References

ACPD

Atmospheric Chemistry and Physics Discussions

ACPD

1680-7375

Copernicus GmbH

Göttingen, Germany

10.5194/acpd-11-6845-2011

α-Pinene Nitrates: synthesis, yields and atmospheric chemistry

S. X.

¹ Rindelaub

J. D.

¹ McAvey

K. M.

¹ Gagare

P. D.

¹ Nault

B. A.

¹ Ramachandran

P. V.

¹ Shepson

P. B.

¹ ²

Department of Chemistry, Purdue University, 560 Oval Dr., West Lafayette, IN 47907, USA

Department of Earth and Atmospheric Sciences, Purdue University, 550 Stadium Mall Dr., West Lafayette, IN 47907, USA

28 02 2011

11 2 6845 6874

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/11/6845/2011/acpd-11-6845-2011.html

The full text article is available as a PDF file from http://www.atmos-chem-phys-discuss.net/11/6845/2011/acpd-11-6845-2011.pdf

The biogenic volatile organic compound α-pinene is one of the dominant monoterpenes emitted to the Earth's atmosphere at an estimated rate of ~50 Tg yr−1. Its atmospheric oxidation products in the presence of NO can lead to ozone production, as well as production of secondary organic aerosol (SOA). The major oxidation pathway of α-pinene is reaction with OH, which in the presence of NO can form either α-pinene nitrates or convert NO to NO2, which can photolyze to form ozone. In this work, we successfully synthesized four α-pinene hydroxy nitrates through three different routes, and have identified the 4 individual isomers in α-pinene/OH/NO reaction chamber experiments. From the experiments, we determined their individual production yields, estimated the total RONO2 yield, and calculated the relative branching ratios of the nitrate precursor peroxy radicals (RO2). The combined yield of the four α-pinene nitrates was found to be 13.0 (±0.7) % at atmospheric pressure and 296 K, and the total organic nitrate yield was estimated to be 0.19 (+0.10/−0.06). We also determined the OH rate constants for two of the isomers, and have calculated their overall atmospheric lifetimes, which range between 22 and 38 h.

References 1

Andreae, M. O. and Crutzen, P. J.: Atmospheric aerosols: Biogeochemical sources and role in atmospheric chemistry, Science, 276, 1052–1058, 1997.

Arey, J., Aschmann, S. M., Kwok, E. S. C., and Atkinson, R.: Alkyl nitrate, hydroxyalkyl nitrate, and hydroxycarbonyl formation from the NOx-air photooxidations of C$_5$–C$_8$ n-alkanes, J. Phys. Chem. A, 105, 1020–1027, 2001.

Aschmann, S. M. and Atkinson, R.: Rate constants for the gas-phase reactions of OH radicals with $E$-7-tetradecene, 2-methyl-1-tridecene and the C$_7$–C$_14$ 1-alkenes at 295 ± 1 K, Phys. Chem. Chem. Phys., 10, 4159–4164, 2008.

Aschmann, S. M., Reissell, A., Atkinson, R., and Arey, J.: Products of the gas phase reactions of the OH radical with α- and β-pinene in the presence of NO, J. Geophys. Res., 103, 25553– 25561, 1998.

Aschmann, S. M., Arey, J., and Atkinson, R.: Atmospheric chemistry of three C10 alkanes, J. Phys. Chem., 105, 7598–7606, 2001.

Aschmann, S. M., Atkinson, R., and Arey, J.: Products of reaction of OH radicals with α-pinene, J. Geophys. Res., 107(D14), 4191–4197,2002.

Atkinson, R. and Arey, J.: Atmospheric degradation of volatile organic compounds, Chem.Rev., 103, 4605–4638, 2003a.

Atkinson, R. and Arey, J.: Gas-phase tropospheric chemistry of biogenic volatile organic compounds: a review, Atmos. Environ., 37, S197–S219, 2003b.

