Articles | Volume 25, issue 22
https://doi.org/10.5194/acp-25-15715-2025
© 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/acp-25-15715-2025
© Author(s) 2025. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
17 Nov 2025
Research article |
| 17 Nov 2025
| 17 Nov 2025
Formation of highly oxygenated organic molecules from α-pinene photooxidation: evidence for the importance of highly oxygenated alkoxy radicals
Sungah Kang
Institute of Energy and Climate Systems, ICE-3, Forschungszentrum Jülich GmbH, 52425, Jülich, Germany
Jürgen Wildt
Institute of Bio- and Geosciences, IBG-2, Forschungszentrum Jülich GmbH, 52425, Jülich, Germany
retired
Iida Pullinen
Institute of Energy and Climate Systems, ICE-3, Forschungszentrum Jülich GmbH, 52425, Jülich, Germany
present address: Department of Applied Physics, University of Eastern Finland, Kuopio, Finland
Luc Vereecken
Institute of Energy and Climate Systems, ICE-3, Forschungszentrum Jülich GmbH, 52425, Jülich, Germany
Cheng Wu
Institute of Energy and Climate Systems, ICE-3, Forschungszentrum Jülich GmbH, 52425, Jülich, Germany
present address: Department of Chemistry and Molecular biology, University of Gothenburg, Göteborg, 41390, Sweden
Andreas Wahner
Institute of Energy and Climate Systems, ICE-3, Forschungszentrum Jülich GmbH, 52425, Jülich, Germany
Institute of Energy and Climate Systems, ICE-3, Forschungszentrum Jülich GmbH, 52425, Jülich, Germany
Thomas F. Mentel
Institute of Energy and Climate Systems, ICE-3, Forschungszentrum Jülich GmbH, 52425, Jülich, Germany
retired
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Preprint archived
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Philip T. M. Carlsson, Luc Vereecken, Anna Novelli, François Bernard, Steven S. Brown, Bellamy Brownwood, Changmin Cho, John N. Crowley, Patrick Dewald, Peter M. Edwards, Nils Friedrich, Juliane L. Fry, Mattias Hallquist, Luisa Hantschke, Thorsten Hohaus, Sungah Kang, Jonathan Liebmann, Alfred W. Mayhew, Thomas Mentel, David Reimer, Franz Rohrer, Justin Shenolikar, Ralf Tillmann, Epameinondas Tsiligiannis, Rongrong Wu, Andreas Wahner, Astrid Kiendler-Scharr, and Hendrik Fuchs
Atmos. Chem. Phys., 23, 3147–3180, https://doi.org/10.5194/acp-23-3147-2023, https://doi.org/10.5194/acp-23-3147-2023, 2023
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We introduce the offline application of FIGAERO-CIMS by analyzing Teflon and quartz filter samples that were collected at a typical urban site in Beijing with the deposition time varying from 30 min to 24 h. This method provides a feasible, simple, and quantitative way to investigate the molecular composition and volatility of OA compounds by using FIGAERO-CIMS to analyze offline samples.
Changmin Cho, Hendrik Fuchs, Andreas Hofzumahaus, Frank Holland, William J. Bloss, Birger Bohn, Hans-Peter Dorn, Marvin Glowania, Thorsten Hohaus, Lu Liu, Paul S. Monks, Doreen Niether, Franz Rohrer, Roberto Sommariva, Zhaofeng Tan, Ralf Tillmann, Astrid Kiendler-Scharr, Andreas Wahner, and Anna Novelli
Atmos. Chem. Phys., 23, 2003–2033, https://doi.org/10.5194/acp-23-2003-2023, https://doi.org/10.5194/acp-23-2003-2023, 2023
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With this study, we investigated the processes leading to the formation, destruction, and recycling of radicals for four seasons in a rural environment. Complete knowledge of their chemistry is needed if we are to predict the formation of secondary pollutants from primary emissions. The results highlight a still incomplete understanding of the paths leading to the formation of the OH radical, which has been observed in several other environments as well and needs to be further investigated.
Wiebke Scholz, Jiali Shen, Diego Aliaga, Cheng Wu, Samara Carbone, Isabel Moreno, Qiaozhi Zha, Wei Huang, Liine Heikkinen, Jean Luc Jaffrezo, Gaelle Uzu, Eva Partoll, Markus Leiminger, Fernando Velarde, Paolo Laj, Patrick Ginot, Paolo Artaxo, Alfred Wiedensohler, Markku Kulmala, Claudia Mohr, Marcos Andrade, Victoria Sinclair, Federico Bianchi, and Armin Hansel
Atmos. Chem. Phys., 23, 895–920, https://doi.org/10.5194/acp-23-895-2023, https://doi.org/10.5194/acp-23-895-2023, 2023
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Dimethyl sulfide (DMS), emitted from the ocean, is the most abundant biogenic sulfur emission into the atmosphere. OH radicals, among others, can oxidize DMS to sulfuric and methanesulfonic acid, which are relevant for aerosol formation. We quantified DMS and nearly all DMS oxidation products with novel mass spectrometric instruments for gas and particle phase at the high mountain station Chacaltaya (5240 m a.s.l.) in the Bolivian Andes in free tropospheric air after long-range transport.
