Articles | Volume 3, issue 2
https://doi.org/10.5194/ar-3-417-2025
© Author(s) 2025. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
https://doi.org/10.5194/ar-3-417-2025
© Author(s) 2025. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
A theory-informed, experiment-based constraint on the rate of autoxidation chemistry – an analytical approach
Lukas Pichelstorfer
CORRESPONDING AUTHOR
pi-numerics, Neumarkt am Wallersee, 5202, Austria
Institute for Atmospheric and Earth System Research/Physics, University of Helsinki, 00560 Helsinki, Finland
Simon P. O'Meara
Department of Earth and Environmental Sciences, University of Manchester, Manchester M13 9PL, UK
National Centre for Atmospheric Science, Leeds LS2 9PH, UK
Gordon McFiggans
Department of Earth and Environmental Sciences, University of Manchester, Manchester M13 9PL, UK
Related authors
Lukas Pichelstorfer, Pontus Roldin, Matti Rissanen, Noora Hyttinen, Olga Garmash, Carlton Xavier, Putian Zhou, Petri Clusius, Benjamin Foreback, Thomas Golin Almeida, Chenjuan Deng, Metin Baykara, Theo Kurten, and Michael Boy
EGUsphere, https://doi.org/10.5194/egusphere-2023-1415, https://doi.org/10.5194/egusphere-2023-1415, 2023
Preprint archived
Short summary
Short summary
Secondary organic aerosols (SOA) form effectively from gaseous precursors via a process called autoxidation. While key chemical reaction types seem to be known, no general description of autoxidation chemistry exists. In the present work, we present a method to create autoxidation chemistry schemes for any atmospherically relevant hydrocarbon. We exemplarily investigate benzene and its potential to form aerosols. We found that autoxidation, under some conditions, can dominate the SOA formation.
Yunqi Shao, Aristeidis Voliotis, Mao Du, Yu Wang, Jacqueline Hamilton, M. Rami Alfarra, and Gordon McFiggans
Aerosol Research Discuss., https://doi.org/10.5194/ar-2025-22, https://doi.org/10.5194/ar-2025-22, 2025
Preprint under review for AR
Short summary
Short summary
This study analysed the average carbon oxidation state (OSc) during secondary organic aerosol formation from mixed volatile organic compounds (VOCs) using three mass spectrometry techniques. Notable discrepancies in OSc were observed across the techniques, with FIGAERO-CIMS keep reporting higher values. The results also shown that OSc in mixed VOC systems is influenced not only by products from individual precursors but also by unique compounds formed through interactions between VOC products.
Olivia M. Jackson, Aristeidis Voliotis, Thomas J. Bannan, Simon P. O'Meara, Gordon McFiggans, Dave Johnson, and Hugh Coe
Atmos. Chem. Phys., 25, 6257–6272, https://doi.org/10.5194/acp-25-6257-2025, https://doi.org/10.5194/acp-25-6257-2025, 2025
Short summary
Short summary
This paper details a novel method of measuring the volatility of pesticides using the Filter Inlet for Gases and AEROsols coupled with a chemical ionisation mass spectrometer (FIGAERO-CIMS) calibrated using a set of poly(ethylene) glycols. This is compared to literature values and common models. The results show that the method used primarily matches current literature values. Additionally, a pesticide’s volatility as an indicator of the likelihood of atmospheric transport occurring is explored.
Rhianna L. Evans, Daniel J. Bryant, Aristeidis Voliotis, Dawei Hu, Huihui Wu, Sara Aisyah Syafira, Osayomwanbor E. Oghama, Gordon McFiggans, Jacqueline F. Hamilton, and Andrew R. Rickard
Atmos. Chem. Phys., 25, 4367–4389, https://doi.org/10.5194/acp-25-4367-2025, https://doi.org/10.5194/acp-25-4367-2025, 2025
Short summary
Short summary
The chemical composition of organic aerosol derived from wood-burning emissions under different burning conditions was characterised. Fresh emissions from flaming and smouldering were largely aromatic in nature, whereas upon aging the aromatic content decreased. This decrease was greater for smouldering due to the loss of toxic polyaromatic species, whereas under flaming conditions highly toxic polyaromatic species were produced. These differences present an important challenge for future policy.
