Articles | Volume 24, issue 1
https://doi.org/10.5194/acp-24-663-2024
© Author(s) 2024. 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-24-663-2024
© Author(s) 2024. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
17 Jan 2024
Research article |
| 17 Jan 2024
| 17 Jan 2024
Temperature-dependent aqueous OH kinetics of C2–C10 linear and terpenoid alcohols and diols: new rate coefficients, structure–activity relationship, and atmospheric lifetimes
Bartłomiej Witkowski
CORRESPONDING AUTHOR
University of Warsaw, Faculty of Chemistry, al. Żwirki i Wigury 101, 02-089 Warsaw, Poland
Priyanka Jain
University of Warsaw, Faculty of Chemistry, al. Żwirki i Wigury 101, 02-089 Warsaw, Poland
Beata Wileńska
University of Warsaw, Faculty of Chemistry, al. Żwirki i Wigury 101, 02-089 Warsaw, Poland
Tomasz Gierczak
University of Warsaw, Faculty of Chemistry, al. Żwirki i Wigury 101, 02-089 Warsaw, Poland
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Cited articles
Adams, G. E., Boag, J. W., and Michael, B. D.: Reactions of the hydroxyl radical, Part 2 – Determination of absolute rate constants, T. Faraday Soc., 61, 1417–1424, https://doi.org/10.1039/TF9656101417, 1965.
Aljawhary, D., Zhao, R., Lee, A. K. Y., Wang, C., and Abbatt, J. P. D.: Kinetics, Mechanism, and Secondary Organic Aerosol Yield of Aqueous Phase Photo-oxidation of α-Pinene Oxidation Products, J. Phys. Chem. A, 120, 1395–1407, https://doi.org/10.1021/acs.jpca.5b06237, 2016.
Amorim, J. V., Wu, S., Klimchuk, K., Lau, C., Williams, F. J., Huang, Y., and Zhao, R.: pH Dependence of the OH Reactivity of Organic Acids in the Aqueous Phase, Environ. Sci. Technol., 54, 12484–12492, https://doi.org/10.1021/acs.est.0c03331, 2020.
Amorim, J. V., Guo, X., Gautam, T., Fang, R., Fotang, C., Williams, F. J., and Zhao, R.: Photo-oxidation of pinic acid in the aqueous phase: a mechanistic investigation under acidic and basic pH conditions, Environ. Sci.-Atmos., 1, 276–287, https://doi.org/10.1039/D1EA00031D, 2021.
Anbar, M., Meyerstein, D., and Neta, P.: Reactivity of aliphatic compounds towards hydroxyl radicals, J. Chem. Soc. B., 742–747, https://doi.org/10.1039/J29660000742, 1966.
Atkinson, R.: Estimations of OH radical rate constants from H-atom abstraction from CH and OH bonds over the temperature range 250–1000 K, Int. J. Chem. Kinet., 18, 555–568, https://doi.org/10.1002/kin.550180506, 1986a.
Atkinson, R.: Kinetics and mechanisms of the gas-phase reactions of the hydroxyl radical with organic compounds under atmospheric conditions, Chem. Rev., 86, 69–201, https://doi.org/10.1021/cr00071a004, 1986b.
Atkinson, R.: A structure-activity relationship for the estimation of rate constants for the gas-phase reactions of OH radicals with organic compounds, Int. J. Chem. Kinet., 19, 799–828, https://doi.org/10.1002/kin.550190903, 1987.
Belsito, D., Bickers, D., Bruze, M., Calow, P., Greim, H., Hanifin, J. M., Rogers, A. E., Saurat, J. H., Sipes, I. G., and Tagami, H.: A toxicologic and dermatologic assessment of cyclic and non-cyclic terpene alcohols when used as fragrance ingredients, Food Chem. Toxicol., 46, S1–S71, https://doi.org/10.1016/j.fct.2008.06.085, 2008.
Bennett, J. E. and Summers, R.: Product Studies of the Mutual Termination Reactions of sec-Alkylperoxy Radicals: Evidence for Non-Cyclic Termination, Can. J. Chem., 52, 1377–1379, https://doi.org/10.1139/v74-209, 1974.
Bräuer, P., Mouchel-Vallon, C., Tilgner, A., Mutzel, A., Böge, O., Rodigast, M., Poulain, L., van Pinxteren, D., Wolke, R., Aumont, B., and Herrmann, H.: Development of a protocol for the auto-generation of explicit aqueous-phase oxidation schemes of organic compounds, Atmos. Chem. Phys., 19, 9209–9239, https://doi.org/10.5194/acp-19-9209-2019, 2019.