Zijun Li, Angela Buchholz, Luis M. F. Barreira, Arttu Ylisirniö, Liqing Hao, Iida Pullinen, Siegfried Schobesberger, and Annele Virtanen
Atmos. Chem. Phys., 23, 203–220, https://doi.org/10.5194/acp-23-203-2023, https://doi.org/10.5194/acp-23-203-2023, 2023
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Interaction between NOx and biogenic emissions can be important in suburban areas. Our study showed that the addition of NOx during α-pinene SOA formation produced considerable amounts of organic nitrates and affected the composition of non-nitrated organic compounds. The compositional difference consequently altered the primary type of aqueous-phase processes during the isothermal particle evaporation.
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
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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.
David M. Bell, Cheng Wu, Amelie Bertrand, Emelie Graham, Janne Schoonbaert, Stamatios Giannoukos, Urs Baltensperger, Andre S. H. Prevot, Ilona Riipinen, Imad El Haddad, and Claudia Mohr
Atmos. Chem. Phys., 22, 13167–13182, https://doi.org/10.5194/acp-22-13167-2022, https://doi.org/10.5194/acp-22-13167-2022, 2022
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A series of studies designed to investigate the evolution of organic aerosol were performed in an atmospheric simulation chamber, using a common oxidant found at night (NO3). The chemical composition steadily changed from its initial composition via different chemical reactions that were taking place inside of the aerosol particle. These results show that the composition of organic aerosol steadily changes during its lifetime in the atmosphere.
Zhaofeng Tan, Hendrik Fuchs, Andreas Hofzumahaus, William J. Bloss, Birger Bohn, Changmin Cho, Thorsten Hohaus, Frank Holland, Chandrakiran Lakshmisha, Lu Liu, Paul S. Monks, Anna Novelli, Doreen Niether, Franz Rohrer, Ralf Tillmann, Thalassa S. E. Valkenburg, Vaishali Vardhan, Astrid Kiendler-Scharr, Andreas Wahner, and Roberto Sommariva
Atmos. Chem. Phys., 22, 13137–13152, https://doi.org/10.5194/acp-22-13137-2022, https://doi.org/10.5194/acp-22-13137-2022, 2022
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During the 2019 JULIAC campaign, ClNO2 was measured at a rural site in Germany in different seasons. The highest ClNO2 level was 1.6 ppbv in September. ClNO2 production was more sensitive to the availability of NO2 than O3. The average ClNO2 production efficiency was up to 18 % in February and September and down to 3 % in December. These numbers are at the high end of the values reported in the literature, indicating the importance of ClNO2 chemistry in rural environments in midwestern Europe.
Silvia M. Calderón, Juha Tonttila, Angela Buchholz, Jorma Joutsensaari, Mika Komppula, Ari Leskinen, Liqing Hao, Dmitri Moisseev, Iida Pullinen, Petri Tiitta, Jian Xu, Annele Virtanen, Harri Kokkola, and Sami Romakkaniemi
Atmos. Chem. Phys., 22, 12417–12441, https://doi.org/10.5194/acp-22-12417-2022, https://doi.org/10.5194/acp-22-12417-2022, 2022
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The spatial and temporal restrictions of observations and oversimplified aerosol representation in large eddy simulations (LES) limit our understanding of aerosol–stratocumulus interactions. In this closure study of in situ and remote sensing observations and outputs from UCLALES–SALSA, we have assessed the role of convective overturning and aerosol effects in two cloud events observed at the Puijo SMEAR IV station, Finland, a diurnal-high aerosol case and a nocturnal-low aerosol case.
Yindong Guo, Hongru Shen, Iida Pullinen, Hao Luo, Sungah Kang, Luc Vereecken, Hendrik Fuchs, Mattias Hallquist, Ismail-Hakki Acir, Ralf Tillmann, Franz Rohrer, Jürgen Wildt, Astrid Kiendler-Scharr, Andreas Wahner, Defeng Zhao, and Thomas F. Mentel
Atmos. Chem. Phys., 22, 11323–11346, https://doi.org/10.5194/acp-22-11323-2022, https://doi.org/10.5194/acp-22-11323-2022, 2022
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The oxidation of limonene, a common volatile emitted by trees and chemical products, by NO3, a nighttime oxidant, forms many highly oxygenated organic molecules (HOM), including C10-30 compounds. Most of the HOM are second-generation organic nitrates, in which carbonyl-substituted C10 nitrates accounted for a major fraction. Their formation can be explained by chemistry of peroxy radicals. HOM, especially low-volatile ones, play an important role in nighttime new particle formation and growth.
Lisa J. Beck, Siegfried Schobesberger, Heikki Junninen, Janne Lampilahti, Antti Manninen, Lubna Dada, Katri Leino, Xu-Cheng He, Iida Pullinen, Lauriane L. J. Quéléver, Anna Franck, Pyry Poutanen, Daniela Wimmer, Frans Korhonen, Mikko Sipilä, Mikael Ehn, Douglas R. Worsnop, Veli-Matti Kerminen, Tuukka Petäjä, Markku Kulmala, and Jonathan Duplissy
Atmos. Chem. Phys., 22, 8547–8577, https://doi.org/10.5194/acp-22-8547-2022, https://doi.org/10.5194/acp-22-8547-2022, 2022
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The presented article introduces an overview of atmospheric ions and their composition above the boreal forest. We provide the results of an extensive airborne measurement campaign with an air ion mass spectrometer and particle measurements, showing their diurnal evolution within the boundary layer and free troposphere. In addition, we compare the airborne dataset with the co-located data from the ground at SMEAR II station, Finland.