Yarê Baker, Sungah Kang, Hui Wang, Rongrong Wu, Jian Xu, Annika Zanders, Quanfu He, Thorsten Hohaus, Till Ziehm, Veronica Geretti, Thomas J. Bannan, Simon P. O'Meara, Aristeidis Voliotis, Mattias Hallquist, Gordon McFiggans, Sören R. Zorn, Andreas Wahner, and Thomas F. Mentel
Atmos. Chem. Phys., 24, 4789–4807, https://doi.org/10.5194/acp-24-4789-2024, https://doi.org/10.5194/acp-24-4789-2024, 2024
Short summary
Short summary
Highly oxygenated organic molecules are important contributors to secondary organic aerosol. Their yield depends on detailed atmospheric chemical composition. One important parameter is the ratio of hydroperoxy radicals to organic peroxy radicals (HO2/RO2), and we show that higher HO2/RO2 ratios lower the secondary organic aerosol yield. This is of importance as laboratory studies are often biased towards organic peroxy radicals.
Lukas Pichelstorfer, Pontus Roldin, Matti Rissanen, Noora Hyttinen, Olga Garmash, Carlton Xavier, Putian Zhou, Petri Clusius, Benjamin Foreback, Thomas Golin Almeida, Chenjuan Deng, Metin Baykara, Theo Kurten, and Michael Boy
EGUsphere, https://doi.org/10.5194/egusphere-2023-1415, https://doi.org/10.5194/egusphere-2023-1415, 2023
Preprint archived
Short summary
Short summary
Secondary organic aerosols (SOA) form effectively from gaseous precursors via a process called autoxidation. While key chemical reaction types seem to be known, no general description of autoxidation chemistry exists. In the present work, we present a method to create autoxidation chemistry schemes for any atmospherically relevant hydrocarbon. We exemplarily investigate benzene and its potential to form aerosols. We found that autoxidation, under some conditions, can dominate the SOA formation.
Ernesto Reyes-Villegas, Douglas Lowe, Jill S. Johnson, Kenneth S. Carslaw, Eoghan Darbyshire, Michael Flynn, James D. Allan, Hugh Coe, Ying Chen, Oliver Wild, Scott Archer-Nicholls, Alex Archibald, Siddhartha Singh, Manish Shrivastava, Rahul A. Zaveri, Vikas Singh, Gufran Beig, Ranjeet Sokhi, and Gordon McFiggans
Atmos. Chem. Phys., 23, 5763–5782, https://doi.org/10.5194/acp-23-5763-2023, https://doi.org/10.5194/acp-23-5763-2023, 2023
Short summary
Short summary
Organic aerosols (OAs), their sources and their processes remain poorly understood. The volatility basis set (VBS) approach, implemented in air quality models such as WRF-Chem, can be a useful tool to describe primary OA (POA) production and aging. However, the main disadvantage is its complexity. We used a Gaussian process simulator to reproduce model results and to estimate the sources of model uncertainty. We do this by comparing the outputs with OA observations made at Delhi, India, in 2018.
Aristeidis Voliotis, Mao Du, Yu Wang, Yunqi Shao, M. Rami Alfarra, Thomas J. Bannan, Dawei Hu, Kelly L. Pereira, Jaqueline F. Hamilton, Mattias Hallquist, Thomas F. Mentel, and Gordon McFiggans
Atmos. Chem. Phys., 22, 14147–14175, https://doi.org/10.5194/acp-22-14147-2022, https://doi.org/10.5194/acp-22-14147-2022, 2022
Short summary
Short summary
Mixing experiments are crucial and highly beneficial for our understanding of atmospheric chemical interactions. However, interpretation quickly becomes complex, and both the experimental design and evaluation need to be scrutinised carefully. Advanced online and offline compositional measurements can reveal substantial additional information to aid in the interpretation of yield data, including components uniquely found in mixtures and property changes in SOA formed from mixtures of VOCs.
Aristeidis Voliotis, Mao Du, Yu Wang, Yunqi Shao, Thomas J. Bannan, Michael Flynn, Spyros N. Pandis, Carl J. Percival, M. Rami Alfarra, and Gordon McFiggans
Atmos. Chem. Phys., 22, 13677–13693, https://doi.org/10.5194/acp-22-13677-2022, https://doi.org/10.5194/acp-22-13677-2022, 2022
Short summary
Short summary
The addition of a low-yield precursor to the reactive mixture of aVOC and bVOC can increase or decrease the SOA volatility that is system-dependent. Therefore, the SOA volatility of the mixtures cannot always be predicted based on the additivity. In complex mixtures the formation of lower-volatility products likely outweighs the formation of products with higher volatility. The unique products of each mixture contribute significantly to the signal, suggesting interactions can be important.