Buxton, G. V., Greenstock, C. L., Helman, W. P., and Ross, A. B.: Critical Review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals (
Carlton, A. G., Christiansen, A. E., Flesch, M. M., Hennigan, C. J., and Sareen, N.: Multiphase Atmospheric Chemistry in Liquid Water: Impacts and Controllability of Organic Aerosol, Acc. Chem. Res., 53, 1715–1723, https://doi.org/10.1021/acs.accounts.0c00301, 2020.
Ceacero-Vega, A. A., Ballesteros, B., Bejan, I., Barnes, I., Jiménez, E., and Albaladejo, J.: Kinetics and Mechanisms of the Tropospheric Reactions of Menthol, Borneol, Fenchol, Camphor, and Fenchone with Hydroxyl Radicals (OH) and Chlorine Atoms (Cl), J. Phys. Chem. A, 116, 4097–4107, https://doi.org/10.1021/jp212076g, 2012.
Chandler, D.: Interfaces and the driving force of hydrophobic assembly, Nature, 437, 640–647, https://doi.org/10.1038/nature04162, 2005.
Chen, H., Su, X., He, J., Zhang, P., Xu, H., and Zhou, C.: Investigation on combustion characteristics of cyclopentanol/diesel fuel blends in an optical engine, Renew. Energ., 167, 811–829, https://doi.org/10.1016/j.renene.2020.11.155, 2021.
Cheng, Y., Zheng, G., Wei, C., Mu, Q., Zheng, B., Wang, Z., Gao, M., Zhang, Q., He, K., Carmichael, G., Pöschl, U., and Su, H.: Reactive nitrogen chemistry in aerosol water as a source of sulfate during haze events in China, Sci. Adv., 2, 1–11, https://doi.org/10.1126/sciadv.1601530, 2016.
Chin, M. and Wine, P. H.: A Temperature-Dependent Competitive Kinetics Study of the Aqueous-Phase Reactions of OH Radicals with Formate, Formic Acid, Acetate, Acetic Acid, and Hydrated Formaldehyde, Symposium on Aquatic and Surface Photochemistry, at the 203rd National Meeting of the American-Chemical-Society, San Francisco, Ca, April 5–10, WOS:A1994, 85–96, eBook ISBN 9781351069847, https://doi.org/10.1201/9781351069847, 1994.
Claeys, M., Iinuma, Y., Szmigielski, R., Surratt, J. D., Blockhuys, F., Van Alsenoy, C., Bołge, O., Sierau, B., Goìmez-Gonzaìlez, Y., Vermeylen, R., Van der Veken, P., Shahgholi, M., Chan, A. W. H., Herrmann, H., Seinfeld, J. H., and Maenhaut, W.: Terpenylic Acid and Related Compounds from the Oxidation of α-Pinene: Implications for New Particle Formation and Growth above Forests, Environ. Sci. Technol., 43, 6976–6982, https://doi.org/10.1021/es9007596, 2009.
Das, P., Das, P. K., and Arunan, E.: Conformational Stability and Intramolecular Hydrogen Bonding in 1,2-Ethanediol and 1,4-Butanediol, J. Phys. Chem. A, 119, 3710–3720, https://doi.org/10.1021/jp512686s, 2015.
Doussin, J. F. and Monod, A.: Structure–activity relationship for the estimation of OH-oxidation rate constants of carbonyl compounds in the aqueous phase, Atmos. Chem. Phys., 13, 11625–11641, https://doi.org/10.5194/acp-13-11625-2013, 2013.
Enami, S. and Sakamoto, Y.: OH-Radical Oxidation of Surface-Active cis-Pinonic Acid at the Air–Water Interface, J. Phys. Chem. A, 120, 3578–3587, https://doi.org/10.1021/acs.jpca.6b01261, 2016.
Ervens, B.: Modeling the Processing of Aerosol and Trace Gases in Clouds and Fogs, Chem. Rev., 115, 4157–4198, https://doi.org/10.1021/cr5005887, 2015.
Ervens, B., Gligorovski, S., and Herrmann, H.: Temperature-dependent rate constants for hydroxyl radical reactions with organic compounds in aqueous solutions, Phys. Chem. Chem. Phys., 5, 1811–1824, https://doi.org/10.1039/B300072A, 2003.
Ervens, B., Sorooshian, A., Aldhaif, A. M., Shingler, T., Crosbie, E., Ziemba, L., Campuzano-Jost, P., Jimenez, J. L., and Wisthaler, A.: Is there an aerosol signature of chemical cloud processing?, Atmos. Chem. Phys., 18, 16099–16119, https://doi.org/10.5194/acp-18-16099-2018, 2018.