Jacky Yat Sing Pang, Anna Novelli, Martin Kaminski, Ismail-Hakki Acir, Birger Bohn, Philip T. M. Carlsson, Changmin Cho, Hans-Peter Dorn, Andreas Hofzumahaus, Xin Li, Anna Lutz, Sascha Nehr, David Reimer, Franz Rohrer, Ralf Tillmann, Robert Wegener, Astrid Kiendler-Scharr, Andreas Wahner, and Hendrik Fuchs
Atmos. Chem. Phys., 22, 8497–8527, https://doi.org/10.5194/acp-22-8497-2022, https://doi.org/10.5194/acp-22-8497-2022, 2022
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This study investigates the radical chemical budget during the limonene oxidation at different atmospheric-relevant NO concentrations in chamber experiments under atmospheric conditions. It is found that the model–measurement discrepancies of HO2 and RO2 are very large at low NO concentrations that are typical for forested environments. Possible additional processes impacting HO2 and RO2 concentrations are discussed.
Mike J. Newland, Camille Mouchel-Vallon, Richard Valorso, Bernard Aumont, Luc Vereecken, Michael E. Jenkin, and Andrew R. Rickard
Atmos. Chem. Phys., 22, 6167–6195, https://doi.org/10.5194/acp-22-6167-2022, https://doi.org/10.5194/acp-22-6167-2022, 2022
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Alkene ozonolysis produces Criegee intermediates, which can act as oxidants or decompose to give a range of closed-shell and radical products, including OH. Therefore it is essential to accurately represent the chemistry of Criegee intermediates in atmospheric models in order to understand their impacts on atmospheric composition. Here we provide a mechanism construction protocol by which the central features of alkene ozonolysis chemistry can be included in an automatic mechanism generator.
Jing Cai, Cheng Wu, Jiandong Wang, Wei Du, Feixue Zheng, Simo Hakala, Xiaolong Fan, Biwu Chu, Lei Yao, Zemin Feng, Yongchun Liu, Yele Sun, Jun Zheng, Chao Yan, Federico Bianchi, Markku Kulmala, Claudia Mohr, and Kaspar R. Daellenbach
Atmos. Chem. Phys., 22, 1251–1269, https://doi.org/10.5194/acp-22-1251-2022, https://doi.org/10.5194/acp-22-1251-2022, 2022
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This study investigates the connection between organic aerosol (OA) molecular composition and particle absorptive properties in autumn in Beijing. We find that the molecular properties of OA compounds in different episodes influence particle light absorption properties differently: the light absorption enhancement of black carbon and light absorption coefficient of brown carbon were mostly related to more oxygenated OA (low C number and four O atoms) and aromatics/nitro-aromatics, respectively.
Noora Hyttinen, Iida Pullinen, Aki Nissinen, Siegfried Schobesberger, Annele Virtanen, and Taina Yli-Juuti
Atmos. Chem. Phys., 22, 1195–1208, https://doi.org/10.5194/acp-22-1195-2022, https://doi.org/10.5194/acp-22-1195-2022, 2022
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Accurate saturation vapor pressure estimates of atmospherically relevant organic compounds are critical for modeling secondary organic aerosol (SOA) formation. We investigated vapor pressures of highly oxygenated SOA constituents using state-of-the-art computational and experimental methods. We found a good agreement between low and extremely low vapor pressures estimated using the two methods, and the smallest molecules detected in our experiment were likely products of thermal decomposition.
Najin Kim, Yafang Cheng, Nan Ma, Mira L. Pöhlker, Thomas Klimach, Thomas F. Mentel, Ovid O. Krüger, Ulrich Pöschl, and Hang Su
Atmos. Meas. Tech., 14, 6991–7005, https://doi.org/10.5194/amt-14-6991-2021, https://doi.org/10.5194/amt-14-6991-2021, 2021
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A broad supersaturation scanning CCN (BS2-CCN) system, in which particles are exposed to a range of supersaturation simultaneously, can measure a broad range of CCN activity distribution with a high time resolution. We describe how the BS2-CCN system can be effectively calibrated and which factors can affect the calibration curve. Intercomparison experiments between typical DMA-CCN and BS2-CCN measurements to evaluate the BS2-CCN system showed high correlation and good agreement.
Zhaofeng Tan, Luisa Hantschke, Martin Kaminski, Ismail-Hakki Acir, Birger Bohn, Changmin Cho, Hans-Peter Dorn, Xin Li, Anna Novelli, Sascha Nehr, Franz Rohrer, Ralf Tillmann, Robert Wegener, Andreas Hofzumahaus, Astrid Kiendler-Scharr, Andreas Wahner, and Hendrik Fuchs
Atmos. Chem. Phys., 21, 16067–16091, https://doi.org/10.5194/acp-21-16067-2021, https://doi.org/10.5194/acp-21-16067-2021, 2021
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The photo-oxidation of myrcene, a monoterpene species emitted by plants, was investigated at atmospheric conditions in the outdoor simulation chamber SAPHIR. The chemical structure of myrcene is partly similar to isoprene. Therefore, it can be expected that hydrogen shift reactions could play a role as observed for isoprene. In this work, their potential impact on the regeneration efficiency of hydroxyl radicals is investigated.