Yunqi Shao, Aristeidis Voliotis, Mao Du, Yu Wang, Kelly Pereira, Jacqueline Hamilton, M. Rami Alfarra, and Gordon McFiggans
Atmos. Chem. Phys., 22, 9799–9826, https://doi.org/10.5194/acp-22-9799-2022, https://doi.org/10.5194/acp-22-9799-2022, 2022
Short summary
Short summary
This study explored the chemical properties of secondary organic aerosol (SOA) that formed from photo-oxidation of single and mixed biogenic and anthropogenic precursors. We showed that SOA chemical properties in a mixed vapour system are mainly affected by the
higher-yield precursor's oxidation products and products from
cross-product formation. This study also identifies potential tracer compounds in a mixed vapour system that might be used in SOA source attribution in future ambient studies.
Mao Du, Aristeidis Voliotis, Yunqi Shao, Yu Wang, Thomas J. Bannan, Kelly L. Pereira, Jacqueline F. Hamilton, Carl J. Percival, M. Rami Alfarra, and Gordon McFiggans
Atmos. Meas. Tech., 15, 4385–4406, https://doi.org/10.5194/amt-15-4385-2022, https://doi.org/10.5194/amt-15-4385-2022, 2022
Short summary
Short summary
Atmospheric chemistry plays a key role in the understanding of aerosol formation and air pollution. We designed chamber experiments for the characterization of secondary organic aerosol (SOA) from a biogenic precursor with inorganic seed. Our results highlight the advantages of a combination of online FIGAERO-CIMS and offline LC-Orbitrap MS analytical techniques to characterize the chemical composition of SOA in chamber studies.
Yu Wang, Aristeidis Voliotis, Dawei Hu, Yunqi Shao, Mao Du, Ying Chen, Judith Kleinheins, Claudia Marcolli, M. Rami Alfarra, and Gordon McFiggans
Atmos. Chem. Phys., 22, 4149–4166, https://doi.org/10.5194/acp-22-4149-2022, https://doi.org/10.5194/acp-22-4149-2022, 2022
Short summary
Short summary
Aerosol water uptake plays a key role in atmospheric physicochemical processes. We designed chamber experiments on aerosol water uptake of secondary organic aerosol (SOA) from mixed biogenic and anthropogenic precursors with inorganic seed. Our results highlight this chemical composition influences the reconciliation of the sub- and super-saturated water uptake, providing laboratory evidence for understanding the chemical controls of water uptake of the multi-component aerosol.
Jessica Slater, Hugh Coe, Gordon McFiggans, Juha Tonttila, and Sami Romakkaniemi
Atmos. Chem. Phys., 22, 2937–2953, https://doi.org/10.5194/acp-22-2937-2022, https://doi.org/10.5194/acp-22-2937-2022, 2022
Short summary
Short summary
This paper shows the specific impact of black carbon (BC) on the aerosol–planetary boundary layer (PBL) feedback and its influence on a Beijing haze episode. Overall, this paper shows that strong temperature inversions prevent BC heating within the PBL from significantly increasing PBL height, while BC above the PBL suppresses PBL development significantly through the day. From this we suggest a method by which both locally and regionally emitted BC may impact urban pollution episodes.
Yunqi Shao, Yu Wang, Mao Du, Aristeidis Voliotis, M. Rami Alfarra, Simon P. O'Meara, S. Fiona Turner, and Gordon McFiggans
Atmos. Meas. Tech., 15, 539–559, https://doi.org/10.5194/amt-15-539-2022, https://doi.org/10.5194/amt-15-539-2022, 2022
Short summary
Short summary
A comprehensive description and characterisation of the Manchester Aerosol Chamber (MAC) was conducted. The MAC has good temperature and relative humidity homogeneity, fast mixing times, and comparable losses of gases and particles with other chambers. The MAC's bespoke control system allows improved duty cycles and repeatable experiments. Moreover, the effect of contamination on performance was also investigated. It is highly recommended to regularly track the chamber's performance.
Aristeidis Voliotis, Yu Wang, Yunqi Shao, Mao Du, Thomas J. Bannan, Carl J. Percival, Spyros N. Pandis, M. Rami Alfarra, and Gordon McFiggans
Atmos. Chem. Phys., 21, 14251–14273, https://doi.org/10.5194/acp-21-14251-2021, https://doi.org/10.5194/acp-21-14251-2021, 2021
Short summary
Short summary
Secondary organic aerosol (SOA) formation from mixtures of volatile precursors can be affected by the molecular interactions of the products. Composition and volatility measurements of SOA formed from mixtures of anthropogenic and biogenic precursors reveal processes that can increase or decrease the SOA volatility. The unique products of the mixture were more oxygenated and less volatile than those from either precursor. Analytical context is provided to explore the SOA volatility in mixtures.