Fichan, I., Larroche, C., and Gros, J. B.: Water Solubility, Vapor Pressure, and Activity Coefficients of Terpenes and Terpenoids, J. Chem. Eng. Data., 44, 56–62, https://doi.org/10.1021/je980070+, 1999.
Fu, P. Q., Kawamura, K., Chen, J., Charrière, B., and Sempéré, R.: Organic molecular composition of marine aerosols over the Arctic Ocean in summer: contributions of primary emission and secondary aerosol formation, Biogeosciences, 10, 653–667, https://doi.org/10.5194/bg-10-653-2013, 2013.
Fuzzi, S., Baltensperger, U., Carslaw, K., Decesari, S., Denier van der Gon, H., Facchini, M. C., Fowler, D., Koren, I., Langford, B., Lohmann, U., Nemitz, E., Pandis, S., Riipinen, I., Rudich, Y., Schaap, M., Slowik, J. G., Spracklen, D. V., Vignati, E., Wild, M., Williams, M., and Gilardoni, S.: Particulate matter, air quality and climate: lessons learned and future needs, Atmos. Chem. Phys., 15, 8217–8299, https://doi.org/10.5194/acp-15-8217-2015, 2015.
Gligorovski, S., Rousse, D., George, C., and Herrmann, H.: Rate constants for the OH reactions with oxygenated organic compounds in aqueous solution, Int. J. Chem. Kinet., 41, 309–326, https://doi.org/10.1002/kin.20405, 2009.
Goldstein, A. H. and Galbally, I. E.: Known and unexplored organic constituents in the earth's atmosphere, Environ. Sci. Technol., 41, 1514–1521, https://doi.org/10.1021/es072476p, 2007.
González-Sánchez, J. M., Brun, N., Wu, J., Morin, J., Temime-Roussel, B., Ravier, S., Mouchel-Vallon, C., Clément, J. L., and Monod, A.: On the importance of atmospheric loss of organic nitrates by aqueous-phase OH oxidation, Atmos. Chem. Phys., 21, 4915–4937, https://doi.org/10.5194/acp-21-4915-2021, 2021.
Guenther, A., Jiang, X., Heald, C. L., Sakulyanontvittaya, T., Duhl, T., Emmons, L., and Wang, X.: The Model of Emissions of Gases and Aerosols from Nature version 2.1 (MEGAN2. 1): an extended and updated framework for modeling biogenic emissions, Geosci. Model. Dev., 5, 1471–1492, https://doi.org/10.5194/gmd-5-1471-2012, 2012.
Hallquist, M., Wenger, J. C., Baltensperger, U., Rudich, Y., Simpson, D., Claeys, M., Dommen, J., Donahue, N. M., George, C., Goldstein, A. H., Hamilton, J. F., Herrmann, H., Hoffmann, T., Iinuma, Y., Jang, M., Jenkin, M. E., Jimenez, J. L., Kiendler-Scharr, A., Maenhaut, W., McFiggans, G., Mentel, T. F., Monod, A., Prévôt, A. S. H., Seinfeld, J. H., Surratt, J. D., Szmigielski, R., and Wildt, J.: The formation, properties and impact of secondary organic aerosol: current and emerging issues, Atmos. Chem. Phys., 9, 5155–5236, https://doi.org/10.5194/acp-9-5155-2009, 2009.
Hart, E. J., Gordon, S., and Thomas, J. K.: A Review of the Radiation Chemistry of Single-Carbon Compounds and Some Reactions of the Hydrated Electron in Aqueous Solution, Radiat. Res., 4, 74–88, 1964.
EPI Suite™: Estimation Program Interface v4.11, https://www.epa.gov/tsca-screening-tools/epi-suitetm-estimation-program-interface, last access: 20 June 2023.
Héral, B., Stierlin, É., Fernandez, X., and Michel, T.: Phytochemicals from the genus Lavandula: a review, Phytochem Rev., 20, 751–771, https://doi.org/10.1007/s11101-020-09719-z, 2021.
Herrmann, H.: Kinetics of aqueous phase reactions relevant for atmospheric chemistry, Chem. Rev., 103, 4691–4716, https://doi.org/10.1021/cr020658q, 2003.
Herrmann, H., Tilgner, A., Barzaghi, P., Majdik, Z., Gligorovski, S., Poulain, L., and Monod, A.: Towards a more detailed description of tropospheric aqueous phase organic chemistry: CAPRAM 3.0, Atmos. Environ., 39, 4351–4363, https://doi.org/10.1016/j.atmosenv.2005.02.016, 2005.