Cheng Wu, David M. Bell, Emelie L. Graham, Sophie Haslett, Ilona Riipinen, Urs Baltensperger, Amelie Bertrand, Stamatios Giannoukos, Janne Schoonbaert, Imad El Haddad, Andre S. H. Prevot, Wei Huang, and Claudia Mohr
Atmos. Chem. Phys., 21, 14907–14925, https://doi.org/10.5194/acp-21-14907-2021, https://doi.org/10.5194/acp-21-14907-2021, 2021
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Night-time reactions of biogenic volatile organic compounds and nitrate radicals can lead to the formation of secondary organic aerosol (BSOANO3). Here, we study the impacts of light exposure on the BSOANO3 from three biogenic precursors. Our results suggest that photolysis causes photodegradation of a substantial fraction of BSOANO3, changes the chemical composition and bulk volatility, and might be a potentially important loss pathway of BSOANO3 during the night-to-day transition.
Philipp G. Eger, Luc Vereecken, Rolf Sander, Jan Schuladen, Nicolas Sobanski, Horst Fischer, Einar Karu, Jonathan Williams, Ville Vakkari, Tuukka Petäjä, Jos Lelieveld, Andrea Pozzer, and John N. Crowley
Atmos. Chem. Phys., 21, 14333–14349, https://doi.org/10.5194/acp-21-14333-2021, https://doi.org/10.5194/acp-21-14333-2021, 2021
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We determine the impact of pyruvic acid photolysis on the formation of acetaldehyde and peroxy radicals during summer and autumn in the Finnish boreal forest using a data-constrained box model. Our results are dependent on the chosen scenario in which the overall quantum yield and the photolysis products are varied. We highlight that pyruvic acid photolysis can be an important contributor to acetaldehyde and peroxy radical formation in remote, forested regions.
Janne Lampilahti, Hanna E. Manninen, Tuomo Nieminen, Sander Mirme, Mikael Ehn, Iida Pullinen, Katri Leino, Siegfried Schobesberger, Juha Kangasluoma, Jenni Kontkanen, Emma Järvinen, Riikka Väänänen, Taina Yli-Juuti, Radovan Krejci, Katrianne Lehtipalo, Janne Levula, Aadu Mirme, Stefano Decesari, Ralf Tillmann, Douglas R. Worsnop, Franz Rohrer, Astrid Kiendler-Scharr, Tuukka Petäjä, Veli-Matti Kerminen, Thomas F. Mentel, and Markku Kulmala
Atmos. Chem. Phys., 21, 12649–12663, https://doi.org/10.5194/acp-21-12649-2021, https://doi.org/10.5194/acp-21-12649-2021, 2021
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We studied aerosol particle formation and growth in different parts of the planetary boundary layer at two different locations (Po Valley, Italy, and Hyytiälä, Finland). The observations consist of airborne measurements on board an instrumented Zeppelin and a small airplane combined with comprehensive ground-based measurements.
Luisa Hantschke, Anna Novelli, Birger Bohn, Changmin Cho, David Reimer, Franz Rohrer, Ralf Tillmann, Marvin Glowania, Andreas Hofzumahaus, Astrid Kiendler-Scharr, Andreas Wahner, and Hendrik Fuchs
Atmos. Chem. Phys., 21, 12665–12685, https://doi.org/10.5194/acp-21-12665-2021, https://doi.org/10.5194/acp-21-12665-2021, 2021
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The reactions of Δ3-carene with ozone and the hydroxyl radical (OH) and the photolysis and OH reaction of caronaldehyde were investigated in the simulation chamber SAPHIR. Reaction rate constants of these reactions were determined. Caronaldehyde yields of the ozonolysis and OH reaction were determined. The organic nitrate yield of the reaction of Δ3-carene and caronaldehyde-derived peroxy radicals with NO was determined. The ROx budget (ROx = OH+HO2+RO2) was also investigated.
Luis M. F. Barreira, Arttu Ylisirniö, Iida Pullinen, Angela Buchholz, Zijun Li, Helina Lipp, Heikki Junninen, Urmas Hõrrak, Steffen M. Noe, Alisa Krasnova, Dmitrii Krasnov, Kaia Kask, Eero Talts, Ülo Niinemets, Jose Ruiz-Jimenez, and Siegfried Schobesberger
Atmos. Chem. Phys., 21, 11781–11800, https://doi.org/10.5194/acp-21-11781-2021, https://doi.org/10.5194/acp-21-11781-2021, 2021
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We present results from PM1 atmospheric composition and concentration measurements performed in a springtime hemiboreal forest. Sesquiterpene mixing ratios and particle-phase concentrations of corresponding oxidation products were rapidly increasing on some early mornings. The particle volatility suggested that condensable sesquiterpene oxidation products are rapidly formed in the atmosphere. The results revealed the importance of sesquiterpenes for secondary organic aerosol particulate mass.
Simon Rosanka, Bruno Franco, Lieven Clarisse, Pierre-François Coheur, Andrea Pozzer, Andreas Wahner, and Domenico Taraborrelli
Atmos. Chem. Phys., 21, 11257–11288, https://doi.org/10.5194/acp-21-11257-2021, https://doi.org/10.5194/acp-21-11257-2021, 2021
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The strong El Niño in 2015 led to a particular dry season in Indonesia and favoured severe peatland fires. The smouldering conditions of these fires and the high carbon content of peat resulted in high volatile organic compound (VOC) emissions. By using a comprehensive atmospheric model, we show that these emissions have a significant impact on the tropospheric composition and oxidation capacity. These emissions are transported into to the lower stratosphere, resulting in a depletion of ozone.
