Articles | Volume 21, issue 17
https://doi.org/10.5194/acp-21-13667-2021
© Author(s) 2021. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
https://doi.org/10.5194/acp-21-13667-2021
© Author(s) 2021. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
14 Sep 2021
Research article |
| 14 Sep 2021
| 14 Sep 2021
Atmospheric oxidation of α,β-unsaturated ketones: kinetics and mechanism of the OH radical reaction
Institute for Atmospheric and Environmental Research, Bergische Universität Wuppertal, 42097 Wuppertal, Germany
Rodrigo Gastón Gibilisco
INQUINOA-UNT-CONICET Institute of Physical Chemistry, Faculty of Biochemistry, Chemistry and Pharmacy, National University of Tucumán, San Lorenzo 456, T4000CAN, San Miguel de Tucumán, Argentina
Iustinian Gabriel Bejan
Faculty of Chemistry and Integrated Centre of Environmental Science Studies in the North Eastern Region Alexandru Ioan Cuza University of Iasi, 11 Carol I, Iasi 700506, Romania
Iulia Patroescu-Klotz
Institute for Atmospheric and Environmental Research, Bergische Universität Wuppertal, 42097 Wuppertal, Germany
Peter Wiesen
Institute for Atmospheric and Environmental Research, Bergische Universität Wuppertal, 42097 Wuppertal, Germany
Related authors
Hendrik Fuchs, Niklas Illmann, Amalia Muñoz, Mila Ródenas, Bénédicte Picquet-Varrault, M. Rami Alfarra, Cecilia Arsene, Iustinian G. Bejan, David M. Bell, Merete Bilde, Alexander Böhmländer, Mixtli Campos-Pineda, Mathieu Cazaunau, Patrice Coll, Véronique Daële, Claudia Di Biagio, Michael Flynn, Paola Formenti, Hartmut Herrmann, Kristina Höhler, Thorsten Hohaus, Matthew S. Johnson, Eija Juurola, Niku Kivekäs, Jan Kaiser, Christos Kaltsonoudis, Paolo Laj, Dario Massabò, Federico Mazzei, Gordon McFiggans, Max R. McGillen, Abdelwahid Mellouki, Peter Mettke, Ottmar Möhler, Falk Mothes, Dennis Niedermeier, Anna Novelli, Romeo I. Olariu, Spyros N. Pandis, Iulia Patroescu-Klotz, Rosa Maria Petracca Altieri, Paolo Prati, Claudiu Roman, Albert A. Ruth, Harald Saathoff, Silvio Schmalfuß, Frank Stratmann, Virginia Vernocchi, Aristeidis Voliotis, Jens Voigtländer, Annele Virtanen, Andreas Wahner, Robert Wagner, John Wenger, Sören Zorn, Peter Wiesen, and Jean-Francois Doussin
EGUsphere, https://doi.org/10.5194/egusphere-2026-1612, https://doi.org/10.5194/egusphere-2026-1612, 2026
This preprint is open for discussion and under review for Atmospheric Measurement Techniques (AMT).
Short summary
Short summary
Atmospheric simulation chambers enable experiments to be conducted under controlled conditions, improving our understanding of, and ability to predict, changes in the composition of the atmosphere. This is important for assessing air quality and its effects on human health, climate, the environment, and the economy. This paper describes the chambers of the European ACTRIS research infrastructure and discusses topics and directions that can be addressed in future chamber experiments.
Niklas Illmann, Iulia Patroescu-Klotz, and Peter Wiesen
Atmos. Chem. Phys., 21, 18557–18572, https://doi.org/10.5194/acp-21-18557-2021, https://doi.org/10.5194/acp-21-18557-2021, 2021
Short summary
Short summary
Understanding the chemistry of biomass burning plumes is of global interest. Within this work we investigated the OH radical reaction of 3-penten-2-one, which has been identified in biomass burning emissions. We observed the primary formation of peroxyacetyl nitrate (PAN), a key NOx reservoir species. Besides, PAN precursors were also identified as main oxidation products. 3-Penten-2-one is shown to be an example explaining rapid PAN formation within young biomass burning plumes.