Herrmann, H., Hoffmann, D., Schaefer, T., Bräuer, P., and Tilgner, A.: Tropospheric Aqueous-Phase Free-Radical Chemistry: Radical Sources, Spectra, Reaction Kinetics and Prediction Tools, ChemPhysChem, 11, 3796–3822, https://doi.org/10.1002/cphc.201000533, 2010.
Herrmann, H., Schaefer, T., Tilgner, A., Styler, S. A., Weller, C., Teich, M., and Otto, T.: Tropospheric Aqueous-Phase Chemistry: Kinetics, Mechanisms, and Its Coupling to a Changing Gas Phase, Chem. Rev., 115, 4259–4334, https://doi.org/10.1021/cr500447k, 2015.
Hiura, T., Yoshioka, H., Matsunaga, S. N., Saito, T., Kohyama, T. I., Kusumoto, N., Uchiyama, K., Suyama, Y., and Tsumura, Y.: Diversification of terpenoid emissions proposes a geographic structure based on climate and pathogen composition in Japanese cedar, Sci. Rep., 11, 8307, https://doi.org/10.1038/s41598-021-87810-x, 2021.
Hoffmann, D., Weigert, B., Barzaghi, P., and Herrmann, H.: Reactivity of poly-alcohols towards OH, NO3 and SO
Hunter, J. F., Carrasquillo, A. J., Daumit, K. E., and Kroll, J. H.: Secondary Organic Aerosol Formation from Acyclic, Monocyclic, and Polycyclic Alkanes, Environ. Sci. Technol., 48, 10227–10234, https://doi.org/10.1021/es502674s, 2014.
IUPAC Task Group on Atmospheric Chemical Kinetic Data Evaluation: https://iupac-aeris.ipsl.fr/show_datasheets.php?category=Systematic+OH, last access: 26 September 2023.
Jimenez, J. L., Canagaratna, M. R., Donahue, N. M., Prevot, A. S. H., Zhang, Q., Kroll, J. H., DeCarlo, P. F., Allan, J. D., Coe, H., Ng, N. L., Aiken, A. C., Docherty, K. S., Ulbrich, I. M., Grieshop, A. P., Robinson, A. L., Duplissy, J., Smith, J. D., Wilson, K. R., Lanz, V. A., Hueglin, C., Sun, Y. L., Tian, J., Laaksonen, A., Raatikainen, T., Rautiainen, J., Vaattovaara, P., Ehn, M., Kulmala, M., Tomlinson, J. M., Collins, D. R., Cubison, M. J., Dunlea, J., Huffman, J. A., Onasch, T. B., Alfarra, M. R., Williams, P. I., Bower, K., Kondo, Y., Schneider, J., Drewnick, F., Borrmann, S., Weimer, S., Demerjian, K., Salcedo, D., Cottrell, L., Griffin, R., Takami, A., Miyoshi, T., Hatakeyama, S., Shimono, A., Sun, J. Y., Zhang, Y. M., Dzepina, K., Kimmel, J. R., Sueper, D., Jayne, J. T., Herndon, S. C., Trimborn, A. M., Williams, L. R., Wood, E. C., Middlebrook, A. M., Kolb, C. E., Baltensperger, U., and Worsnop, D. R.: Evolution of Organic Aerosols in the Atmosphere, Science, 326, 1525–1529, https://doi.org/10.1126/science.1180353, 2009.
Klein, R. A.: Hydrogen bonding in diols and binary diol–water systems investigated using DFT methods. II. Calculated infrared OH-stretch frequencies, force constants, and NMR chemical shifts correlate with hydrogen bond geometry and electron density topology. A reevaluation of geometrical criteria for hydrogen bonding, J. Comput. Chem., 24, 1120–1131, https://doi.org/10.1002/jcc.10256, 2003.
Konjeviæ, L., Racar, M., Ilinèiæ, P., and Faraguna, F.: A comprehensive study on application properties of diesel blends with propanol, butanol, isobutanol, pentanol, hexanol, octanol and dodecanol, Energy, 262, 125430, https://doi.org/10.1016/j.energy.2022.125430, 2023.
Kopinke, F.-D. and Georgi, A.: What Controls Selectivity of Hydroxyl Radicals in Aqueous Solution? Indications for a Cage Effect, J. Phys. Chem. A, 121, 7947–7955, https://doi.org/10.1021/acs.jpca.7b05782, 2017.
Krofliè, A., Schaefer, T., Huš, M., Phuoc Le, H., Otto, T., and Herrmann, H.: OH radicals reactivity towards phenol-related pollutants in water: temperature dependence of the rate constants and novel insights into the [OH–phenol]ÿ adduct formation, Phys. Chem. Chem. Phys., 22, 1324–1332, https://doi.org/10.1039/C9CP05533A, 2020.