Atkinson, R., Aschmann, S. M., Carter, W. P. L., Winer, A. M., Pitts Jr., J. N.: Alkyl nitrate formation form the NOx-air photooxidations of C2–C$_8$ n-alkanes, J. Phys. Chem., 86, 4563–4569, 1982.

Barker, J. R., Lohr, L. L., Shroll, R., and Reading, S.: Modeling the organic nitrate yields in the reaction of alkyl peroxy radicals with nitric oxide, 2. Reaction simulations, J. Phys. Chem. A, 107, 7434–7444, 2003.

Constantino, M. G., Lacerda, V., Invernize, P. R., da Silva, L. C., da Silva, G. V. J.: Opening of Epoxide Rings Catalyzed by Niobium Pentachloride, Synthetic Commun., 37, 3529–3539, 2007.

Espada, C., Grossenbacher, J., Ford, K., Couch, T., Shepson, P. B.: The Production of Organic Nitrates from Various Anthropogenic Volatile Organic Compounds, Int. J. Chem. Kinet, 37, 675–685, 2005.

Grosjean, D., Williams II, E. L., and Seinfeld, J. H.: Atmospheric oxidation of selected terpenes and related carbonyls: Gas-phase carbonyl products, Environ. Sci. Technol., 26, 1526–1533, 1992.

Guenther, A. B., Zimmerman, P. R., Harley, P. C., Monson, R. K., and Fall, R.: Isoprene and monoterpene emission ratevariability-model evaluations and sensitivity analyses, J. Geophys. Res., 9, 12609–12617, 2003.

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, http://dx.doi.org/10.5194/acp-6-3181-2006doi:10.5194/acp-6-3181-2006, 2006.

Hakola, H., Arey, J., Aschmann, S. M., and Atkinson, R.: Product formation from the gas-phase reactions of OH radicals and O3 with a series of monoterpenes, J. Atmos. Chem., 18(1), 75–102, 1994.

Hatakeyama, S., Izumi, K., Fukuyama, T., Akimoto, H., and Washida, N.: Reaction of OH with α-pinene and $\beta $-pinene in air: estimate of global CO production from the atmospheric oxidation of terpenes, J. Geophys. Res., 96, 947–958, 1991.

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. F.: Observational constraints on the chemistry of isoprene nitrates over the eastern United States, J. Geophys. Res., 12, D12S08, http://dx.doi.org/10.1029/2006JD007747doi:10.1029/2006JD007747, 2007.

Isaksen, I. S. A. and Hov., O.: Calculation of trends in the tropospheric concentration of ozone, hydroxyl, carbon monoxide, methane, and nitrogen oxides, Tellus, 39B, 271–285, 1987.

Kalabokas, P., Bartzis, J. G., Bomboi, T., Ciccioli, P., Cieslik, S., Dlugi, R., Foster, P., Kotzias, D., and Steinbrecher, R.: Ambient atmospheric trace gas concentrations and meteorological parameters during the first BEMA measuring campaign on May 1994 at Castelporziano, Italy, Atmos. Environ., 31(S1), 67–77, 1997.

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(14), 1685–1695, 1995.

Larsen, B. R., Di Bella, D., Glasius, M., Winterhalter, R., Jensen, N. R., and Hjorth, J.: Gas-phase OH oxidation of monoterpenes: gaseous and particulate products, J. Atmos. Chem., 38, 231–276, 2001.

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., 111, D17305, 1–25, 2006.

Libardoni, M., Waite, J. H., and Sacks, R.: Electrically Heated, Air-Cooled Thermal Modulator and at-Column Heating for Comprehensive Two-Dimensional Gas Chromatography, Anal. Chem., 77, 2786–2794, 2005.