Ernesto Reyes-Villegas, Upasana Panda, Eoghan Darbyshire, James M. Cash, Rutambhara Joshi, Ben Langford, Chiara F. Di Marco, Neil J. Mullinger, Mohammed S. Alam, Leigh R. Crilley, Daniel J. Rooney, W. Joe F. Acton, Will Drysdale, Eiko Nemitz, Michael Flynn, Aristeidis Voliotis, Gordon McFiggans, Hugh Coe, James Lee, C. Nicholas Hewitt, Mathew R. Heal, Sachin S. Gunthe, Tuhin K. Mandal, Bhola R. Gurjar, Shivani, Ranu Gadi, Siddhartha Singh, Vijay Soni, and James D. Allan
Atmos. Chem. Phys., 21, 11655–11667, https://doi.org/10.5194/acp-21-11655-2021, https://doi.org/10.5194/acp-21-11655-2021, 2021
Short summary
Short summary
This paper shows the first multisite online measurements of PM1 in Delhi, India, with measurements over different seasons in Old Delhi and New Delhi in 2018. Organic aerosol (OA) source apportionment was performed using positive matrix factorisation (PMF). Traffic was the main primary aerosol source for both OAs and black carbon, seen with PMF and Aethalometer model analysis, indicating that control of primary traffic exhaust emissions would make a significant reduction to Delhi air pollution.
Yu Wang, Aristeidis Voliotis, Yunqi Shao, Taomou Zong, Xiangxinyue Meng, Mao Du, Dawei Hu, Ying Chen, Zhijun Wu, M. Rami Alfarra, and Gordon McFiggans
Atmos. Chem. Phys., 21, 11303–11316, https://doi.org/10.5194/acp-21-11303-2021, https://doi.org/10.5194/acp-21-11303-2021, 2021
Short summary
Short summary
Aerosol phase behaviour plays a profound role in atmospheric physicochemical processes. We designed dedicated chamber experiments to study the phase state of secondary organic aerosol from biogenic and anthropogenic mixed precursors. Our results highlight the key role of the organic–inorganic ratio and relative humidity in phase state, but the sources and organic composition are less important. The result provides solid laboratory evidence for understanding aerosol phase in a complex atmosphere.
Michael Priestley, Thomas J. Bannan, Michael Le Breton, Stephen D. Worrall, Sungah Kang, Iida Pullinen, Sebastian Schmitt, Ralf Tillmann, Einhard Kleist, Defeng Zhao, Jürgen Wildt, Olga Garmash, Archit Mehra, Asan Bacak, Dudley E. Shallcross, Astrid Kiendler-Scharr, Åsa M. Hallquist, Mikael Ehn, Hugh Coe, Carl J. Percival, Mattias Hallquist, Thomas F. Mentel, and Gordon McFiggans
Atmos. Chem. Phys., 21, 3473–3490, https://doi.org/10.5194/acp-21-3473-2021, https://doi.org/10.5194/acp-21-3473-2021, 2021
Short summary
Short summary
A significant fraction of emissions from human activity consists of aromatic hydrocarbons, e.g. benzene, which oxidise to form new compounds important for particle growth. Characterisation of benzene oxidation products highlights the range of species produced as well as their chemical properties and contextualises them within relevant frameworks, e.g. MCM. Cluster analysis of the oxidation product time series distinguishes behaviours of CHON compounds that could aid in identifying functionality.
Simon Patrick O'Meara, Shuxuan Xu, David Topping, M. Rami Alfarra, Gerard Capes, Douglas Lowe, Yunqi Shao, and Gordon McFiggans
Geosci. Model Dev., 14, 675–702, https://doi.org/10.5194/gmd-14-675-2021, https://doi.org/10.5194/gmd-14-675-2021, 2021
Short summary
Short summary
User-friendly and open-source software for simulating aerosol chambers is a valuable tool for research scientists in designing and analysing their experiments. This paper describes a new version of such software and will therefore provide a useful reference for those applying it. Central to the paper is an assessment of the software's accuracy through comparison against previously published simulations.