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.
Leviss, D. H., Van Ry, D. A., and Hinrichs, R. Z.: Multiphase Ozonolysis of Aqueous á-Terpineol, Environ. Sci. Technol., 50, 11698–11705, https://doi.org/10.1021/acs.est.6b03612, 2016.
Lim, Y. B. and Ziemann, P. J.: Effects of Molecular Structure on Aerosol Yields from OH Radical-Initiated Reactions of Linear, Branched, and Cyclic Alkanes in the Presence of NOx, Environ. Sci. Technol., 43, 2328–2334, https://doi.org/10.1021/es803389s, 2009.
Lin, G., Sillman, S., Penner, J. E., and Ito, A.: Global modeling of SOA: the use of different mechanisms for aqueous-phase formation, Atmos. Chem. Phys., 14, 5451–5475, https://doi.org/10.5194/acp-14-5451-2014, 2014.
Mahilang, M., Deb, M. K., and Pervez, S.: Biogenic secondary organic aerosols: A review on formation mechanism, analytical challenges and environmental impacts, Chemosphere, 262, 127771, https://doi.org/10.1016/j.chemosphere.2020.127771, 2021.
Matheson, M. S., Mamou, A., Silverman, J., and Rabani, J.: Reaction of hydroxyl radicals with polyethylene oxide in aqueous solution, J. Phys. Chem. , 77, 2420–2424, https://doi.org/10.1021/j100639a011, 1973.
McGillen, Carter, W. P. L., Mellouki, A., Orlando, J. J., Picquet-Varrault, B., and Wallington, T. J.: Database for the kinetics of the gas-phase atmospheric reactions of organic compounds, Earth Syst. Sci. Data, 12, 1203–1216, https://doi.org/10.5194/essd-12-1203-2020, 2020.
McGillen, M. R., Carter, W. P. L., Mellouki, A., Orlando, J. J., Picquet-Varrault, B., and Wallington, T. J.: Database for the Kinetics of the Gas-Phase Atmospheric Reactions of Organic Compounds, Eurochamp Data Center [data set], https://doi.org/10.25326/mh4q-y215, 2021.
McNeill, V. F.: Aqueous Organic Chemistry in the Atmosphere: Sources and Chemical Processing of Organic Aerosols, Environ. Sci. Technol. , 49, 1237–1244, https://doi.org/10.1021/es5043707, 2015.
McVay, R. and Ervens, B.: A microphysical parameterization of aqSOA and sulfate formation in clouds, Geophys. Res. Lett., 44, 7500–7509, https://doi.org/10.1002/2017gl074233, 2017.
Mekic, M. and Gligorovski, S.: Ionic strength effects on heterogeneous and multiphase chemistry: Clouds versus aerosol particles, Atmos. Environ., 244, 117911, https://doi.org/10.1016/j.atmosenv.2020.117911, 2021.
Mellouki, A., Le Bras, G., and Sidebottom, H.: Kinetics and Mechanisms of the Oxidation of Oxygenated Organic Compounds in the Gas Phase, Chem. Rev., 103, 5077–5096, https://doi.org/10.1021/cr020526x, 2003.
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.
Merz, J. H. and Waters, W. A.: A. – Electron-transfer reactions, The mechanism of oxidation of alcohols with Fenton's reagent, Discuss. Faraday Soc., 2, 179–188, https://doi.org/10.1039/DF9470200179, 1947.
Mitroka, S., Zimmeck, S., Troya, D., and Tanko, J. M.: How Solvent Modulates Hydroxyl Radical Reactivity in Hydrogen Atom Abstractions, J. Am. Chem. Soc., 132, 2907–2913, https://doi.org/10.1021/ja903856t, 2010.
Monod, A. and Doussin, J. F.: Structure-activity relationship for the estimation of OH-oxidation rate constants of aliphatic organic compounds in the aqueous phase: alkanes, alcohols, organic acids and bases, Atmos. Environ., 42, 7611–7622, https://doi.org/10.1016/j.atmosenv.2008.06.005, 2008.
Monod, A., Poulain, L., Grubert, S., Voisin, D., and Wortham, H.: Kinetics of OH-initiated oxidation of oxygenated organic compounds in the aqueous phase: new rate constants, structure–activity relationships and atmospheric implications, Atmos. Environ., 39, 7667–7688, https://doi.org/10.1016/j.atmosenv.2005.03.019, 2005.
Murakami, M. and Ishida, N.: â-Scission of Alkoxy Radicals in Synthetic Transformations, Chem. Lett, 46, 1692–1700, https://doi.org/10.1246/cl.170834, 2017.
