Articles | Volume 23, issue 23
https://doi.org/10.5194/acp-23-15135-2023
© Author(s) 2023. 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-23-15135-2023
© Author(s) 2023. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
08 Dec 2023
Research article |
| 08 Dec 2023
| 08 Dec 2023
Direct formation of HONO through aqueous-phase photolysis of organic nitrates
Juan Miguel González-Sánchez
CORRESPONDING AUTHOR
Aix Marseille Univ, CNRS, LCE, Marseille, France
Aix Marseille Univ, CNRS, ICR, Marseille, France
Miquel Huix-Rotllant
Aix Marseille Univ, CNRS, ICR, Marseille, France
Nicolas Brun
Aix Marseille Univ, CNRS, LCE, Marseille, France
Aix Marseille Univ, CNRS, ICR, Marseille, France
Julien Morin
Aix Marseille Univ, CNRS, LCE, Marseille, France
Carine Demelas
Aix Marseille Univ, CNRS, LCE, Marseille, France
Amandine Durand
Aix Marseille Univ, CNRS, LCE, Marseille, France
Sylvain Ravier
Aix Marseille Univ, CNRS, LCE, Marseille, France
Jean-Louis Clément
Aix Marseille Univ, CNRS, ICR, Marseille, France
Anne Monod
CORRESPONDING AUTHOR
Aix Marseille Univ, CNRS, LCE, Marseille, France
Related authors
Juan Miguel González-Sánchez, Nicolas Brun, Junteng Wu, Sylvain Ravier, Jean-Louis Clément, and Anne Monod
Atmos. Chem. Phys., 23, 5851–5866, https://doi.org/10.5194/acp-23-5851-2023, https://doi.org/10.5194/acp-23-5851-2023, 2023
Short summary
Short summary
Organic nitrates play a crucial role in air pollution, as they are NOx reservoirs. This work investigated for the first time their reactivity with light in the aqueous phase (cloud and fog and wet aerosol), proving it slower than in the gas phase. Therefore, our findings reveal that partitioning of organic nitrates in the aqueous phase leads to longer atmospheric lifetimes of these compounds and thus a broader spatial distribution of their related pollution.
Junteng Wu, Nicolas Brun, Juan Miguel González-Sánchez, Badr R'Mili, Brice Temime Roussel, Sylvain Ravier, Jean-Louis Clément, and Anne Monod
Atmos. Meas. Tech., 15, 3859–3874, https://doi.org/10.5194/amt-15-3859-2022, https://doi.org/10.5194/amt-15-3859-2022, 2022
Short summary
Short summary
This work quantified and tentatively identified the organic impurities on ammonium sulfate aerosols generated in the laboratory. They are likely low volatile and high mass molecules containing oxygen, nitrogen, and/or sulfur. Our results show that these organic impurities likely originate from the commercial AS crystals. It is recommended to use AS seeds with caution, especially when small particles are used, in terms of AS purity and water purity when aqueous solutions are used for atomization.
Juan Miguel González-Sánchez, Nicolas Brun, Junteng Wu, Julien Morin, Brice Temime-Roussel, Sylvain Ravier, Camille Mouchel-Vallon, Jean-Louis Clément, and Anne Monod
Atmos. Chem. Phys., 21, 4915–4937, https://doi.org/10.5194/acp-21-4915-2021, https://doi.org/10.5194/acp-21-4915-2021, 2021
Short summary
Short summary
Organic nitrates play a crucial role in air pollution as they are considered NOx reservoirs. This work lights up the importance of their reactions with OH radicals in the aqueous phase (cloud/fog, wet aerosol), which is slower than in the gas phase. For compounds that significantly partition in water such as polyfunctional biogenic nitrates, these aqueous-phase reactions should drive their atmospheric removal, leading to a broader spatial distribution of NOx than previously accounted for.