Ana A. Piedehierro, André Welti, Angela Buchholz, Kimmo Korhonen, Iida Pullinen, Ilkka Summanen, Annele Virtanen, and Ari Laaksonen
Atmos. Chem. Phys., 21, 11069–11078, https://doi.org/10.5194/acp-21-11069-2021, https://doi.org/10.5194/acp-21-11069-2021, 2021
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Ice crystals in cirrus clouds contain particles that start ice formation. We study whether particles forming above boreal forests can help in the making of cirrus clouds and if the water content in the particles affects this property. In the laboratory, we made boreal-forest-like particles and cooled and humidified them to measure whether an ice crystal develops. We found that only when dry can these particles form an ice crystal but no better than solution droplets.
Rongrong Wu, Luc Vereecken, Epameinondas Tsiligiannis, Sungah Kang, Sascha R. Albrecht, Luisa Hantschke, Defeng Zhao, Anna Novelli, Hendrik Fuchs, Ralf Tillmann, Thorsten Hohaus, Philip T. M. Carlsson, Justin Shenolikar, François Bernard, John N. Crowley, Juliane L. Fry, Bellamy Brownwood, Joel A. Thornton, Steven S. Brown, Astrid Kiendler-Scharr, Andreas Wahner, Mattias Hallquist, and Thomas F. Mentel
Atmos. Chem. Phys., 21, 10799–10824, https://doi.org/10.5194/acp-21-10799-2021, https://doi.org/10.5194/acp-21-10799-2021, 2021
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Isoprene is the biogenic volatile organic compound with the largest emissions rates. The nighttime reaction of isoprene with the NO3 radical has a large potential to contribute to SOA. We classified isoprene nitrates into generations and proposed formation pathways. Considering the potential functionalization of the isoprene nitrates we propose that mainly isoprene dimers contribute to SOA formation from the isoprene NO3 reactions with at least a 5 % mass yield.
Simon Rosanka, Rolf Sander, Andreas Wahner, and Domenico Taraborrelli
Geosci. Model Dev., 14, 4103–4115, https://doi.org/10.5194/gmd-14-4103-2021, https://doi.org/10.5194/gmd-14-4103-2021, 2021
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The Jülich Aqueous-phase Mechanism of Organic Chemistry (JAMOC) is developed and implemented into the Module Efficiently Calculating the Chemistry of the Atmosphere (MECCA). JAMOC is an explicit in-cloud oxidation scheme for oxygenated volatile organic compounds (OVOCs), which is suitable for global model applications. Within a box-model study, we show that JAMOC yields reduced gas-phase concentrations of most OVOCs and oxidants, except for nitrogen oxides.
Simon Rosanka, Rolf Sander, Bruno Franco, Catherine Wespes, Andreas Wahner, and Domenico Taraborrelli
Atmos. Chem. Phys., 21, 9909–9930, https://doi.org/10.5194/acp-21-9909-2021, https://doi.org/10.5194/acp-21-9909-2021, 2021
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In-cloud destruction of ozone depends on hydroperoxyl radicals in cloud droplets, where they are produced by oxygenated volatile organic compound (OVOC) oxygenation. Only rudimentary representations of these processes, if any, are currently available in global atmospheric models. By using a comprehensive atmospheric model that includes a complex in-cloud OVOC oxidation scheme, we show that atmospheric oxidants are reduced and models ignoring this process will underpredict clouds as ozone sinks.
Defeng Zhao, Iida Pullinen, Hendrik Fuchs, Stephanie Schrade, Rongrong Wu, Ismail-Hakki Acir, Ralf Tillmann, Franz Rohrer, Jürgen Wildt, Yindong Guo, Astrid Kiendler-Scharr, Andreas Wahner, Sungah Kang, Luc Vereecken, and Thomas F. Mentel
Atmos. Chem. Phys., 21, 9681–9704, https://doi.org/10.5194/acp-21-9681-2021, https://doi.org/10.5194/acp-21-9681-2021, 2021
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The reaction of isoprene, a biogenic volatile organic compound with the globally largest emission rates, with NO3, an nighttime oxidant influenced heavily by anthropogenic emissions, forms a large number of highly oxygenated organic molecules (HOM). These HOM are formed via one or multiple oxidation steps, followed by autoxidation. Their total yield is much higher than that in the daytime oxidation of isoprene. They may play an important role in nighttime organic aerosol formation and growth.
Marvin Glowania, Franz Rohrer, Hans-Peter Dorn, Andreas Hofzumahaus, Frank Holland, Astrid Kiendler-Scharr, Andreas Wahner, and Hendrik Fuchs
Atmos. Meas. Tech., 14, 4239–4253, https://doi.org/10.5194/amt-14-4239-2021, https://doi.org/10.5194/amt-14-4239-2021, 2021
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Three instruments that use different techniques to measure gaseous formaldehyde concentrations were compared in experiments in the atmospheric simulation chamber SAPHIR at Forschungszentrum Jülich. The results demonstrated the need to correct the baseline in measurements by instruments that use the Hantzsch reaction or make use of cavity ring-down spectroscopy. After applying corrections, all three methods gave accurate and precise measurements within their specifications.