Otto, S. and Engberts, J. B. F. N.: Hydrophobic interactions and chemical reactivity, Org. Biomol. Chem., 1, 2809–2820, https://doi.org/10.1039/B305672D, 2003.
Otto, T., Schaefer, T., and Herrmann, H.: Aqueous-Phase Oxidation of Terpene-Derived Acids by Atmospherically Relevant Radicals, J. Phys. Chem. A, 122, 9233–9241, https://doi.org/10.1021/acs.jpca.8b08922, 2018.
Pai, S. J., Heald, C. L., Pierce, J. R., Farina, S. C., Marais, E. A., Jimenez, J. L., Campuzano-Jost, P., Nault, B. A., Middlebrook, A. M., Coe, H., Shilling, J. E., Bahreini, R., Dingle, J. H., and Vu, K.: An evaluation of global organic aerosol schemes using airborne observations, Atmos. Chem. Phys., 20, 2637–2665, https://doi.org/10.5194/acp-20-2637-2020, 2020.
Peduzzi, P., Concato, J., Kemper, E., Holford, T. R., and Feinstein, A. R.: A simulation study of the number of events per variable in logistic regression analysis, J. Clin. Epidemiol., 49, 1373–1379, https://doi.org/10.1016/S0895-4356(96)00236-3, 1996.
Prutz, W. A. and Vogel, S.: Specific rate constants of hydroxyl radical and hydrated electron reaction determined by RCL method, Z. Naturforsch., 31, 1501–1510, https://doi.org/10.1515/znb-1976-1115, 1976.
Pye, H. O. T., Ward-Caviness, C. K., Murphy, B. N., Appel, K. W., and Seltzer, K. M.: Secondary organic aerosol association with cardiorespiratory disease mortality in the United States, Nat. Commun., 12, 7215, https://doi.org/10.1038/s41467-021-27484-1, 2021.
Rauk, A., Boyd, R. J., Boyd, S. L., Henry, D. J., and Radom, L.: Alkoxy radicals in the gaseous phase: â-scission reactions and formation by radical addition to carbonyl compounds, Can. J. Chem., 81, 431–442, https://doi.org/10.1139/v02-206, 2003.
Reuvers, A. P., Greenstock, C. L., Borsa, J., and Chapman, J. D.: Studies on the Mechanism of Chemical Radioprotection by Dimethyl Sulphoxide, Int. J. Radiat. Biol. Relat. Stud. Phys. Chem. Med., 24, 533–536, https://doi.org/10.1080/09553007314551431, 1973.
Richters, S., Herrmann, H., and Berndt, T.: Gas-phase rate coefficients of the reaction of ozone with four sesquiterpenes at 295 ± 2 K, Phys. Chem. Chem. Phys., 17, 11658–11669, https://doi.org/10.1039/C4CP05542J, 2015.
Ross, P. D. and Rekharsky, M. V.: Thermodynamics of hydrogen bond and hydrophobic interactions in cyclodextrin complexes, Biophys. J., 71, 2144–2154, https://doi.org/10.1016/S0006-3495(96)79415-8, 1996.
Russell, G. A.: Deuterium-isotope Effects in the Autoxidation of Aralkyl Hydrocarbons, Mechanism of the Interaction of PEroxy Radicals1, J. Am. Chem. Soc., 79, 3871–3877, https://doi.org/10.1021/ja01571a068, 1957.
Sander, R.: Compilation of Henry's law constants (version 4.0) for water as solvent, Atmos. Chem. Phys., 15, 4399–4981, https://doi.org/10.5194/acp-15-4399-2015, 2015.
Sarang, K., Otto, T., Rudzinski, K., Schaefer, T., Grgiæ, I., Nestorowicz, K., Herrmann, H., and Szmigielski, R.: Reaction Kinetics of Green Leaf Volatiles with Sulfate, Hydroxyl, and Nitrate Radicals in Tropospheric Aqueous Phase, Environ. Sci. Technol., 55, 13666–13676, https://doi.org/10.1021/acs.est.1c03276, 2021.
Sato, K., Jia, T., Tanabe, K., Morino, Y., Kajii, Y., and Imamura, T.: Terpenylic acid and nine-carbon multifunctional compounds formed during the aging of α-pinene ozonolysis secondary organic aerosol, Atmos. Environ., 130, 127–135, https://doi.org/10.1016/j.atmosenv.2015.08.047, 2016.