Chiara Giorio, Anne Monod, Valerio Di Marco, Pierre Herckes, Denise Napolitano, Amy Sullivan, Gautier Landrot, Daniel Warnes, Marika Nasti, Sara D'Aronco, Agathe Gérardin, Nicolas Brun, Karine Desboeufs, Sylvain Triquet, Servanne Chevaillier, Claudia Di Biagio, Francesco Battaglia, Frédéric Burnet, Stuart J. Piketh, Andreas Namwoonde, Jean-François Doussin, and Paola Formenti
Atmos. Chem. Phys., 25, 16107–16125, https://doi.org/10.5194/acp-25-16107-2025, https://doi.org/10.5194/acp-25-16107-2025, 2025
Short summary
Short summary
We present a comparison between concentrations of dissolved trace metals in pairs of total suspended particulate (TSP) and fog samples collected in Henties Bay, Namibia, during the AErosols, Radiation and CLOuds in southern Africa (AEROCLO-sA) field campaign. We found enhanced concentrations of dissolved metals in fog samples, which we attributed to metal–ligand complex formation in the early stages of particle activation into droplets that can then remain in a kinetically stable form in fog or lead to the formation of colloidal nanoparticles.
Julie Camman, Benjamin Chazeau, Nicolas Marchand, Amandine Durand, Grégory Gille, Ludovic Lanzi, Jean-Luc Jaffrezo, Henri Wortham, and Gaëlle Uzu
Atmos. Chem. Phys., 24, 3257–3278, https://doi.org/10.5194/acp-24-3257-2024, https://doi.org/10.5194/acp-24-3257-2024, 2024
Short summary
Short summary
Fine particle (PM1) pollution is a major health issue in the city of Marseille, which is subject to numerous pollution sources. Sampling carried out during the summer enabled a fine characterization of the PM1 sources and their oxidative potential, a promising new metric as a proxy for health impact. PM1 came mainly from combustion sources, secondary ammonium sulfate, and organic nitrate, while the oxidative potential of PM1 came from these sources and from resuspended dust in the atmosphere.
Anil Kumar Mandariya, Junteng Wu, Anne Monod, Paola Formenti, Bénédicte Picquet-Varrault, Mathieu Cazaunau, Stephan Mertes, Laurent Poulain, Antonin Berge, Edouard Pangui, Andreas Tilgner, Thomas Schaefer, Liang Wen, Hartmut Herrmann, and Jean-François Doussin
Atmos. Meas. Tech. Discuss., https://doi.org/10.5194/amt-2023-206, https://doi.org/10.5194/amt-2023-206, 2024
Publication in AMT not foreseen
Short summary
Short summary
An optimized and controlled protocol for generating quasi-adiabatic expansion clouds under simulated dark and light conditions was presented. The irradiated clouds clearly showed a gradual activation of seed particles into droplets. In contrast, non-irradiated clouds faced a flash activation. This paper will lay the foundation for multiphase photochemical studies implying water-soluble volatile organic compounds and particulate matter formation during cloud formation-evaporation cycles.
Juan Miguel González-Sánchez, Nicolas Brun, Junteng Wu, Sylvain Ravier, Jean-Louis Clément, and Anne Monod
Atmos. Chem. Phys., 23, 5851–5866, https://doi.org/10.5194/acp-23-5851-2023, https://doi.org/10.5194/acp-23-5851-2023, 2023
Short summary
Short summary
Organic nitrates play a crucial role in air pollution, as they are NOx reservoirs. This work investigated for the first time their reactivity with light in the aqueous phase (cloud and fog and wet aerosol), proving it slower than in the gas phase. Therefore, our findings reveal that partitioning of organic nitrates in the aqueous phase leads to longer atmospheric lifetimes of these compounds and thus a broader spatial distribution of their related pollution.
Junteng Wu, Nicolas Brun, Juan Miguel González-Sánchez, Badr R'Mili, Brice Temime Roussel, Sylvain Ravier, Jean-Louis Clément, and Anne Monod
Atmos. Meas. Tech., 15, 3859–3874, https://doi.org/10.5194/amt-15-3859-2022, https://doi.org/10.5194/amt-15-3859-2022, 2022
Short summary
Short summary
This work quantified and tentatively identified the organic impurities on ammonium sulfate aerosols generated in the laboratory. They are likely low volatile and high mass molecules containing oxygen, nitrogen, and/or sulfur. Our results show that these organic impurities likely originate from the commercial AS crystals. It is recommended to use AS seeds with caution, especially when small particles are used, in terms of AS purity and water purity when aqueous solutions are used for atomization.