Hendrik Fuchs, Niklas Illmann, Amalia Muñoz, Mila Ródenas, Bénédicte Picquet-Varrault, M. Rami Alfarra, Cecilia Arsene, Iustinian G. Bejan, David M. Bell, Merete Bilde, Alexander Böhmländer, Mixtli Campos-Pineda, Mathieu Cazaunau, Patrice Coll, Véronique Daële, Claudia Di Biagio, Michael Flynn, Paola Formenti, Hartmut Herrmann, Kristina Höhler, Thorsten Hohaus, Matthew S. Johnson, Eija Juurola, Niku Kivekäs, Jan Kaiser, Christos Kaltsonoudis, Paolo Laj, Dario Massabò, Federico Mazzei, Gordon McFiggans, Max R. McGillen, Abdelwahid Mellouki, Peter Mettke, Ottmar Möhler, Falk Mothes, Dennis Niedermeier, Anna Novelli, Romeo I. Olariu, Spyros N. Pandis, Iulia Patroescu-Klotz, Rosa Maria Petracca Altieri, Paolo Prati, Claudiu Roman, Albert A. Ruth, Harald Saathoff, Silvio Schmalfuß, Frank Stratmann, Virginia Vernocchi, Aristeidis Voliotis, Jens Voigtländer, Annele Virtanen, Andreas Wahner, Robert Wagner, John Wenger, Sören Zorn, Peter Wiesen, and Jean-Francois Doussin
EGUsphere, https://doi.org/10.5194/egusphere-2026-1612, https://doi.org/10.5194/egusphere-2026-1612, 2026
This preprint is open for discussion and under review for Atmospheric Measurement Techniques (AMT).
Short summary
Short summary
Atmospheric simulation chambers enable experiments to be conducted under controlled conditions, improving our understanding of, and ability to predict, changes in the composition of the atmosphere. This is important for assessing air quality and its effects on human health, climate, the environment, and the economy. This paper describes the chambers of the European ACTRIS research infrastructure and discusses topics and directions that can be addressed in future chamber experiments.
James D'Souza Metcalf, Ruth K. Winkless, Caterina Mapelli, C. Rob McElroy, Claudiu Roman, Cecilia Arsene, Romeo I. Olariu, Iustinian G. Bejan, and Terry J. Dillon
Atmos. Chem. Phys., 25, 9169–9181, https://doi.org/10.5194/acp-25-9169-2025, https://doi.org/10.5194/acp-25-9169-2025, 2025
Short summary
Short summary
Oxymethylene ethers are a class of sustainable compounds that could be used to replace harmful organic solvents in a range of applications. In this work, we use lab-based experiments to identify the main breakdown routes of these compounds in the atmosphere. We have determined that they likely contribute less to air pollution than the compounds that they replace.
Frank A. F. Winiberg, William J. Warman, Charlotte A. Brumby, Graham Boustead, Iustinian G. Bejan, Thomas H. Speak, Dwayne E. Heard, Daniel Stone, and Paul W. Seakins
Atmos. Meas. Tech., 16, 4375–4390, https://doi.org/10.5194/amt-16-4375-2023, https://doi.org/10.5194/amt-16-4375-2023, 2023
Short summary
Short summary
OH and HO2 are key reactive intermediates in the Earth's atmosphere. Accurate measurements in either the field or simulation chambers provide a good test for chemical mechanisms. Fluorescence techniques have the appropriate sensitivity for detection but require calibration. This paper compares different methods of calibration and specifically how calibration factors vary across a temperature range relevant to atmospheric and chamber determinations.
Caterina Mapelli, Juliette V. Schleicher, Alex Hawtin, Conor D. Rankine, Fiona C. Whiting, Fergal Byrne, C. Rob McElroy, Claudiu Roman, Cecilia Arsene, Romeo I. Olariu, Iustinian G. Bejan, and Terry J. Dillon
Atmos. Chem. Phys., 22, 14589–14602, https://doi.org/10.5194/acp-22-14589-2022, https://doi.org/10.5194/acp-22-14589-2022, 2022
Short summary
Short summary
Solvents represent an important source of pollution from the chemical industry. New "green" solvents aim to replace toxic solvents with new molecules made from renewable sources and designed to be less harmful. Whilst these new molecules are selected according to toxicity and other characteristics, no consideration has yet been included on air quality. Studying the solvent breakdown in air, we found that TMO has a lower impact on air quality than traditional solvents with similar properties.
