Articles | Volume 22, issue 22
https://doi.org/10.5194/acp-22-14589-2022
© Author(s) 2022. 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-22-14589-2022
© Author(s) 2022. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
17 Nov 2022
Research article |
| 17 Nov 2022
| 17 Nov 2022
Atmospheric breakdown chemistry of the new “green” solvent 2,2,5,5-tetramethyloxolane via gas-phase reactions with OH and Cl radicals
Caterina Mapelli
Department of Chemistry, University of York, York, YO10 5DD, UK
Juliette V. Schleicher
Department of Chemistry, University of York, York, YO10 5DD, UK
now at: École Polytechnique Fédérale de Lausanne, 1015 Lausanne,
Switzerland
Alex Hawtin
Department of Chemistry, University of York, York, YO10 5DD, UK
Conor D. Rankine
Department of Chemistry, University of York, York, YO10 5DD, UK
Department of Chemistry, Newcastle University, Newcastle upon Tyne,
NE1 7RU, UK
Fiona C. Whiting
Department of Chemistry, University of York, York, YO10 5DD, UK
Fergal Byrne
Department of Chemistry, University of York, York, YO10 5DD, UK
Department of Chemistry, Maynooth University, Maynooth, Co. Kildare,
W23 F2H6, Ireland
C. Rob McElroy
Department of Chemistry, University of York, York, YO10 5DD, UK
Claudiu Roman
Faculty of Chemistry, “Alexandru Ioan Cuza” University of Iasi, 11th Carol I, 700506,
Iasi, Romania
Integrated Center of Environmental Science Studies in the North
Eastern Region – CERNESIM, “Alexandru Ioan Cuza” University of Iasi, 11th Carol I, 700506,
Iasi, Romania
Cecilia Arsene
Faculty of Chemistry, “Alexandru Ioan Cuza” University of Iasi, 11th Carol I, 700506,
Iasi, Romania
Integrated Center of Environmental Science Studies in the North
Eastern Region – CERNESIM, “Alexandru Ioan Cuza” University of Iasi, 11th Carol I, 700506,
Iasi, Romania
Romeo I. Olariu
Faculty of Chemistry, “Alexandru Ioan Cuza” University of Iasi, 11th Carol I, 700506,
Iasi, Romania
Integrated Center of Environmental Science Studies in the North
Eastern Region – CERNESIM, “Alexandru Ioan Cuza” University of Iasi, 11th Carol I, 700506,
Iasi, Romania
Iustinian G. Bejan
Faculty of Chemistry, “Alexandru Ioan Cuza” University of Iasi, 11th Carol I, 700506,
Iasi, Romania
Integrated Center of Environmental Science Studies in the North
Eastern Region – CERNESIM, “Alexandru Ioan Cuza” University of Iasi, 11th Carol I, 700506,
Iasi, Romania
Department of Chemistry, University of York, York, YO10 5DD, UK
Related authors
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.
Caterina Mapelli, James K. Donnelly, Úna E. Hogan, Andrew R. Rickard, Abbie T. Robinson, Fergal Byrne, Con Rob McElroy, Basile F. E. Curchod, Daniel Hollas, and Terry J. Dillon
Atmos. Chem. Phys., 23, 7767–7779, https://doi.org/10.5194/acp-23-7767-2023, https://doi.org/10.5194/acp-23-7767-2023, 2023
Short summary
Short summary
Solvents are chemical compounds with countless uses in the chemical industry, and they also represent one of the main sources of pollution in the chemical sector. Scientists are trying to develop new
greensafer solvents which present favourable advantages when compared to traditional solvents. Since the assessment of these green solvents often lacks air quality considerations, this study aims to understand the behaviour of these compounds, investigating their reactivity in the troposphere.
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, James K. Donnelly, Úna E. Hogan, Andrew R. Rickard, Abbie T. Robinson, Fergal Byrne, Con Rob McElroy, Basile F. E. Curchod, Daniel Hollas, and Terry J. Dillon
Atmos. Chem. Phys., 23, 7767–7779, https://doi.org/10.5194/acp-23-7767-2023, https://doi.org/10.5194/acp-23-7767-2023, 2023
Short summary
Short summary
Solvents are chemical compounds with countless uses in the chemical industry, and they also represent one of the main sources of pollution in the chemical sector. Scientists are trying to develop new
greensafer solvents which present favourable advantages when compared to traditional solvents. Since the assessment of these green solvents often lacks air quality considerations, this study aims to understand the behaviour of these compounds, investigating their reactivity in the troposphere.