Schaefer, T., Wen, L., Estelmann, A., Maak, J., and Herrmann, H.: pH- and Temperature-Dependent Kinetics of the Oxidation Reactions of OH with Succinic and Pimelic Acid in Aqueous Solution, Atmosphere, 11, 320–334, https://doi.org/10.3390/atmos11040320, 2020.
Scholes, G. and Willson, R. L.: ã-Radiolysis of aqueous thymine solutions. Determination of relative reaction rates of OH radicals, Trans. Faraday Soc., 63, 2983–2993, https://doi.org/10.1039/TF9676302983, 1967.
Schöne, L., Schindelka, J., Szeremeta, E., Schaefer, T., Hoffmann, D., Rudzinski, K. J., Szmigielski, R., and Herrmann, H.: Atmospheric aqueous phase radical chemistry of the isoprene oxidation products methacrolein, methyl vinyl ketone, methacrylic acid and acrylic acid – kinetics and product studies, Phys. Chem. Chem. Phys., 16, 6257–6272, https://doi.org/10.1039/C3CP54859G, 2014.
Shrivastava, M., Cappa, C. D., Fan, J., Goldstein, A. H., Guenther, A. B., Jimenez, J. L., Kuang, C., Laskin, A., Martin, S. T., Ng, N. L., Petaja, T., Pierce, J. R., Rasch, P. J., Roldin, P., Seinfeld, J. H., Shilling, J., Smith, J. N., Thornton, J. A., Volkamer, R., Wang, J., Worsnop, D. R., Zaveri, R. A., Zelenyuk, A., and Zhang, Q.: Recent advances in understanding secondary organic aerosol: Implications for global climate forcing, Rev. Geophys., 55, 509–559, https://doi.org/10.1002/2016RG000540, 2017.
Sindelarova, K., Granier, C., Bouarar, I., Guenther, A., Tilmes, S., Stavrakou, T., Müller, J. F., Kuhn, U., Stefani, P., and Knorr, W.: Global data set of biogenic VOC emissions calculated by the MEGAN model over the last 30 years, Atmos. Chem. Phys., 14, 9317–9341, https://doi.org/10.5194/acp-14-9317-2014, 2014.
Sindelarova, K., Markova, J., Simpson, D., Huszar, P., Karlicky, J., Darras, S., and Granier, C.: High-resolution biogenic global emission inventory for the time period 2000–2019 for air quality modelling, Earth Syst. Sci. Data, 14, 251–270, https://doi.org/10.5194/essd-14-251-2022, 2022.
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.
Stemmler, K. and von Gunten, U.: OH radical-initiated oxidation of organic compounds in atmospheric water phases: part 1. Reactions of peroxyl radicals derived from 2-butoxyethanol in water, Atmos. Environ., 34, 4241–4252, https://doi.org/10.1016/S1352-2310(00)00218-1, 2000.
Su, H., Cheng, Y., and Pöschl, U.: New Multiphase Chemical Processes Influencing Atmospheric Aerosols, Air Quality, and Climate in the Anthropocene, Acc. Chem. Res., 53, 2034–2043, https://doi.org/10.1021/acs.accounts.0c00246, 2020.
Swain, C. G. and Lupton, E. C.: Field and resonance components of substituent effects, J. Am. Chem. Soc., 90, 4328–4337, https://doi.org/10.1021/ja01018a024, 1968.
Tsigaridis, K. and Kanakidou, M.: The Present and Future of Secondary Organic Aerosol Direct Forcing on Climate, Curr. Clim. Change Rep., 4, 84–98, https://doi.org/10.1007/s40641-018-0092-3, 2018.
Tsui, W. G., Woo, J. L., and McNeill, V. F.: Impact of Aerosol-Cloud Cycling on Aqueous Secondary Organic Aerosol Formation, Atmosphere, 10, 666–678, https://doi.org/10.3390/atmos10110666, 2019.
von Sonntag, C. and Schuchmann, H.-P.: The Elucidation of Peroxyl Radical Reactions in Aqueous Solution with the Help of Radiation-Chemical Methods, Angew. Chem., Int. Ed. Engl., 30, 1229–1253, https://doi.org/10.1002/anie.199112291, 1991.
Willson, R. L., Greenstock, C. L., Adams, G. E., Wageman, R., and Dorfman, L. M.: The standardization of hydroxyl radical rate data from radiation chemistry, Int. J. Radiat. Phys. Chem., 3, 211–220, https://doi.org/10.1016/0020-7055(71)90023-4, 1971.
Witkowski, B.: Kinetic dataset – aqueous oxidation of aliphatic molecules by hydroxyl radical, RepOD [data set], https://doi.org/10.18150/CPIWK1, 2023.
