, 2006.
Talbot, R W., Andreae, M O., Berresheim, H., Jacob, D J., and Beecher, K M.: Sources and sinks of formic, acetic, and pyruvic acids over Central Amazonia: 2. Wet season, J. Geophys. Res., 95, 799–16, 1990.
Talbot, R W., Mosher, B W., Heikes, B G., Jacob, D J., Munger, J W., Daube, B C., Keene, W C., Maben, J R., and Artz, R S.: Carboxylic acids in the rural continental atmosphere over the eastern United States during the Shenandoah Cloud and Photochemistry Experiment, J. Geophys. Res., 100, 9335–9344, 1995.
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, Int. J. Chem. Kin., 22, 1221–1236, 1990.
van Donkelaar, A., Martin, R V., Park, R J., Heald, C L., Fu, T M., Liao, H., and Guenther, A.: Model evidence for a significant source of secondary organic aerosol from isoprene, Atmos. Environ., 41, 1267–1274, 2007.
von Kuhlmann, R., Lawrence, M G., Pöschl, U., and Crutzen, P J.: Sensitivities in global scale modeling of isoprene, Atmos. Chem. Phys., 4, 1–17, 2004.
Wall, K J., Schiller, C L., and Harris, G W.: Measurements of the HONO photodissociation constant, J. Amos. Chem., 55, 31–54, 2006.
Walser, M L., Park, J., Gomez, A L., Russell, A R., and Nizkorodov, S A.: Photochemical aging of secondary organic aerosol particles generated from the oxidation of d-limonene, J. Phys. Chem. A., 111, 1907–1913, 2007.
Wavefunction Inc.: Spartan'06, 2006.
Wiedinmyer, C., Tie, X., Guenther, A., Neilson, R., and Granier, C.: Future changes in biogenic isoprene emissions: How might they affect regional and global atmospheric chemistry?, Earth Interactions, 10, 1–19, 2006.