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, Rodrigo Gastón Gibilisco, Iustinian Gabriel Bejan, Iulia Patroescu-Klotz, and Peter Wiesen
Atmos. Chem. Phys., 21, 13667–13686, https://doi.org/10.5194/acp-21-13667-2021, https://doi.org/10.5194/acp-21-13667-2021, 2021
Short summary
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.
Cited articles
Andersen, C., Nielsen, O. J., Østerstrøm, F. F., Ausmeel,
S., Nilsson, E. J. K., and Sulbaek Andersen, M. P.: Atmospheric Chemistry of
Tetrahydrofuran, 2-Methyltetrahydrofuran, and 2,5-Dimethyltetrahydrofuran:
Kinetics of Reactions with Chlorine Atoms, OD Radicals, and Ozone, J. Phys.
Chem. A, 120, 7320–7326, https://doi.org/10.1021/acs.jpca.6b06618, 2016.
Anderson, R. S., Huang, L., Iannone, R., and Rudolph, J.: Measurements of
the 12C/13C kinetic isotope effects in the gas-phase reactions of light
alkanes with chlorine atoms, J. Phys. Chem. A, 111, 495–504,
https://doi.org/10.1021/jp064634p, 2007.
Ariya, P. A., Niki, H., Harris, G. W., Anlauf, K. G., and Worthy, D. E. J.:
Polar sunrise experiment 1995: hydrocarbon measurements and tropospheric Cl
and Br-atoms chemistry, Atmos. Environ., 33, 931–938,
https://doi.org/10.1016/S1352-2310(98)00254-4, 1999.
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, 1986.
Atkinson, R. and Arey, J.: Atmospheric Degradation of Volatile Organic
Compounds, Chem. Rev., 103, 4605–4638, https://doi.org/10.1021/cr0206420, 2003.
Atkinson, R. and Aschmann, S. M.: Kinetics of the Gas Phase Reaction of Cl
Atoms with a Series of Organics at 296 & 2 K and Atmospheric Pressure,
Int. J. Chem. Kinet., 17, 33–41, https://doi.org/10.1002/kin.550170105, 1985.
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.
Becke, A. D.: Density functional thermochemistry. 3. The role of exact
exchange, J. Chem. Phys., 98, 5648–5652, https://doi.org/10.1063/1.464913, 1993.
Bloss, C., Wagner, V., Jenkin, M. E., Volkamer, R., Bloss, W. J., Lee, J. D., Heard, D. E., Wirtz, K., Martin-Reviejo, M., Rea, G., Wenger, J. C., and Pilling, M. J.: Development of a detailed chemical mechanism (MCMv3.1) for the atmospheric oxidation of aromatic hydrocarbons, Atmos. Chem. Phys., 5, 641–664, https://doi.org/10.5194/acp-5-641-2005, 2005.
Byrne, F., Forier, B., Bossaert, G., Hoebers, C., Farmer, T. J., Clark, J.
H., and Hunt, A. J.: 2,2,5,5-Tetramethyltetrahydrofuran (TMTHF): a
non-polar, non-peroxide forming ether replacement for hazardous hydrocarbon
solvents, Green Chem., 19, 3671–3678, https://doi.org/10.1039/C7GC01392B, 2017.
Ceacero-Vega, A. A., Ballesteros, B., Albaladejo, J., Bejan, I., and Barnes,
I.: Temperature dependence of the gas-phase reactions of Cl atoms with
propene and 1-butene between
Christianson, M. G., Doner, A. C., Koritzke, A. L., Frandsen, K., and
Rotavera, B.: Vacuum-ultraviolet absorption cross-sections of functionalized
cyclic hydrocarbons: Five-membered rings, J. Quant. Spectrosc. Ra., 258, 107274, https://doi.org/10.1016/j.jqsrt.2020.107274, 2021.
Curtiss, L. A., Redfern, P. C., and Raghavachari, K.: Gaussian-4 theory, J.
Chem. Phys., 126, 124105, https://doi.org/10.1063/1.2436888, 2007.
DeMore, W. B. and Bayes, K. D.: Rate Constants for the Reactions of Hydroxyl
Radical with Several Alkanes, Cycloalkanes, and Dimethyl Ether, J. Phys.
Chem. A, 103, 2649–2654, https://doi.org/10.1021/jp983273d, 1999.
Dillon, T. J., Holscher, D., and Sivakumaran, V.: Kinetics of the reactions
of HO with methanol (210–351 K) and with ethanol (216–368 K), Phys. Chem.
Chem. Phys., 7, 349–355, https://doi.org/10.1039/b413961e, 2005.