Monks, P. S., Granier, C., Fuzzi, S., Stohl, A., Williams, M. L., Akimoto, H., Amann, M., Baklanov, A., Baltensperger, U., Bey, I., Blanke, N., Blake, R. S., Carslaw, K., Cooper, O. R., Dentener, F., Fowler, D., Fragkou, E., Frost, G.J., Generoso, S., Ginoux, P., Grewe, V., Guenther, A., Hansson, H. C., Henne, S., Hjorth, J., Hofzumahaus, A., Huntrieser, H., Isaksen, I.S.A., Jenkin, M. E., Kaiser, J., Kanakidou, M., Klimont, Z., Kulmala, M., Laj, P., Lawrence, M. G., Lee, J. D., Liousse, C., Maione, M., McFiggans, G., Metzger, A., Mieville, A., Moussiopoulos, N., Orlando, J.J., O' Dowd, C.D., Palmer, P. I., Parrish, D. D., Petzold, A., Platt, U., Pöschl, U., Pr$\acute\rm e$v$\hat\rm o$t, A. S. H., Reeves, C. E., Reimann, S., Rudich, Y., Sellegri, K., Steinbrecher, R., Simpson, D., ten Brink, H., Theloke, J., van der Werf, G. R., Vautard, R., Vestreng, V., Vlachokostas, Ch., and von Glasow, R.: Atmospheric composition change: global and regional air quality, Atmos. Environ., 43, 5268–5350, 2009.

Nozière, B., Barnes, I., and Becker, K. H.: Product study and mechanisms of the reactions of α-pinene and pinonaldehyde with OH radicals, J. Geophys. Res., 104, 23645–23656, 1999.

Nozière, B., Ekström, S., Alsberg, T., and Holmström, S.: Radical-initiated formation of organosulfates and surfactants in atmospheric aerosols, Geophys. Res. Lett., 37, L05806, http://dx.doi.org/10.1029/2009GL041683doi:10.1029/2009GL041683, 2010.

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 C2–C6 alkenes with OH in the presence of NO, J. Phys. Chem. A, 102, 8903–8908, 1998.

Orlando, J. J., Nozière, B., Tyndall, G. S., Orzechowska, G. E., Paulson, S. E., and Rudich, Y.: Product studies of OH- and ozone-initiated oxidation of some monoterpenes, J. Geophys. Res., 105, 11561–11572, 2000.

Owen, S., Boissard, C., Street, R. A., Duckham, S. C., Csiky, O. and Hewitt, N. C.: Screening of 18 Mediterranean plant species for volatile organic compound emissions, Atmos. Environ., 31(S1), 101–117, 1997.

Pathak, R. K., Presto, A. A., Lane, T. E., Stanier, C. O., Donahue, N. M., and Pandis, S. N.: Ozonolysis of α-pinene: parameterization of secondary organic aerosol mass fraction, Atmos. Chem. Phys., 7, 3811–3821, http://dx.doi.org/10.5194/acp-7-3811-2007doi:10.5194/acp-7-3811-2007, 2007.

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.

Prinn, R. G., Huang, J., Weiss, R. F., Cunnold, D. M., Fraser, P. J., Simmonds, P. G., McCulloch, A., Harth, C., Reimann, S., Salameh, P., O�Doherty, S., Wang, R. H. J., Porter, L. W., Miller, B. R., and Krummel, P. B.: Evidence for variability of atmospheric hydroxyl radicals over the past quarter century, Geophys. Res. Lett., 32, L07809, http://dx.doi.org/10.1029/2004GL022228doi:10.1029/2004GL022228, 2005.

Reissell, A., Harry, Ch., Aschmann, S. H., Atkinson, R., and Arey, J.: Formation of acetone from the OH radical- and O3-initiated reactions of a series of monoterpenes, J. Geophys. Res., 104(13), 13869–13,880, 1999.

Rollins, A. W., Fry, J. L., Hunter, J. F., Kroll, J. H., Worsnop, D. R., Singaram, S. W., and Cohen, R. C.: Elemental analysis of aerosol organic nitrates with electron ionization high-resolution mass spectrometry, Atmos. Meas. Tech., 3, 301–310, http://dx.doi.org/10.5194/amt-3-301-2010doi:10.5194/amt-3-301-2010, 2010.