Witkowski, B. and Gierczak, T.: cis-Pinonic Acid Oxidation by Hydroxyl Radicals in the Aqueous Phase under Acidic and Basic Conditions: Kinetics and Mechanism, Environ. Sci. Technol., 51, 9765–9773, https://doi.org/10.1021/acs.est.7b02427, 2017.
Witkowski, B., Al-sharafi, M., and Gierczak, T.: Kinetics of Limonene Secondary Organic Aerosol Oxidation in the Aqueous Phase, Environ. Sci. Technol., 52, 11583–11590, https://doi.org/10.1021/acs.est.8b02516, 2018a.
Witkowski, B., Jurdana, S., and Gierczak, T.: Limononic Acid Oxidation by Hydroxyl Radicals and Ozone in the Aqueous Phase, Environ. Sci. Technol., 52, 3402–3411, https://doi.org/10.1021/acs.est.7b04867, 2018b.
Witkowski, B., Al-sharafi, M., and Gierczak, T.: Kinetics and products of the aqueous-phase oxidation of â-caryophyllonic acid by hydroxyl radicals, Atmos. Environ., 213, 231–238, https://doi.org/10.1016/j.atmosenv.2019.06.016, 2019.
Witkowski, B., Chi, J., Jain, P., Błaziak, K., and Gierczak, T.: Aqueous OH kinetics of saturated C6–C10 dicarboxylic acids under acidic and basic conditions between 283 and 318 K; new structure-activity relationship parameters, Atmos. Environ., 267, 118761, https://doi.org/10.1016/j.atmosenv.2021.118761, 2021.
Witkowski, B., al-Sharafi, M., Błaziak, K., and Gierczak, T.: Aging of α-Pinene Secondary Organic Aerosol by Hydroxyl Radicals in the Aqueous Phase: Kinetics and Products, Environ. Sci. Technol., 57, 6040–6051, https://doi.org/10.1021/acs.est.2c07630, 2023.
Xu, L., Du, L., Tsona, N. T., and Ge, M.: Anthropogenic Effects on Biogenic Secondary Organic Aerosol Formation, Adv. Atmos. Sci., 38, 1053–1084, https://doi.org/10.1007/s00376-020-0284-3, 2021.
Yamabe, S. and Yamazaki, S.: A DFT study of proton transfers for the reaction of phenol and hydroxyl radical leading to dihydroxybenzene and H2O in the water cluster, Int. J. Quantum Chem., 118, e25510, https://doi.org/10.1002/qua.25510, 2018.
Yasmeen, F., Szmigielski, R., Vermeylen, R., Gómez-González, Y., Surratt, J. D., Chan, A. W. H., Seinfeld, J. H., Maenhaut, W., and Claeys, M.: Mass spectrometric characterization of isomeric terpenoic acids from the oxidation of α-pinene, α-pinene, d-limonene, and Ä3-carene in fine forest aerosol, J. Mass Spectrom., 46, 425–442, https://doi.org/10.1002/jms.1911, 2011.
Zhao, R., Aljawhary, D., Lee, A. K. Y., and Abbatt, J. P. D.: Rapid Aqueous-Phase Photooxidation of Dimers in the α-Pinene Secondary Organic Aerosol, Environ. Sci. Technol. Lett., 4, 205–210, https://doi.org/10.1021/acs.estlett.7b00148, 2017.
Zhou, W., Mekic, M., Liu, J., Loisel, G., Jin, B., Vione, D., and Gligorovski, S.: Ionic strength effects on the photochemical degradation of acetosyringone in atmospheric deliquescent aerosol particles, Atmos. Environ., 198, 83–88, https://doi.org/10.1016/j.atmosenv.2018.10.047, 2019.
Zhu, Y., Tilgner, A., Hoffmann, E. H., Herrmann, H., Kawamura, K., Yang, L., Xue, L., and Wang, W.: Multiphase MCM–CAPRAM modeling of the formation and processing of secondary aerosol constituents observed during the Mt. Tai summer campaign in 2014, Atmos. Chem. Phys., 20, 6725–6747, https://doi.org/10.5194/acp-20-6725-2020, 2020.
Short summary
This article reports the results of the kinetic measurements for the aqueous oxidation of the 29 aliphatic alcohols by hydroxyl radical (OH) at different temperatures. The data acquired and the literature data were used to optimize a model for predicting the aqueous OH reactivity of alcohols and carboxylic acids and to estimate the atmospheric lifetimes of five terpenoic alcohols. The kinetic data provided new insights into the mechanism of aqueous oxidation of aliphatic molecules by the OH.
This article reports the results of the kinetic measurements for the aqueous oxidation of the 29...
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