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
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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.
Changmin Cho, Andreas Hofzumahaus, Hendrik Fuchs, Hans-Peter Dorn, Marvin Glowania, Frank Holland, Franz Rohrer, Vaishali Vardhan, Astrid Kiendler-Scharr, Andreas Wahner, and Anna Novelli
Atmos. Meas. Tech., 14, 1851–1877, https://doi.org/10.5194/amt-14-1851-2021, https://doi.org/10.5194/amt-14-1851-2021, 2021
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This study describes the implementation and characterization of the chemical modulation reactor (CMR) used in the laser-induced fluorescence instrument of the Forschungszentrum Jülich. The CMR allows for interference-free OH radical measurement in ambient air. During a field campaign in a rural environment, the observed interference was mostly below the detection limit of the instrument and fully explained by the known ozone interference.
Arttu Ylisirniö, Luis M. F. Barreira, Iida Pullinen, Angela Buchholz, John Jayne, Jordan E. Krechmer, Douglas R. Worsnop, Annele Virtanen, and Siegfried Schobesberger
Atmos. Meas. Tech., 14, 355–367, https://doi.org/10.5194/amt-14-355-2021, https://doi.org/10.5194/amt-14-355-2021, 2021
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FIGAERO-ToF-CIMS enables online volatility measurements of chemical compounds in ambient aerosols. Previously published volatility calibration results however differ from each other significantly. In this study we investigate the reason for this discrepancy. We found a major source of error in the widely used syringe deposition method and propose a new method for volatility calibration by using atomized calibration compounds.
Huan Song, Xiaorui Chen, Keding Lu, Qi Zou, Zhaofeng Tan, Hendrik Fuchs, Alfred Wiedensohler, Daniel R. Moon, Dwayne E. Heard, María-Teresa Baeza-Romero, Mei Zheng, Andreas Wahner, Astrid Kiendler-Scharr, and Yuanhang Zhang
Atmos. Chem. Phys., 20, 15835–15850, https://doi.org/10.5194/acp-20-15835-2020, https://doi.org/10.5194/acp-20-15835-2020, 2020
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Accurate calculation of the HO2 uptake coefficient is one of the key parameters to quantify the co-reduction of both aerosol and ozone pollution. We modelled various lab measurements of γHO2 based on a gas-liquid phase kinetic model and developed a state-of-the-art parameterized equation. Based on a dataset from a comprehensive field campaign in the North China Plain, we proposed that the determination of the heterogeneous uptake process for HO2 should be included in future field campaigns.
Cited articles
Aschmann, S. M., Atkinson, R., and Arey, J.: Products of reaction of OH radicals with α-pinene, J. Geophys. Res.-Atmos., 107, 4191, https://doi.org/10.1029/2001jd001098, 2002.
Assaf, E., Schoemaecker, C., Vereecken, L., and Fittschen, C.: Experimental and theoretical investigation of the reaction of RO2 radicals with OH radicals: Dependence of the HO2 yield on the size of the alkyl group, Int. J. Chem. Kin., 50, 670–680, https://doi.org/10.1002/kin.21191, 2018.
Atkinson, R.: Rate constants for the atmospheric reactions of alkoxy radicals: An updated estimation method, Atmos. Environ., 41, 8468–8485, https://doi.org/10.1016/j.atmosenv.2007.07.002, 2007.
Atkinson, R. and Arey, J.: Gas-phase tropospheric chemistry of biogenic volatile organic compounds: a review, Atmos. Environ., 37, S197–S219, 2003a.
Atkinson, R. and Arey, J.: Atmospheric degradation of volatile organic compounds, Chem. Rev., 103, 4605–4638, https://doi.org/10.1021/cr0206420, 2003b.
Berndt, T.: Peroxy Radical Processes and Product Formation in the OH Radical-Initiated Oxidation of α-Pinene for Near-Atmospheric Conditions, J. Phys. Chem. A, 125, 9151–9160, https://doi.org/10.1021/acs.jpca.1c05576, 2021.
Berndt, T., Richters, S., Kaethner, R., Voigtlaender, J., Stratmann, F., Sipilae, M., Kulmala, M., and Herrmann, H.: Gas-Phase Ozonolysis of Cycloalkenes: Formation of Highly Oxidized RO2 Radicals and Their Reactions with NO, NO2, SO2, and Other RO2 Radicals, J. Phys. Chem. A, 119, 10336–10348, https://doi.org/10.1021/acs.jpca.5b07295, 2015.
Berndt, T., Richters, S., Jokinen, T., Hyttinen, N., Kurten, T., Otkjaer, R. V., Kjaergaard, H. G., Stratmann, F., Herrmann, H., Sipila, M., Kulmala, M., and Ehn, M.: Hydroxyl radical-induced formation of highly oxidized organic compounds, Nat. Commun., 7, https://doi.org/10.1038/ncomms13677, 2016.
Berndt, T., Mender, 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., Trostl, J., Junninen, H., Frege, C., Henne, S., Hoyle, C. R., Molteni, U., Herrmann, E., Adamov, A., Bukowiecki, N., Chen, X., Duplissy, J., Gysel, M., Hutterli, M., Kangasluoma, J., Kontkanen, J., Kurten, A., Manninen, H. E., Munch, S., Perakyla, O., Petaja, T., Rondo, L., Williamson, C., Weingartner, E., Curtius, J., Worsnop, D. R., Kulmala, M., Dommen, J., and Baltensperger, U.: New particle formation in the free troposphere: A question of chemistry and timing, Science, 352, 1109–1112, https://doi.org/10.1126/science.aad5456, 2016.