Patrick Chazette, Cyrille Flamant, Harald Sodemann, Julien Totems, Anne Monod, Elsa Dieudonné, Alexandre Baron, Andrew Seidl, Hans Christian Steen-Larsen, Pascal Doira, Amandine Durand, and Sylvain Ravier
Atmos. Chem. Phys., 21, 10911–10937, https://doi.org/10.5194/acp-21-10911-2021, https://doi.org/10.5194/acp-21-10911-2021, 2021
Short summary
Short summary
To gain understanding on the vertical structure of atmospheric water vapour above mountain lakes and to assess its link to the isotopic composition of the lake water and small-scale dynamics, the L-WAIVE field campaign was conducted in the Annecy valley in the French Alps in June 2019. Based on a synergy between ground-based, boat-borne, and airborne measuring platforms, significant gradients of isotopic content have been revealed at the transitions to the lake and to the free troposphere.
Juan Miguel González-Sánchez, Nicolas Brun, Junteng Wu, Julien Morin, Brice Temime-Roussel, Sylvain Ravier, Camille Mouchel-Vallon, Jean-Louis Clément, and Anne Monod
Atmos. Chem. Phys., 21, 4915–4937, https://doi.org/10.5194/acp-21-4915-2021, https://doi.org/10.5194/acp-21-4915-2021, 2021
Short summary
Short summary
Organic nitrates play a crucial role in air pollution as they are considered NOx reservoirs. This work lights up the importance of their reactions with OH radicals in the aqueous phase (cloud/fog, wet aerosol), which is slower than in the gas phase. For compounds that significantly partition in water such as polyfunctional biogenic nitrates, these aqueous-phase reactions should drive their atmospheric removal, leading to a broader spatial distribution of NOx than previously accounted for.
Evangelia Kostenidou, Alvaro Martinez-Valiente, Badr R'Mili, Baptiste Marques, Brice Temime-Roussel, Amandine Durand, Michel André, Yao Liu, Cédric Louis, Boris Vansevenant, Daniel Ferry, Carine Laffon, Philippe Parent, and Barbara D'Anna
Atmos. Chem. Phys., 21, 4779–4796, https://doi.org/10.5194/acp-21-4779-2021, https://doi.org/10.5194/acp-21-4779-2021, 2021
Short summary
Short summary
Passenger vehicle emissions can be a significant source of particulate matter in urban areas. In this study the particle-phase emissions of seven Euro 5 passenger vehicles were characterized. Changes in engine technologies and after-treatment devices can alter the chemical composition and the size of the emitted particulate matter. The condition of the diesel particle filter (DPF) plays an important role in the emitted pollutants.
Cited articles
Bonfrate, S., Ferré, N., and Huix-Rotllant, M.: An efficient electrostatic embedding QM/MM method using periodic boundary conditions based on particle-mesh Ewald sums and electrostatic potential fitted charge operators, J. Chem. Phys., 158, 21101, https://doi.org/10.1063/5.0133646, 2023.
Brun, N., González-Sánchez, J. M., Demelas, C., Clément, J.-L., and Monod, A.: A fast and efficient method for the analysis of α-dicarbonyl compounds in aqueous solutions: Development and application, Chemosphere, 137977, https://doi.org/10.1016/J.CHEMOSPHERE.2023.137977, 2023.
Carbajo, P. G. and Orr-Ewing, A. J.: NO2 quantum yields from ultraviolet photodissociation of methyl and isopropyl nitrate, Phys. Chem. Chem. Phys., 12, 6084–6091, https://doi.org/10.1039/c001425g, 2010.
Darer, A. I., Cole-Filipiak, N. C., O'Connor, A. E., and Elrod, M. J.: Formation and stability of atmospherically relevant isoprene-derived organosulfates and organonitrates, Environ. Sci. Technol., 45, 1895–1902, https://doi.org/10.1021/es103797z, 2011.
Finlayson-Pitts, B. J. and Pitts Jr., J. N.: Chemistry of the Upper and Lower Atmosphere, Academic P., Elsevier, https://doi.org/10.1016/b978-0-12-257060-5.x5000-x, 2000.