Jessica Slater, Juha Tonttila, Gordon McFiggans, Paul Connolly, Sami Romakkaniemi, Thomas Kühn, and Hugh Coe
Atmos. Chem. Phys., 20, 11893–11906, https://doi.org/10.5194/acp-20-11893-2020, https://doi.org/10.5194/acp-20-11893-2020, 2020
Short summary
Short summary
The feedback effect between aerosol particles, radiation and meteorology reduces turbulent motion and results in increased surface aerosol concentrations during Beijing haze. Observational analysis and regional modelling studies have examined the feedback effect but these studies are limited. In this work, we set up a high-resolution model for the Beijing environment to examine the sensitivity of the aerosol feedback effect to initial meteorological conditions and aerosol loading.
Cited articles
Aumont, B., Szopa, S., and Madronich, S.: Modelling the evolution of organic carbon during its gas-phase tropospheric oxidation: development of an explicit model based on a self generating approach, Atmos. Chem. Phys., 5, 2497–2517, https://doi.org/10.5194/acp-5-2497-2005, 2005.
Bergman, T., Makkonen, R., Schrödner, R., Swietlicki, E., Phillips, V. T. J., Le Sager, P., and van Noije, T.: Description and evaluation of a secondary organic aerosol and new particle formation scheme within TM5-MP v1.2, Geosci. Model Dev., 15, 683–713, https://doi.org/10.5194/gmd-15-683-2022, 2022.
Berndt, T., Mentler, B., Scholz, W., Fischer, L., Herrmann, H., Kulmala, M., and Hansel, A.: Accretion Product Formation from Ozonolysis and OH Radical Reaction of α-Pinene: Mechanistic Insight and the Influence of Isoprene and Ethylene, Environ. Sci. Technol., 52, 11069–11077, https://doi.org/10.1021/acs.est.8b02210, 2018a.
Berndt, T., Scholz, W., Mentler, B., Fischer, L., Herrmann, H., Kulmala, M., and Hansel, A.: Accretion Product Formation from Self- and Cross-Reactions of RO2 Radicals in the Atmosphere, Angew. Chem. Int. Edit., 57, 3820–3824, https://doi.org/10.1002/anie.201710989, 2018b.
Bianchi, F., Kurtén, T., Riva, M., Mohr, C., Rissanen, M. P., Roldin, P., Berndt, T., Crounse, J. D., Wennberg, P. O., Mentel, T. F., Wildt, J., Junninen, H., Jokinen, T., Kulmala, M., Worsnop, D. R., Thornton, J. A., Donahue, N., Kjaergaard, H. G., and Ehn, M.: Highly Oxygenated Organic Molecules (HOM) from Gas-Phase Autoxidation Involving Peroxy Radicals: A Key Contributor to Atmospheric Aerosol, Chem. Rev., 119, 3472–3509, https://doi.org/10.1021/acs.chemrev.8b00395, 2019.
Blake, N. J. and Blake, D. R.: TROPOSPHERIC CHEMISTRY AND COMPOSITION | VOCs: Overview, in: Encyclopedia of Atmospheric Sciences, Elsevier, 2438–2446, https://doi.org/10.1016/B0-12-227090-8/00422-X, 2003.
Camredon, M., Aumont, B., Lee-Taylor, J., and Madronich, S.: The SOA/VOC/NOx system: an explicit model of secondary organic aerosol formation, Atmos. Chem. Phys., 7, 5599–5610, https://doi.org/10.5194/acp-7-5599-2007, 2007.
Clusius, P., Xavier, C., Pichelstorfer, L., Zhou, P., Olenius, T., Roldin, P., and Boy, M.: Atmospherically Relevant Chemistry and Aerosol box model – ARCA box (version 1.2), Geosci. Model Dev., 15, 7257–7286, https://doi.org/10.5194/gmd-15-7257-2022, 2022.
Cox, R. A. and Cole, J. A.: Chemical aspects of the autoignition of hydrocarbon air mixtures, Combust. Flame, 60, 109–123, https://doi.org/10.1016/0010-2180(85)90001-X, 1985.
Crounse, J. D., Nielsen, L. B., Jørgensen, S., Kjaergaard, H. G., and Wennberg, P. O.: Autoxidation of Organic Compounds in the Atmosphere, J. Phys. Chem. Lett., 4, 3513–3520, https://doi.org/10.1021/jz4019207, 2013.