Bianchi, F., Kurten, 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.
Capouet, M., Müller, J.-F., Ceulemans, K., Compernolle, S., Vereecken, L., and Peeters, J.: Modeling aerosol formation in α-pinene photo-oxidation experiments, J. Geophys. Res., 113, D02308, https://doi.org/10.1029/2007JD008995, 2008.
Cox, R. A. and Cole, J. A.: Chemical aspects of the autoignition of hydrocarbon-air mixtures, Combustion and Flame, 60, 109–123, https://doi.org/10.1016/0010-2180(85)90001-x, 1985.
Crounse, J. D., Knap, H. C., Ornso, K. B., Jorgensen, S., Paulot, F., Kjaergaard, H. G., and Wennberg, P. O.: Atmospheric Fate of Methacrolein. 1. Peroxy Radical Isomerization Following Addition of OH and O-2, Journal of Physical Chemistry A, 116, 5756–5762, https://doi.org/10.1021/jp211560u, 2012.
Crounse, J. D., Nielsen, L. B., Jorgensen, S., Kjaergaard, H. G., and Wennberg, P. O.: Autoxidation of Organic Compounds in the Atmosphere, Journal of Physical Chemistry Letters, 4, 3513–3520, https://doi.org/10.1021/jz4019207, 2013.
Dames, E. E. and Green, W. H.: The Effect of Alcohol and Carbonyl Functional Groups on the Competition between Unimolecular Decomposition and Isomerization in C4 and C5 Alkoxy Radicals, Int. J. Chem. Kinet., 48, 544–555, https://doi.org/10.1002/kin.21015, 2016.
Davidson, C. I., Phalen, R. F., and Solomon, P. A.: Airborne particulate matter and human health: A review, Aerosol Sci. Tech., 39, 737–749, https://doi.org/10.1080/02786820500191348, 2005.
Eddingsaas, N. C., Loza, C. L., Yee, L. D., Seinfeld, J. H., and Wennberg, P. O.: α-pinene photooxidation under controlled chemical conditions – Part 1: Gas-phase composition in low- and high-NOx environments, Atmos. Chem. Phys., 12, 6489–6504, https://doi.org/10.5194/acp-12-6489-2012, 2012a.
Eddingsaas, N. C., Loza, C. L., Yee, L. D., Chan, M., Schilling, K. A., Chhabra, P. S., Seinfeld, J. H., and Wennberg, P. O.: α-pinene photooxidation under controlled chemical conditions – Part 2: SOA yield and composition in low- and high-NOx environments, Atmos. Chem. Phys., 12, 7413–7427, https://doi.org/10.5194/acp-12-7413-2012, 2012b.
Ehhalt, D. H.: Chemical reactions in the troposphere, in: Global Aspects of Atmospheric Chemistry, edited by: Zellner, R. G. E., Topics in Physical Chemistry, Steinkopff, Darmstadt, 60–94, ISBN 978-3798511279, 1999.
Ehn, M., Kleist, E., Junninen, H., Petäjä, T., Lönn, G., Schobesberger, S., Dal Maso, M., Trimborn, A., Kulmala, M., Worsnop, D. R., Wahner, A., Wildt, J., and Mentel, Th. F.: Gas phase formation of extremely oxidized pinene reaction products in chamber and ambient air, Atmos. Chem. Phys., 12, 5113–5127, https://doi.org/10.5194/acp-12-5113-2012, 2012.
Ehn, M., Thornton, J. A., Kleist, E., Sipila, 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., Kurten, T., Nielsen, L. B., Jorgensen, S., Kjaergaard, H. G., Canagaratna, M., Maso, M. D., Berndt, T., Petaja, 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.
Ehn, M., Berndt, T., Wildt, J., and Mentel, T.: Highly Oxygenated Molecules from Atmospheric Autoxidation of Hydrocarbons: A Prominent Challenge for Chemical Kinetics Studies, Int. J. Chem. Kinet., 49, 821–831, https://doi.org/10.1002/kin.21130, 2017.
Eisele, F. L. and Tanner, D. J.: Measurement of the gas-phase concentration of H2SO4 and Methane Sulfonic Acid and estimates of H2SO4 production and loss in the atmosphere, J. Geophys. Res.-Atmos., 98, 9001–9010, https://doi.org/10.1029/93jd00031, 1993.
Färber, M., Fuchs, H., Bohn, B., Carlsson, P. T., Gkatzelis, G. I., Marcillo Lara, A. C., Rohrer, F., Vereecken, L., Wedel, S., and Wahner, A.: Effect of the Alkoxy Radical Chemistry on the Ozone Formation from Anthropogenic Organic Compounds Investigated in Chamber Experiments, ACS ES&T Air, 1, 1096–1111, 2024.
Fittschen, C.: The reaction of peroxy radicals with OH radicals, Chem. Phys. Lett., 725, 102–108, https://doi.org/10.1016/j.cplett.2019.04.002, 2019.
Guenther, A. B., Jiang, X., Heald, C. L., Sakulyanontvittaya, T., Duhl, T., Emmons, L. K., 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, 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.