Fischer, M. and Warneck, P.: Photodecomposition of nitrite and undissociated nitrous acid in aqueous solution, J. Phys. Chem., 100, 18749–18756, https://doi.org/10.1021/jp961692+, 1996.
Goldstein, S., Lind, J., and Merenyi, G.: Reaction of Organic Peroxyl Radicals with NO2 and NO in Aqueous Solution: Intermediacy of Organic Peroxynitrate and Peroxynitrite Species, J. Phys. Chem. A, 108, 1719–1725, https://doi.org/10.1021/jp037431z, 2004.
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.
González-Sánchez, J. M., Brun, N., Wu, J., Ravier, S., Clément, J.-L., and Monod, A.: On the importance of multiphase photolysis of organic nitrates on their global atmospheric removal, Atmos. Chem. Phys., 23, 5851–5866, https://doi.org/10.5194/acp-23-5851-2023, 2023a.
González-Sánchez, J. M., Huix-Rotllant, M., Brun, N., Morin, J., Demelas, C., Durand, A., Ravier, S., Clément, J.-L., and Monod, A.: Replication Data for: Direct formation of HONO through aqueous-phase photolysis of organic nitrates, V1, Harvard Dataverse [data set], https://doi.org/10.7910/DVN/USWU6V, 2023b.
Hu, K. S., Darer, A. I., and Elrod, M. J.: Thermodynamics and kinetics of the hydrolysis of atmospherically relevant organonitrates and organosulfates, Atmos. Chem. Phys., 11, 8307–8320, https://doi.org/10.5194/acp-11-8307-2011, 2011.
Huix-Rotllant, M., Schwinn, K., Pomogaev, V., Farmani, M., Ferré, N., Lee, S., and Choi, C. H.: Photochemistry of Thymine in Solution and DNA Revealed by an Electrostatic Embedding QM/MM Combined with Mixed-Reference Spin-Flip TDDFT, J. Chem. Theory Comput., 19, 147–156, https://doi.org/10.1021/acs.jctc.2c01010, 2023.
Kiendler-Scharr, A., Mensah, A. A., Friese, E., Topping, D., Nemitz, E., Prevot, A. S. H., Äijälä, M., Allan, J., Canonaco, F., Canagaratna, M., Carbone, S., Crippa, M., Dall Osto, M., Day, D. A., De Carlo, P., Di Marco, C. F., Elbern, H., Eriksson, A., Freney, E., Hao, L., Herrmann, H., Hildebrandt, L., Hillamo, R., Jimenez, J. L., Laaksonen, A., McFiggans, G., Mohr, C., O'Dowd, C., Otjes, R., Ovadnevaite, J., Pandis, S. N., Poulain, L., Schlag, P., Sellegri, K., Swietlicki, E., Tiitta, P., Vermeulen, A., Wahner, A., Worsnop, D., and Wu, H. C.: Ubiquity of organic nitrates from nighttime chemistry in the European submicron aerosol, Geophys. Res. Lett., 43, 7735–7744, https://doi.org/10.1002/2016GL069239, 2016.
Kim, D. H., Lee, J., Ryu, J., Kim, K., and Choi, W.: Arsenite oxidation initiated by the uv photolysis of nitrite and nitrate, Environ. Sci. Technol., 48, 4030–4037, https://doi.org/10.1021/es500001q, 2014.
Lee, S., Filatov, M., Lee, S., and Choi, C. H.: Eliminating spin-contamination of spin-flip time dependent density functional theory within linear response formalism by the use of zeroth-order mixed-reference (MR) reduced density matrix, J. Chem. Phys., 149, 104101, https://doi.org/10.1063/1.5044202, 2018.
Mack, J. and Bolton, J. R.: Photochemistry of nitrite and nitrate in aqueous solution: a review, J. Photochem. Photobiol. A Chem., 128, 1–13, https://doi.org/10.1016/S1010-6030(99)00155-0, 1999.