Carmen Maria Tovar, Ian Barnes, Iustinian Gabriel Bejan, and Peter Wiesen
Atmos. Chem. Phys., 22, 6989–7004, https://doi.org/10.5194/acp-22-6989-2022, https://doi.org/10.5194/acp-22-6989-2022, 2022
Short summary
Short summary
This work explores the kinetics and reactivity of epoxides towards the OH radical using two different simulation chambers. Estimation of the rate coefficients has also been made using different structure–activity relationship (SAR) approaches. The results indicate a direct influence of the structural and geometric properties of the epoxides not considered in SAR estimations, influencing the reactivity of these compounds. The outcomes of this work are in very good agreement with previous studies.
Claudiu Roman, Cecilia Arsene, Iustinian Gabriel Bejan, and Romeo Iulian Olariu
Atmos. Chem. Phys., 22, 2203–2219, https://doi.org/10.5194/acp-22-2203-2022, https://doi.org/10.5194/acp-22-2203-2022, 2022
Short summary
Short summary
Gas-phase reaction rate coefficients of OH radicals with four nitrocatechols have been investigated for the first time by using ESC-Q-UAIC chamber facilities. The reactivity of all investigated nitrocatechols is influenced by the formation of the intramolecular H-bonds that are connected to the deactivating electromeric effect of the NO2 group. For the 3-nitrocatechol compounds, the electromeric effect of the
freeOH group is diminished by the deactivating E-effect of the NO2 group.
Niklas Illmann, Iulia Patroescu-Klotz, and Peter Wiesen
Atmos. Chem. Phys., 21, 18557–18572, https://doi.org/10.5194/acp-21-18557-2021, https://doi.org/10.5194/acp-21-18557-2021, 2021
Short summary
Short summary
Understanding the chemistry of biomass burning plumes is of global interest. Within this work we investigated the OH radical reaction of 3-penten-2-one, which has been identified in biomass burning emissions. We observed the primary formation of peroxyacetyl nitrate (PAN), a key NOx reservoir species. Besides, PAN precursors were also identified as main oxidation products. 3-Penten-2-one is shown to be an example explaining rapid PAN formation within young biomass burning plumes.
Cited articles
Allen, G., Remedios, J. J., Newnham, D. A., Smith, K. M., and Monks, P. S.: Improved mid-infrared cross-sections for peroxyacetyl nitrate (PAN) vapour, Atmos. Chem. Phys., 5, 47–56, https://doi.org/10.5194/acp-5-47-2005, 2005.
Aschmann, S. M., Arey, J., and Atkinson, R.: Atmospheric Chemistry of Selected Hydroxycarbonyls, J. Phys. Chem. A, 104, 3998–4003, https://doi.org/10.1021/jp9939874, 2000.
Atkinson, R: Kinetics and Mechanisms of the Gas-Phase Reactions of the NO3 Radical with Organic Compounds, J. Phys. Chem. Ref. Data, 20, 459–507, https://doi.org/10.1063/1.555887, 1991.
Atkinson, R: Rate constants for the atmospheric reactions of alkoxy radicals: An updated estimation method, Atmos. Environ., 41, 8468–8485, https://doi.org/10.1016/j.atmosenv.2007.07.002, 2007.
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, https://doi.org/10.5194/acp-6-3625-2006, 2006.
Barnes, I., Becker, K. H., and Zhu, T.: Near UV Absorption Spectra and Photolysis Products of Difunctional Organic Nitrates: Possible Importance as NOx Reservoirs, J. Atmos. Chem., 17, 353–373, https://doi.org/10.1007/BF00696854, 1993.