ECHA: Toluene – Substance Information,
https://echa.europa.eu/substance-information/-/substanceinfo/100.003.297,
last access: May 2022.
EEA: Air quality in Europe – 2020 report9/2020, https://doi.org/10.2800/786656, 2020.
Frisch, M. J., Trucks, G. W., Schlegel, H. B., Scuseria, G. E., Robb, M. A.,
Cheeseman, J. R., Scalmani, G., Barone, V., Petersson, G. A., Nakatsuji, H.,
Li, X., Caricato, M., Marenich, A. V., Bloino, J., Janesko, B. G., Gomperts,
R., Mennucci, B., Hratchian, H. P., Ortiz, J. V., Izmaylov, A. F.,
Sonnenberg, J. L., Williams, Ding, F., Lipparini, F., Egidi, F., Goings, J.,
Peng, B., Petrone, A., Henderson, T., Ranasinghe, D., Zakrzewski, V. G.,
Gao, J., Rega, N., Zheng, G., Liang, W., Hada, M., Ehara, M., Toyota, K.,
Fukuda, R., Hasegawa, J., Ishida, M., Nakajima, T., Honda, Y., Kitao, O.,
Nakai, H., Vreven, T., Throssell, K., Montgomery Jr., J. A., Peralta, J. E.,
Ogliaro, F., Bearpark, M. J., Heyd, J. J., Brothers, E. N., Kudin, K. N.,
Staroverov, V. N., Keith, T. A., Kobayashi, R., Normand, J., Raghavachari,
K., Rendell, A. P., Burant, J. C., Iyengar, S. S., Tomasi, J., Cossi, M.,
Millam, J. M., Klene, M., Adamo, C., Cammi, R., Ochterski, J. W., Martin, R.
L., Morokuma, K., Farkas, O., Foresman, J. B., and Fox, D. J.: Gaussian 09
Rev. D.01, Gaussian Inc., Wallingford CT, 2009 [code], https://www.gaussian.com (last access: June 2022), 2016.
Giri, B. R. and Roscoe, J. M.: Kinetics of the reactions of Cl atoms with
several ethers, J. Phys. Chem. A, 114, 8369–8375, https://doi.org/10.1021/jp1037409, 2010.
Hansen, D. A., Atkinson, R., and Pitts, J. N.: Rate constants for reaction
of OH radicals with a series of aromatic hydrocarbons, J. Phys. Chem., 79,
1763–1766, https://doi.org/10.1021/j100584a004, 1975.
Hess, W. P. and Tully, F. P.: Hydrogen-Atom Abstraction from Methanol by OH,
J. Am. Chem. Soc., 93, 1944–1947, 1989.
Illes, A., Farkas, M., Zugner, G. L., Novodarszki, G., Mihalyi, M., and
Dobe, S.: Direct and relative rate coefficients for the gas-phase reaction
of OH radicals with 2-methyltetrahydrofuran at room temperature, React.
Kinet. Mech. Catal., 119, 5–18, https://doi.org/10.1007/s11144-016-1037-2, 2016.
Jenkin, M. E., Saunders, S. M., and Pilling, M. J.: The tropospheric
degradation of volatile organic compounds: A protocol for mechanism
development, Atmos. Environ., 31, 81–104, https://doi.org/10.1016/s1352-2310(96)00105-7,
1997.
Jenkin, M. E., Derwent, R. G., and Wallington, T. J.: Photochemical ozone
creation potentials for volatile organic compounds: Rationalization and
estimation, Atmos. Environ., 163, 128–137, https://doi.org/10.1016/j.atmosenv.2017.05.024,
2017.
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.
Jiménez, E., Gilles, M. K., and Ravishankara, A. R.: Kinetics of the
reactions of the hydroxyl radical with CH3OH and C2H5OH
between 235 and 360 K, J. Photochem. Photobiol. A Chem., 157, 237–245,
https://doi.org/10.1016/S1010-6030(03)00073-X, 2003.
Jimenez-Gonzalez, C., Ponder, C. S., Broxterman, Q. B., and Manley, J. B.:
Using the Right Green Yardstick: Why Process Mass Intensity Is Used in the
Pharmaceutical Industry To Drive More Sustainable Processes, Org. Process
Res. Dev., 15, 912–917, https://doi.org/10.1021/op200097d, 2011.
Lee, C. T., Yang, W. T., and Parr, R. G.: Development of the Colle-Salvetti
correlation-energy formula into a functional of the electron-density, Phys.
Rev. B, 37, 785–789, https://doi.org/10.1103/PhysRevB.37.785, 1988.