Ng, N. L., Brown, S. S., Archibald, A. T., Atlas, E., Cohen, R. C., Crowley, J. N., Day, D. A., Donahue, N. M., Fry, J. L., Fuchs, H., Griffin, R. J., Guzman, M. I., Herrmann, H., Hodzic, A., Iinuma, Y., Jimenez, J. L., Kiendler-Scharr, A., Lee, B. H., Luecken, D. J., Mao, J., McLaren, R., Mutzel, A., Osthoff, H. D., Ouyang, B., Picquet-Varrault, B., Platt, U., Pye, H. O. T., Rudich, Y., Schwantes, R. H., Shiraiwa, M., Stutz, J., Thornton, J. A., Tilgner, A., Williams, B. J., and Zaveri, R. A.: Nitrate radicals and biogenic volatile organic compounds: oxidation, mechanisms, and organic aerosol, Atmos. Chem. Phys., 17, 2103–2162, https://doi.org/10.5194/acp-17-2103-2017, 2017.
Nguyen, T. B., Crounse, J. D., Teng, A. P., Clair, J. M. S., Paulot, F., Wolfe, G. M., and Wennberg, P. O.: Rapid deposition of oxidized biogenic compounds to a temperate forest, P. Natl. Acad. Sci. USA, 112, E392–E401, https://doi.org/10.1073/pnas.1418702112, 2015.
Perring, A. E., Pusede, S. E., and Cohen, R. C.: An observational perspective on the atmospheric impacts of alkyl and multifunctional nitrates on ozone and secondary organic aerosol, Chem. Rev., 113, 5848–5870, https://doi.org/10.1021/cr300520x, 2013.
Poulain, L., Katrib, Y., Isikli, E., Liu, Y., Wortham, H., Mirabel, P., Le Calvé, S., and Monod, A.: In-cloud multiphase behaviour of acetone in the troposphere: Gas uptake, Henry's law equilibrium and aqueous phase photooxidation, Chemosphere, 81, 312–320, https://doi.org/10.1016/j.chemosphere.2010.07.032, 2010.
Rindelaub, J. D., McAvey, K. M., and Shepson, P. B.: The photochemical production of organic nitrates from α-pinene and loss via acid-dependent particle phase hydrolysis, Atmos. Environ., 100, 193–201, https://doi.org/10.1016/j.atmosenv.2014.11.010, 2015.
Romer Present, P. S., Zare, A., and Cohen, R. C.: The changing role of organic nitrates in the removal and transport of NOx, Atmos. Chem. Phys., 20, 267–279, https://doi.org/10.5194/acp-20-267-2020, 2020.
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.
Shepson, P. B.: Organic nitrates, Blackwell Publishing Ltd, Oxford, UK, 58–63 pp., https://doi.org/10.1358/dnp.1999.12.1.863615, 1999.
Takeuchi, M. and Ng, N. L.: Organic nitrates and secondary organic aerosol (SOA) formation from oxidation of biogenic volatile organic compounds, in: ACS Symposium Series, vol. 1299, American Chemical Society, 105–125, https://doi.org/10.1021/bk-2018-1299.ch006, 2018.
Talukdar, R. K., Burkholder, J. B., Hunter, M., Gilles, M. K., Roberts, J. M., and Ravishankara, A. R.: Atmospheric fate of several alkyl nitrates: Part 2. UV absorption cross-sections and photodissociation quantum yields, J. Chem. Soc. – Faraday Transactions, 93, 2797–2805, https://doi.org/10.1039/a701781b, 1997.
Vione, D., Belmondo, S., and Carnino, L.: A kinetic study of phenol nitration and nitrosation with nitrous acid in the dark, Environ. Chem. Lett., 2, 135–139, https://doi.org/10.1007/s10311-004-0088-1, 2004.
Wang, Y., Piletic, I. R., Takeuchi, M., Xu, T., France, S., and Ng, N. L.: Synthesis and Hydrolysis of Atmospherically Relevant Monoterpene-Derived Organic Nitrates, Environ. Sci. Technol., 55, 14595–14606, https://doi.org/10.1021/acs.est.1c05310, 2021.
Short summary
Organic nitrates play a crucial role in air pollution, as they are nitrogen oxide (NOx) reservoirs. This work investigated the reaction products and mechanisms of their reactivity with light in the aqueous phase (cloud and fog conditions and wet aerosol). Our findings reveal that this chemistry leads to the formation of atmospheric nitrous acid (HONO).
Organic nitrates play a crucial role in air pollution, as they are nitrogen oxide (NOx)...
Altmetrics
Final-revised paper
Preprint