Barnes, I., Becker, K. H., and Mihalopoulos, N.: An FTIR Product Study of the Photooxidation of Dimethyl Disulfide, J. Atmos. Chem., 18, 267–289, https://doi.org/10.1007/BF00696783, 1994.
Bickers, D. R., Calow, P., Greim, H. A., Hanifin, J. M., Rogers, A. E., Saurat, J.-H., Sipes, I. G., Smith, R. L., and Tagami, H.: The safety assessment of fragrance materials, Regul. Toxicol. Pharm., 37, 218–273, https://doi.org/10.1016/S0273-2300(03)00003-5, 2003.
Blanco, M. B., Barnes, I., and Wiesen, P.: Kinetic Investigation of the OH Radical and Cl Atom Initiated Degradation of Unsaturated Ketones at Atmospheric Pressure and 298 K, J. Phys. Chem. A, 116, 6033–6040, https://doi.org/10.1021/jp2109972, 2012.
Bloss, W. J., Evans, M. J., Lee, J. D., Sommariva, R., Heard, D. E., and Piling, M. J.: The oxidative capacity of the troposphere: Coupling of field measurements of OH and a global chemistry transport model, Faraday Discuss., 130, 425–436, https://doi.org/10.1039/B419090D, 2005.
Calvert, J. G., Atkinson, R., Kerr, J. A., Madronich, S., Moortgat, G. K., Wallington, T. J., and Yarwood, G.: The mechanisms of atmospheric oxidation of the alkenes, Oxford University Press, New York, 2000.
Calvert, J. G., Mellouki, A., Orlando, J. J., Pilling, M. J., and Wallington, T. J.: The mechanisms of atmospheric oxidation of the oxygenates, Oxford University Press, New York, 2011.
Calvert, J. G., Orlando, J. J., Stockwell, W. R., and Wallington, T. J.: The Mechanisms of Reactions Influencing Atmospheric Ozone, Oxford University Press, New York, 2015.
Canosa-Mas, C. E., Flugge, M. L., King, M. D., and Wayne, R. P.: An experimental study of the gas-phase reaction of the NO3 radical with α,β-unsaturated carbonyl compounds, Phys. Chem. Chem. Phys., 7, 643–650, https://doi.org/10.1039/B416574H, 2005.
Carrasco, N., Doussin, J.-F., Picquet-Varrault, B., and Carlier, P.: Tropospheric degradation of 2-hydroxy-2-methylpropanal, a photo-oxidation product of 2-methyl-3-buten-2-ol: Kinetic and mechanistic study of its photolysis and its reaction with OH radicals, Atmos. Environ., 40, 2011–2019, https://doi.org/10.1016/j.atmosenv.2005.11.042, 2006.
Carrasco, N, Doussin, J. F., O'Connor, M., Wenger, J. C., Picquet-Varrault, B., Durand-Jolibois, R., and Carlier, P: Simulation Chamber Studies of the Atmospheric Oxidation of 2-Methyl-3-buten-2-ol: Reaction with Hydroxyl Radicals and Ozone Under a Variety of Conditions, J. Atmos. Chem., 56, 33–55, https://doi.org/10.1007/s10874-006-9041-y, 2007.
Chapuis, C. and Jacoby, D.: Catalysis in the preparation of fragrances and flavours, Appl. Catal. A-Gen., 221, 93–117, https://doi.org/10.1016/S0926-860X(01)00798-0, 2001.
Etzkorn, T., Klotz, B., Sørensen, S., Patroescu, I. V., Barnes, I., Becker, K. H., and Platt, U.: Gas-phase absorption cross sections of 24 monocyclic hydrocarbons in the UV and IR spectral ranges, Atmos. Environ., 33, 525–540, https://doi.org/10.1016/S1352-2310(98)00289-1, 1999.
Ezell, M. J., Wang, W., Ezell, A. A., Soskin, G., and Finlayson-Pitts, B. J.: Kinetics of reactions of chlorine atoms with a series of alkenes at 1 atm and 298 K: structure and reactivity, Phys. Chem. Chem. Phys., 4, 5813–5820, https://doi.org/10.1039/B207529F, 2002.