Daellenbach, K. R., Uzu, G., Jiang, J., Cassagnes, L.-E., Leni, Z., Vlachou, A., Stefenelli, G., Canonaco, F., Weber, S., Segers, A., Kuenen, J. J. P., Schaap, M., Favez, O., Albinet, A., Aksoyoglu, S., Dommen, J., Baltensperger, U., Geiser, M., El Haddad, I., Jaffrezo, J.-L., and Prévôt, A. S. H.: Sources of particulate-matter air pollution and its oxidative potential in Europe, Nature, 587, 414–419, https://doi.org/10.1038/s41586-020-2902-8, 2020.
Donahue, N. M., Robinson, A. L., Stanier, C. O., and Pandis, S. N.: Coupled Partitioning, Dilution, and Chemical Aging of Semivolatile Organics, Environ. Sci. Technol., 40, 2635–2643, https://doi.org/10.1021/es052297c, 2006.
Donahue, N. M., Epstein, S. A., Pandis, S. N., and Robinson, A. L.: A two-dimensional volatility basis set: 1. organic-aerosol mixing thermodynamics, Atmos. Chem. Phys., 11, 3303–3318, https://doi.org/10.5194/acp-11-3303-2011, 2011.
Ehn, M., Thornton, J. A., Kleist, E., Sipilä, M., Junninen, H., Pullinen, I., Springer, M., Rubach, F., Tillmann, R., Lee, B., Lopez-Hilfiker, F., Andres, S., Acir, I.-H., Rissanen, M., Jokinen, T., Schobesberger, S., Kangasluoma, J., Kontkanen, J., Nieminen, T., Kurtén, T., Nielsen, L. B., Jørgensen, S., Kjaergaard, H. G., Canagaratna, M., Maso, M. D., Berndt, T., Petäjä, T., Wahner, A., Kerminen, V.-M., Kulmala, M., Worsnop, D. R., Wildt, J., and Mentel, T. F.: A large source of low-volatility secondary organic aerosol, Nature, 506, 476–479, https://doi.org/10.1038/nature13032, 2014.
Franzon, L., Camredon, M., Valorso, R., Aumont, B., and Kurtén, T.: Ether and ester formation from peroxy radical recombination: a qualitative reaction channel analysis, Atmos. Chem. Phys., 24, 11679–11699, https://doi.org/10.5194/acp-24-11679-2024, 2024.
Goldman, M. J., Green, W. H., and Kroll, J. H.: Chemistry of Simple Organic Peroxy Radicals under Atmospheric through Combustion Conditions: Role of Temperature, Pressure, and NOx Level, J. Phys. Chem. A, 125, 10303–10314, https://doi.org/10.1021/acs.jpca.1c07203, 2021.
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, Th. 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.
Hyttinen, N., Otkjær, R. V., Iyer, S., Kjaergaard, H. G., Rissanen, M. P., Wennberg, P. O., and Kurtén, T.: Computational Comparison of Different Reagent Ions in the Chemical Ionization of Oxidized Multifunctional Compounds, J. Phys. Chem. A, 122, 269–279, https://doi.org/10.1021/acs.jpca.7b10015, 2018.
Iyer, S., Kumar, A., Savolainen, A., Barua, S., Daub, C., Pichelstorfer, L., Roldin, P., Garmash, O., Seal, P., Kurtén, T., and Rissanen, M.: Molecular rearrangement of bicyclic peroxy radicals is a key route to aerosol from aromatics, Nat. Commun., 14, 4984, https://doi.org/10.1038/s41467-023-40675-2, 2023.
IPCC: Climate Change 2023: Synthesis Report, Contribution of Working Groups I, II and III to the Sixth Assessment Report of the Intergovernmental Panel on Climate Change, edited by: Core Writing Team, Lee, H., and Romero, J., Intergovernmental Panel on Climate Change (IPCC), Geneva, Switzerland, https://doi.org/10.59327/IPCC/AR6-9789291691647, 2023.
Jenkin, M. E., Saunders, S. M., Wagner, V., and Pilling, M. J.: Protocol for the development of the Master Chemical Mechanism, MCM v3 (Part B): tropospheric degradation of aromatic volatile organic compounds, Atmos. Chem. Phys., 3, 181–193, https://doi.org/10.5194/acp-3-181-2003, 2003.
Jenkin, M. E., Valorso, R., Aumont, B., and Rickard, A. R.: Estimation of rate coefficients and branching ratios for reactions of organic peroxy radicals for use in automated mechanism construction, Atmos. Chem. Phys., 19, 7691–7717, https://doi.org/10.5194/acp-19-7691-2019, 2019.
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., E., 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.