Rollins, A. W., Smith, J. D., Wilson, K. R., and Cohen, R. C.: Real time in situ detection of organic nitrates in atmospheric aerosols, Enivron. Sci. Technol., 44, 5540–5545, 2010b.

Ruppert, L., Becker, K. H., Nozière, B., and Spittler, M.: Development of monoterpene oxidation mechanisms: results from laboratory and smog chamber studies, eited by: Borrell, P. M. and Borrell, P., Transport and Chemical Transformation in the Troposphere, Proceedings of the EUROTRAC-2 Symposium, 8, 63–68, 1999.

Shepson, P. B., Mackay, E., and Muthuramu, K.: Henry's law constants and removal processes for several atmospheric β-hydroxy alkyl nitrates, Environ. Sci. Technol., 30, 3618–3623, 1996.

Steinbrecher, R., Smiatek, G., Köble, R., Seufert, G., Theloke, J., Hauff, K., Ciccioli, P., Vautard, R., and Curci, G.: Intra- and inter-annual variability of VOC emissions from natural and semi-natural vegetation in Europe and neighboring countries, Atmos. Environ., 43(7), 1380–1391, 2009.

Seufert, G., Bartzis, J., Bomboi, T., Ciccioli, P., Cieslik, S., Dlugi, R., Foster, P., Hewitt, C. N., Kesselmeier, J., Kotzias, D., Lenz, R., Manes, F., Perez Pastor, R., Steinbrecher, R. Torres, L., Valentin, R., and Versino, B.: An overview of the Castelporziano experiments, Atmos. Environ., 31(S1), 5–17, 1997.

Treves, K. and Rudich, Y.: The atmospheric fate of C3–C6 hydroxyalkyl nitrates, J. Phys. Chem. A, 107, 7809–7817, 2003.

Vereecken, L., Muller, J. F., and Peeters, J.: Low-volatility poly-oxygenates in the OH-initiated atmospheric oxidation of α-pinene: impact of non-traditional peroxyl radical chemistry, Phys. Chem. Chem. Phys., 9, 5241–5248, 2007.

Vinckier, C., Compernolle, F., Saleh, A. M., Van Hoof, N., and Van Hees, I.: Product yields of the α-pinene reaction with hydroxyl radicals and the implication on the global emission of trace compounds in the atmosphere, Fresen. Environ. Bull., 7, 361–368, 1998.

Vanhees, I., Van den Bergh, V., Schildermans, V. R., De Boer, R., Compernolle, F., and Vinckier, C.: Determination of the oxidation products of the reaction between a-pinene and hydroxyl radicals by high-performance liquid chromatography, J. Chromatogr. A, 915, 75–83, 2001.

Van den Bergh, V., Vanhees, I., De Boer, R., Compernolle, F. and Vinckier, C.: Identification of the oxidation products of the reaction between a-pinene and hydroxyl radicals by gas and high-performance liquid chromatography with mass spectrometric detection, J. Chromatogr. A, 896, 135–148, 2000.

Wängberg, I., Barnes, I., and Becker, K. H.: Product and mechanistic study of the reaction of NO3 radicals with α-pinene, Environ. Sci. Technol., 31, 2130–2135, 1997.

Wisthaler, A., Jensenb, N. R., Winterhalterb, R., Lindingera, W., and Hjorthb, J.: Measurements of acetone and other gas phase product yields from the OH-initiated oxidation of terpenes by proton-transfer-reaction mass spectrometry (PTR-MS), Atmos. Environ., 35, 6181–6191, 2001.

Zhang, J., Dransfield, Y., and Donahue, N. M.: On the Mechanism for Nitrate Formation via the Peroxy Radical + NO Reaction, J. Phys. Chem. A, 108, 9082–9095, 2004.