Fischer, E. V., Jacob, D. J., Yantosca, R. M., Sulprizio, M. P., Millet, D. B., Mao, J., Paulot, F., Singh, H. B., Roiger, A., Ries, L., Talbot, R. W., Dzepina, K., and Pandey Deolal, S.: Atmospheric peroxyacetyl nitrate (PAN): a global budget and source attribution, Atmos. Chem. Phys., 14, 2679–2698, https://doi.org/10.5194/acp-14-2679-2014, 2014.
Frost, M. J. and Smith, I. W. M.: Rate Constants for the Reactions of CH3O and C2H5O with NO2 over a Range of Temperature and Total Pressure, J. Chem. Soc. Faraday T., 86, 1751–1756, https://doi.org/10.1039/FT9908601751, 1990.
Fu, T.-M., Jacob, D. J., Wittrock, F., Burrows, J. P., Vrekoussis, M., and Henze, D. K.: Global budgets of atmospheric glyoxal and methylglyoxal, and implications for formation of secondary organic aerosols, J. Geophys. Res. Atmos., 113, 1–17, https://doi.org/10.1029/2007JD009505, 2008.
Fuchs, H., Albrecht, S., Acir, I., Bohn, B., Breitenlechner, M., Dorn, H.-P., Gkatzelis, G. I., Hofzumahaus, A., Holland, F., Kaminski, M., Keutsch, F. N., Novelli, A., Reimer, D., Rohrer, F., Tillmann, R., Vereecken, L., Wegener, R., Zaytsev, A., Kiendler-Scharr, A., and Wahner, A.: Investigation of the oxidation of methyl vinyl ketone (MVK) by OH radicals in the atmospheric simulation chamber SAPHIR, Atmos. Chem. Phys., 18, 8001–8016, https://doi.org/10.5194/acp-18-8001-2018, 2018.
Galloway, M. M., Huisman, A. J., Yee, L. D., Chan, A. W. H., Loza, C. L., Seinfeld, J. H., and Keutsch, F. N.: Yields of oxidized volatile organic compounds during the OH radical initiated oxidation of isoprene, methyl vinyl ketone, and methacrolein under high−NOx conditions, Atmos. Chem. Phys., 11, 10779–10790, https://doi.org/10.5194/acp-11-10779-2011, 2011.
Gaona-Colmán, E., Blanco, M. B., and Teruel, M. A.: Kinetics and product identification of the reactions of (E)-2-hexenyl acetate and 4-methyl-3-penten-2-one with OH radicals and Cl atoms at 298 K and atmospheric pressure, Atmos. Environ, 161, 155–166, https://doi.org/10.1016/j.atmosenv.2017.04.033, 2017.
Gratien, A., Nilsson, E., Doussin, J.-F., Johnson, M. S., Nielsen, C. J., Stenstrøm, Y., and Picquet-Varrault, B.: UV and IR Absorption Cross-sections of HCHO, HCDO, and DCDO, J. Phys. Chem. A, 111, 11506–11513, https://doi.org/10.1021/jp074288r, 2007.
Green, M., Yarwood, G., and Niki, H.: FTIR Study of the Cl-Atom Initiated Oxidation of Methylglyoxal, Int. J. Chem. Kinet., 22, 689–699, https://doi.org/10.1002/kin.550220705, 1990.
Grosjean, D. and Williams II, E. L.: Environmental persistence of organic compounds estimated from structure-reactivity and linear free-energy relationships. Unsaturated Aliphatics, Atmos. Environ. A-Gen., 26, 1395–1405, https://doi.org/10.1016/0960-1686(92)90124-4, 1992.
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, https://doi.org/10.5194/acp-6-3181-2006, 2006.
Hatch, L. E., Yokelson, R. J., Stockwell, C. E., Veres, P. R., Simpson, I. J., Blake, D. R., Orlando, J. J., and Barsanti, K. C.: Multi-instrument comparison and compilation of non-methane organic gas emissions from biomass burning and implications for smoke-derived secondary organic aerosol precursors, Atmos. Chem. Phys., 17, 1471–1489, https://doi.org/10.5194/acp-17-1471-2017, 2017.