Jokinen, T., Sipilä, M., Junninen, H., Ehn, M., Lönn, G., Hakala, J., Petäjä, T., Mauldin III, R. L., Kulmala, M., and Worsnop, D. R.: Atmospheric sulphuric acid and neutral cluster measurements using CI-APi-TOF, Atmos. Chem. Phys., 12, 4117–4125, https://doi.org/10.5194/acp-12-4117-2012, 2012.
Jokinen, T., Sipilä, M., Richters, S., Kerminen, V., Paasonen, P., Stratmann, F., Worsnop, D., Kulmala, M., Ehn, M., Herrmann, H., and Berndt, T.: Rapid Autoxidation Forms Highly Oxidized RO2 Radicals in the Atmosphere, Angew. Chem. Int. Ed., 53, 14596–14600, https://doi.org/10.1002/anie.201408566, 2014.
Kroll, J. H. and Seinfeld, J. H.: Chemistry of secondary organic aerosol: Formation and evolution of low-volatility organics in the atmosphere, Atmos. Environ., 42, 3593–3624, https://doi.org/10.1016/j.atmosenv.2008.01.003, 2008.
Kroll, J. H., Ng, N. L., Murphy, S. M., Flagan, R. C., and Seinfeld, J. H.: Secondary organic aerosol formation from isoprene photooxidation under high-NOx conditions, Geophys. Res. Lett., 32, L18808, https://doi.org/10.1029/2005GL023637, 2005.
Mentel, T. F., Springer, M., Ehn, M., Kleist, E., Pullinen, I., Kurtén, T., Rissanen, M., Wahner, A., and Wildt, J.: Formation of highly oxidized multifunctional compounds: autoxidation of peroxy radicals formed in the ozonolysis of alkenes – deduced from structure–product relationships, Atmos. Chem. Phys., 15, 6745–6765, https://doi.org/10.5194/acp-15-6745-2015, 2015.
O'Meara, S. P., Xu, S., Topping, D., Alfarra, M. R., Capes, G., Lowe, D., Shao, Y., and McFiggans, G.: PyCHAM (v2.1.1): a Python box model for simulating aerosol chambers, Geosci. Model Dev., 14, 675–702, https://doi.org/10.5194/gmd-14-675-2021, 2021.
Orlando, J. J. and Tyndall, G. S.: Laboratory studies of organic peroxy radical chemistry: an overview with emphasis on recent issues of atmospheric significance, Chem. Soc. Rev., 41, 6294, https://doi.org/10.1039/c2cs35166h, 2012.
Orlando, J. J., Tyndall, G. S., and Wallington, T. J.: The Atmospheric Chemistry of Alkoxy Radicals, Chem. Rev., 103, 4657–4690, https://doi.org/10.1021/cr020527p, 2003.
Pichelstorfer, L.: data for article “Theory informed, experiment based, constraint on the rate of autoxidation chemistry – An analytical approach”, Version v1, Zenodo [data set], https://doi.org/10.5281/zenodo.14223708, 2024.
Pichelstorfer, L., Roldin, P., Rissanen, M., Hyttinen, N., Garmash, O., Xavier, C., Zhou, P., Clusius, P., Foreback, B., Golin Almeida, T., Deng, C., Baykara, M., Kurtén, T., and Boy, M.: Towards automated inclusion of autoxidation chemistry in models: from precursors to atmospheric implications, Environmental Science: Atmospheres, 4, 879–896, https://doi.org/10.1039/D4EA00054D, 2024.
Praske, E., Otkjær, R. V., Crounse, J. D., Hethcox, J. C., Stoltz, B. M., Kjaergaard, H. G., and Wennberg, P. O.: Atmospheric autoxidation is increasingly important in urban and suburban North America, P. Natl. Acad. Sci. USA, 115, 64–69, https://doi.org/10.1073/pnas.1715540115, 2018.
Rissanen, M. P., Kurtén, T., Sipilä, M., Thornton, J. A., Kangasluoma, J., Sarnela, N., Junninen, H., Jørgensen, S., Schallhart, S., Kajos, M. K., Taipale, R., Springer, M., Mentel, T. F., Ruuskanen, T., Petäjä, T., Worsnop, D. R., Kjaergaard, H. G., and Ehn, M.: The Formation of Highly Oxidized Multifunctional Products in the Ozonolysis of Cyclohexene, J. Am. Chem. Soc., 136, 15596–15606, https://doi.org/10.1021/ja507146s, 2014.