Lelieveld, J., Gromov, S., Pozzer, A., and Taraborrelli, D.: Global tropospheric hydroxyl distribution, budget and reactivity, Atmos. Chem. Phys., 16, 12477–12493, https://doi.org/10.5194/acp-16-12477-2016, 2016.
Lelieveld, J., Klingmuller, K., Pozzer, A., Poschl, U., Fnais, M., Daiber,
A., and Munzel, T.: Cardiovascular disease burden from ambient air pollution
in Europe reassessed using novel hazard ratio functions, Eur. Heart J., 40,
1590–1596, https://doi.org/10.1093/eurheartj/ehz135, 2019.
Li, M. Z., Karu, E., Brenninkmeijer, C., Fischer, H., Lelieveld, J., and
Williams, J.: Tropospheric OH and stratospheric OH and Cl concentrations
determined from CH4, CH3Cl, and SF6 measurements, NPJ Clim. Atmos., 1, 29,
https://doi.org/10.1038/s41612-018-0041-9, 2018.
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.
Montgomery, J. A., Frisch, M. J., Ochterski, J. W., and Petersson, G. A.: A
complete basis set model chemistry. VI. Use of density functional geometries
and frequencies, J. Chem. Phys., 110, 2822–2827, https://doi.org/10.1063/1.477924, 1999.
Moriarty, J., Sidebottom, H., Wenger, J., Mellouki, A., and Le Bras, G.:
Kinetic Studies on the Reactions of Hydroxyl Radicals with Cyclic Ethers and
Aliphatic Diethers, J. Phys. Chem. A, 107, 1499–1505, https://doi.org/10.1021/jp021267i,
2003.
Roman, C., Arsene, C., Bejan, I. G., and Olariu, R. I.: Investigations into the gas-phase photolysis and OH radical kinetics of nitrocatechols: implications of intramolecular interactions on their atmospheric behaviour, Atmos. Chem. Phys., 22, 2203–2219, https://doi.org/10.5194/acp-22-2203-2022, 2022.
Saunders, S. M., Jenkin, M. E., Derwent, R. G., and Pilling, M. J.: World
wide web site of a master chemical mechanism (MCM) for use in tropospheric
chemistry models, Atmos. Environ., 31, 1249, https://doi.org/10.1016/S1352-2310(97)85197-7, 1997.
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, https://doi.org/10.5194/acp-3-161-2003, 2003.
Shannon, R. J., Blitz, M. A., Goddard, A., and Heard, D. E.: Accelerated
chemistry in the reaction between the hydroxyl radical and methanol at
interstellar temperatures facilitated by tunnelling, Nat. Chem., 5, 745–749,
https://doi.org/10.1038/nchem.1692, 2013.
Taylor, W. D., Allston, T. D., Moscato, M. J., Fazekas, G. B., Kozlowski,
R., and Takacs, G. A.: Atmospheric photo-dissociation lifetimes for
nitromethane, methyl nitrite and methyl nitrate, Int. J. Chem. Kinet., 12,
231–240, https://doi.org/10.1002/kin.550120404, 1980.
Thornton, J. A., Kercher, J. P., Riedel, T. P., Wagner, N. L., Cozic, J.,
Holloway, J. S., Dube, W. P., Wolfe, G. M., Quinn, P. K., Middlebrook, A.
M., Alexander, B., and Brown, S. S.: A large atomic chlorine source inferred
from mid-continental reactive nitrogen chemistry, Nature, 464, 271–274,
https://doi.org/10.1038/nature08905, 2010.
Wallington, T. J., Dagaut, P., Liu, R., and Kurylo, M. J.: Rate constants
for the gas phase reactions of OH with C5 through C7 aliphatic alcohols and
ethers: Predicted and experimental values, Int. J. Chem. Kinet., 20,
541–547, https://doi.org/10.1002/kin.550200704, 1988.
Wallington, T. J., Ninomiya, Y., Mashino, M., Kawasaki, M., Orkin, V. L.,
Huie, R. E., and Kurylo, M. J.: Atmospheric oxidation mechanism of methyl
pivalate, (CH3)(3)CC(O)OCH3, J. Phys. Chem. A, 105,
7225–7235, https://doi.org/10.1021/jp010308s, 2001.
Wollenhaupt, M., Carl, S. A., Horowitz, A., and Crowley, J. N.: Rate
Coefficients for Reaction of OH with Acetone between 202 and 395 K, J. Phys.
Chem. A, 104, 2695–2705, https://doi.org/10.1021/jp993738f, 2000.
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.
Solvents represent an important source of pollution from the chemical industry. New "green"...
Altmetrics
Final-revised paper
Preprint