Illmann, J. N., Patroescu-Klotz, I., and Wiesen, P.: Gas-phase reactivity of acyclic α,β-unsaturated carbonyls towards ozone, Phys. Chem. Chem. Phys., 23, 3455–3466, https://doi.org/10.1039/D0CP05881E, 2021a.
Illmann, N., Patroescu-Klotz, I., and Wiesen, P.: Biomass burning plume chemistry: OH radical initiated oxidation of 3-penten-2-one and its main oxidation product 2-hydroxypropanal, Atmos. Chem. Phys. Discuss. [preprint], https://doi.org/10.5194/acp-2021-575, in review, 2021b.
Jenkin, M. E., Valorso, R., Aumont, B., Rickard, A. R., and Wallington, T. J.: Estimation of rate coefficients and branching ratios for gas-phase reactions of OH with aliphatic organic compounds for use in automated mechanism construction, Atmos. Chem. Phys., 18, 9297–9328, https://doi.org/10.5194/acp-18-9297-2018, 2018.
Kanakidou, M., Seinfeld, J. H., Pandis, S. N., Barnes, I., Dentener, F. J., Facchini, M. C., Van Dingenen, R., Ervens, B., Nenes, A., Nielsen, C. J., Swietlicki, E., Putaud, J. P., Balkanski, Y., Fuzzi, S., Horth, J., Moortgat, G. K., Winterhalter, R., Myhre, C. E. L., Tsigaridis, K., Vignati, E., Stephanou, E. G., and Wilson, J.: Organic aerosol and global climate modelling: a review, Atmos. Chem. Phys., 5, 1053–1123, https://doi.org/10.5194/acp-5-1053-2005, 2005.
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, https://doi.org/10.1016/1352-2310(95)00069-B, 1995.
Li, W., Dan. G., Chen, M., Wang, Z., Zhao, Y., Wang, F., Li, F., Tong, S., and Ge, M.: The gas-phase reaction kinetics of different structure of unsaturated alcohols and ketones with O3, Atmos. Environ., 254, 118394, https://doi.org/10.1016/j.atmosenv.2021.118394, 2021.
Logan, J. A.: Tropospheric Ozone: Seasonal Behavior, Trends, and Anthropogenic Influence, J. Geophys. Res., 90, 10463–10482, https://doi.org/10.1029/JD090iD06p10463, 1985.
Matsunaga, A. and Ziemann, P. J.: Yields of β-hydroxynitrates, dihydroxynitrates, and trihydroxynitrates formed from OH radical-initiated reactions of 2-methyl-1-alkenes, P. Natl. Acad. Sci. USA, 107, 6664–6669, https://doi.org/10.1073/pnas.0910585107, 2010.
Mellouki, A., Wallington, T. J., and Chen, J.: Atmospheric Chemistry of Oxygenated Volatile Organic Compounds: Impacts on Air Quality and Climate, Chem. Rev., 115, 3984–4014, https://doi.org/10.1021/cr500549n, 2015.
Mellouki, A., Ammann, M., Cox, R. A., Crowley, J. N., Herrmann, H., Jenkin, M. E., McNeill, V. F., Troe, J., and Wallington, T. J.: Evaluated kinetic and photochemical data for atmospheric chemistry: volume VIII – gas-phase reactions of organic species with four, or more, carbon atoms (≥C4), Atmos. Chem. Phys., 21, 4797–4808, https://doi.org/10.5194/acp-21-4797-2021, 2021.
Mund, C., Fockenberg, C., and Zellner, R.: LIF Spectra of n-Propoxy Radicals and Kinetics of their Reactions with O2 and NO2, Ber. Bunsenges. Phys. Chem., 102, 709–715, https://doi.org/10.1002/bbpc.19981020502, 1998.
Nakanaga, T., Kondo, S., and Saëki, S.: Infrared band intensities of formaldehyde and formaldehyde-d2, J. Chem. Phys., 76, 3860–3865, https://doi.org/10.1063/1.443527, 1982.