Rissanen, M. P., Kurtén, T., Sipilä, M., Thornton, J. A., Kausiala, O., Garmash, O., Kjaergaard, H. G., Petäjä, T., Worsnop, D. R., Ehn, M., and Kulmala, M.: Effects of Chemical Complexity on the Autoxidation Mechanisms of Endocyclic Alkene Ozonolysis Products: From Methylcyclohexenes toward Understanding α-Pinene, J. Phys. Chem. A, 119, 4633–4650, https://doi.org/10.1021/jp510966g, 2015.
Roldin, P., Eriksson, A. C., Nordin, E. Z., Hermansson, E., Mogensen, D., Rusanen, A., Boy, M., Swietlicki, E., Svenningsson, B., Zelenyuk, A., and Pagels, J.: Modelling non-equilibrium secondary organic aerosol formation and evaporation with the aerosol dynamics, gas- and particle-phase chemistry kinetic multilayer model ADCHAM, Atmos. Chem. Phys., 14, 7953–7993, https://doi.org/10.5194/acp-14-7953-2014, 2014.
Roldin, P., Ehn, M., Kurtén, T., Olenius, T., Rissanen, M. P., Sarnela, N., Elm, J., Rantala, P., Hao, L., Hyttinen, N., Heikkinen, L., Worsnop, D. R., Pichelstorfer, L., Xavier, C., Clusius, P., Öström, E., Petäjä, T., Kulmala, M., Vehkamäki, H., Virtanen, A., Riipinen, I., and Boy, M.: The role of highly oxygenated organic molecules in the Boreal aerosol-cloud-climate system, Nat. Commun., 10, 4370, https://doi.org/10.1038/s41467-019-12338-8, 2019.
Salo, V.-T., Valiev, R., Lehtola, S., and Kurtén, T.: Gas-Phase Peroxyl Radical Recombination Reactions: A Computational Study of Formation and Decomposition of Tetroxides, J. Phys. Chem. A, 126, 4046–4056, https://doi.org/10.1021/acs.jpca.2c01321, 2022.
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.
Schervish, M. and Donahue, N. M.: Peroxy radical chemistry and the volatility basis set, Atmos. Chem. Phys., 20, 1183–1199, https://doi.org/10.5194/acp-20-1183-2020, 2020.
Shrivastava, M., Fan, J., Zhang, Y., Rasool, Q. Z., Zhao, B., Shen, J., Pierce, J. R., Jathar, S. H., Akherati, A., Zhang, J., Zaveri, R. A., Gaudet, B., Liu, Y., Andreae, M. O., Pöhlker, M. L., Donahue, N. M., Wang, Y., and Seinfeld, J. H.: Intense formation of secondary ultrafine particles from Amazonian vegetation fires and their invigoration of deep clouds and precipitation, One Earth, 7, 1029–1043, https://doi.org/10.1016/j.oneear.2024.05.015, 2024.
Tsimpidi, A. P., Karydis, V. A., Zavala, M., Lei, W., Molina, L., Ulbrich, I. M., Jimenez, J. L., and Pandis, S. N.: Evaluation of the volatility basis-set approach for the simulation of organic aerosol formation in the Mexico City metropolitan area, Atmos. Chem. Phys., 10, 525–546, https://doi.org/10.5194/acp-10-525-2010, 2010.
Vereecken, L. and Nozière, B.: H migration in peroxy radicals under atmospheric conditions, Atmos. Chem. Phys., 20, 7429–7458, https://doi.org/10.5194/acp-20-7429-2020, 2020.
Vereecken, L. and Peeters, J.: A structure–activity relationship for the rate coefficient of H-migration in substituted alkoxy radicals, Phys. Chem. Chem. Phys., 12, 12608, https://doi.org/10.1039/c0cp00387e, 2010.
Wang, Z. and Sarathy, S. M.: Third O2 addition reactions promote the low-temperature auto-ignition of n-alkanes, Combust. Flame, 165, 364–372, https://doi.org/10.1016/j.combustflame.2015.12.020, 2016.
Short summary
Quantification of autoxidation chemistry is a complex task essential to our understanding of atmospheric secondary aerosol formation and its impact on climate. In this work, we introduce the autoCONSTRAINT module, a semi-empirical method for deducing reaction rate coefficients for lumped autoxidation chemistry schemes based on experimental data. The theoretical approach is analytical and provides mathematically correct though non-unique solutions with low computational cost.
Quantification of autoxidation chemistry is a complex task essential to our understanding of...
Altmetrics
Final-revised paper
Preprint