Noda, J., Hallquist, M., Langer, S., and Ljungström, E.: Products from the gas-phase reaction of some unsaturated alcohols with nitrate radicals, Phys. Chem. Chem. Phys., 2, 2555–2564, https://doi.org/10.1039/B000251H, 2000.
Notario, A., Le Bras, G., and Mellouki, A.: Absolute Rate Constants for the Reactions of Cl Atoms with a Series of Esters, J. Phys. Chem. A., 102, 3112–3117, https://doi.org/10.1021/jp980416n, 1998.
Orlando, J. J., Tyndall, G. S., Vereecken, L., and Peeters, J.: The Atmospheric Chemistry of the Acetonoxy Radical, J. Phys. Chem. A, 104, 11578–11588, https://doi.org/10.1021/jp0026991, 2000.
Orlando, J. J., Tyndall, G. S., and Wallington, T. J.: The Atmospheric Chemistry of Alkoxy Radicals, Chem. Rev., 103, 4657–4689, https://doi.org/10.1021/cr020527p, 2003.
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, https://doi.org/10.5194/acp-9-1479-2009, 2009.
Picquet-Varrault, B., Doussin, J.-F., Durand-Jolibois, R., Pirali, O., and Carlier, P.: Kinetic and Mechanistic Study of the Atmospheric Oxidation by OH Radicals of Allyl Acetate, Environ. Sci. Technol., 36, 4081–4086, https://doi.org/10.1021/es0200138, 2002.
Picquet-Varrault, B., Suarez-Bertoa, R., Duncianu, M., Cazaunau, M., Pangui, E., David, M., and Doussin, J.-F.: Photolysis and oxidation by OH radicals of two carbonyl nitrates: 4-nitrooxy-2-butanone and 5-nitrooxy-2-pentanone, Atmos. Chem. Phys., 20, 487–498, https://doi.org/10.5194/acp-20-487-2020, 2020.
Praske, E., Crounse, J. D., Bates, K. H., Kurtén, T., Kjaergaard, H. G., and Wennberg, P. O.: Atmospheric Fate of Methyl Vinyl Ketone: Peroxy Radical Reactions with NO and HO2, J. Phys. Chem. A, 119, 4562–4572, https://doi.org/10.1021/jp5107058, 2015.
Profeta, L. T. M., Sams, R. L., and Johnson, T. J.: Quantitative Infrared Intensity Studies of Vapor-Phase Glyoxal, Methylglyoxal, and 2,3-Butanedione (Diacetyl), with Vibrational Assignments, J. Phys. Chem. A, 115, 9886–9900, https://doi.org/10.1021/jp204532x, 2011.
Sato, K., Klotz, B., Taketsuga, T., and Takaynagi, T.: Kinetic measurments for the reactions of ozone with crotonaldehyde and its methyl derivatives and calculations of transition-state theory, Phys. Chem. Chem. Phys., 6, 3696–3976, https://doi.org/10.1039/B402496F, 2004.
Siegel, H. and Eggersdorfer, M.: Ketones, Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH Verlag, Weinheim, https://doi.org/10.1002/14356007.a15_077, 2000.
Sifniades, S., Levy, A. B., and Bahl, H.: Acetone, Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH Verlag, Weinheim, https://doi.org/10.1002/14356007.a01_079.pub3, 2011.
Smith, I. W. M. and Ravishankara, A. R.: Role of Hydrogen-Bonded Intermediates in the Bimolecular Reactions of the Hydroxyl Radical, J. Phys. Chem. A, 106, 4798–4807, https://doi.org/10.1021/jp014234w, 2002.
Spittler, M.: Untersuchungen zur troposphärischen Oxidation von Limonen: Produktanalysen, Aerosolbildung und Photolyse von Produkten, PhD thesis, Bergische Universität Wuppertal, Germany, 2001.
Suarez-Bertoa, R., Picquet-Varrault, B., Tamas, W., Pangui, E., and Doussin, J.-F.: Atmospheric Fate of a Series of Carbonyl Nitrates: Photolysis Frequencies and OH-Oxidation Rate Constants, Environ. Sci. Technol., 46, 12502–12509, https://doi.org/10.1021/es302613x, 2012.
Talukdar, R. K., Zhu, L., Feierabend, K. J., and Burkholder, J. B.: Rate coefficients for the reaction of methylglyoxal (CH3COCHO) with OH and NO3 and glyoxal (HCO)2 with NO3, Atmos. Chem. Phys., 11, 10837–10851, https://doi.org/10.5194/acp-11-10837-2011, 2011.
Taylor, W. D., Allston, T. D., Moscato, M. J., Fazekas, G. B., Kozlowski, R., and Takacs, G. A.: Atmospheric photodissociation lifetimes for nitromethane, methyl nitrite, and methyl nitrate, Int. J. Chem. Kinet., 12, 231–240, https://doi.org/10.1002/kin.550120404, 1980.
Tuazon, E. C. and Atkinson, R.: A Product Study of the Gas-Phase Reaction of Methyl Vinyl Ketone with the OH Radical in the Presence of NOX, Int. J. Chem. Kinet., 21, 1141–1152, https://doi.org/10.1002/kin.550211207, 1989.
Tuazon, E. C., MacLeod, H., Atkinson R., and Carter, W. P. L.: α-Dicarbonyl yields from the NOx-air photooxidation of a series of aromatic hydrocarbons in air, Environ. Sci. Technol., 20, 383–387, https://doi.org/10.1021/es00146a010, 1986.
US EPA: Estimation Programs Interface Suite™ for Microsoft® Windows, v 4.11. United States Environmental Protection Agency, Washington, DC, USA, 2021.
Vereecken, L. and Peeters, J.: Decomposition of substituted alkoxy radicals – part I: a generalized structure-activity relationship for reaction barrier heights, Phys. Chem. Chem. Phys., 11, 9062–9074, https://doi.org/10.1039/B909712K, 2009.
Vyskocil, A., Viau, C., and Lamy, S.: Peroxyacetyl nitrate: review of toxicity, Hum. Exp. Toxicol., 17, 212–220, https://doi.org/10.1177/096032719801700403, 1998.
Wang, J., Zhou, L., Wang, W., and Ge, M.: Gas-phase reaction of two unsaturated ketones with atomic Cl and O3: kinetics and products, Phys. Chem. Chem. Phys., 17, 12000–12012, https://doi.org/10.1039/C4CP05461J, 2015.
Wang, X., Hong, P., Kiss, A. A., Wang, Q., Li, L., Wang, H., and Qiu, T.: From Batch to Continuos Sustainable Production of 3-Methyl-3-penten-2-one for Synthetic Ketone Fragrances, ACS Sustain. Chem. Eng., 8, 17201–17214, https://doi.org/10.1021/acssuschemeng.0c05908, 2020.
Wingenter, O. W., Kubo, M. K., Blake, N. J., Smith Jr., T. W., Blake, D. R., and Rowland, F. S.: Hydrocarbon and halocarbon measurements as photochemical and dynamical indicators of atmospheric hydroxyl, atomic chlorine, and vertical mixing obtained during Lagrangian flights, J. Geophys. Res., 101, 4331–4340, https://doi.org/10.1029/95JD02457, 1996.
Winiberg, F. A. F., Dillon, T. J., Orr, S. C., Groß, C. B. M., Bejan, I., Brumby, C. A., Evans, M. J., Smith, S. C., Heard, D. E., and Seakins, P. W.: Direct measurements of OH and other product yields from the HO2+CH3C(O)O2 reaction, Atmos. Chem. Phys., 16, 4023–4042, https://doi.org/10.5194/acp-16-4023-2016, 2016.
Short summary
Within this work we determined the rate coefficients and products of the reaction of unsaturated ketones with OH radicals in an effort to complete the gaps in the knowledge needed for modelling chemistry in the atmosphere. Both substances are potentially emitted by biomass burning, industrial activities or formed in the troposphere by oxidation of terpenes. As products we identified aldehydes and ketones which in turn are known to be responsible for the transportation of NOx species.
Within this work we determined the rate coefficients and products of the reaction of unsaturated...
Altmetrics
Final-revised paper
Preprint