Hasan, G., Salo, V. T., Valiev, R. R., Kubecka, J., and Kurtén, T.: Comparing Reaction Routes for 3(RO⚫⚫⚫OR′) Intermediates Formed in Peroxy Radical Self- and Cross-Reactions, J. Phys. Chem. A, 124, 8305–8320, https://doi.org/10.1021/acs.jpca.0c05960, 2020.
Hyttinen, N., Rissanen, M. P., and Kurtén, T.: Computational Comparison of Acetate and Nitrate Chemical Ionization of Highly Oxidized Cyclohexene Ozonolysis Intermediates and Products, J. Phys. Chem. A, 121, 2172–2179, https://doi.org/10.1021/acs.jpca.6b12654, 2017.
Iyer, S., Reiman, H., Møller, K. H., Rissanen, M. P., Kjaergaard, H. G., and Kurtén, T.: Computational Investigation of RO2 + HO2 and RO2 + RO2 Reactions of Monoterpene Derived First-Generation Peroxy Radicals Leading to Radical Recycling, J. Phys. Chem. A, 122, 9542–9552, https://doi.org/10.1021/acs.jpca.8b09241, 2018.
Iyer, S., Rissanen, M. P., and Kurtén, T.: Reaction between Peroxy and Alkoxy Radicals Can Form Stable Adducts, J. Phys. Chem. Lett., 10, 2051–2057, https://doi.org/10.1021/acs.jpclett.9b00405, 2019.
Iyer, S., Rissanen, M. P., Valiev, R., Barua, S., Krechmer, J. E., Thornton, J., Ehn, M., and Kurtén, T.: Molecular mechanism for rapid autoxidation in α-pinene ozonolysis, Nat. Commun., 12, 878, https://doi.org/10.1038/s41467-021-21172-w, 2021.
Jaoui, M., Piletic, I. R., Szmigielski, R., Rudzinski, K. J., Lewandowski, M., Riedel, T. P., and Kleindienst, T. E.: Rapid production of highly oxidized molecules in isoprene aerosol via peroxy and alkoxy radical isomerization pathways in low and high NOx environments: Combined laboratory, computational and field studies, Sci. Total Environ., 775, 145592, https://doi.org/10.1016/j.scitotenv.2021.145592, 2021.
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.
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.
Johnson, D. and Marston, G.: The gas-phase ozonolysis of unsaturated volatile organic compounds in the troposphere, Chem. Soc. Rev., 37, 699–716, https://doi.org/10.1039/b704260b, 2008.
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., Berndt, T., Makkonen, R., Kerminen, V. M., Junninen, H., Paasonen, P., Stratmann, F., Herrmann, H., Guenther, A. B., Worsnop, D. R., Kulmala, M., Ehn, M., and Sipilä, M.: Production of extremely low volatile organic compounds from biogenic emissions: Measured yields and atmospheric implications, P. Natl. Acad. Sci. USA, 112, 7123–7128, https://doi.org/10.1073/pnas.1423977112, 2015.
Jokinen, T., Kontkanen, J., Lehtipalo, K., Manninen, H. E., Aalto, J., Porcar-Castell, A., Garmash, O., Nieminen, T., Ehn, M., Kangasluoma, J., Junninen, H., Levula, J., Duplissy, J., Ahonen, L. R., Rantala, P., Heikkinen, L., Yan, C., Sipilä, M., Worsnop, D. R., Bäck, J., Petäjä, T., Kerminen, V. M., and Kulmala, M.: Solar eclipse demonstrating the importance of photochemistry in new particle formation, Scientific Reports, 7, https://doi.org/10.1038/srep45707, 2017.
Junninen, H., Ehn, M., Petäjä, T., Luosujärvi, L., Kotiaho, T., Kostiainen, R., Rohner, U., Gonin, M., Fuhrer, K., Kulmala, M., and Worsnop, D. R.: A high-resolution mass spectrometer to measure atmospheric ion composition, Atmos. Meas. Tech., 3, 1039–1053, https://doi.org/10.5194/amt-3-1039-2010, 2010.
Kanakidou, M., Seinfeld, J. H., Pandis, S. N., Barnes, I., Dentener, F. J., Facchini, M. C., Van Dingenen, R., Ervens, B., Nenes, A., Nielsen, C. J., Swietlicki, E., Putaud, J. P., Balkanski, Y., Fuzzi, S., Horth, J., Moortgat, G. K., Winterhalter, R., Myhre, C. E. L., Tsigaridis, K., Vignati, E., Stephanou, E. G., and Wilson, J.: Organic aerosol and global climate modelling: a review, Atmos. Chem. Phys., 5, 1053–1123, https://doi.org/10.5194/acp-5-1053-2005, 2005.
Kang, S., Wildt, J., Pullinen, I., Vereecken, L., Wu, C., Wahner, A., Zorn, S. R., and Mentel, T. F.: Supplementary data for Formation of highly oxygenated organic molecules from α-pinene photooxidation: evidence for the importance of highly oxygenated alkoxy radicals, Jülich DATA [data set], https://doi.org/10.26165/JUELICH-DATA/0MTPDO, 2025.
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.
Kurtén, T., Petäjä, T., Smith, J., Ortega, I. K., Sipilä, M., Junninen, H., Ehn, M., Vehkamäki, H., Mauldin, L., Worsnop, D. R., and Kulmala, M.: The effect of H2SO4 – amine clustering on chemical ionization mass spectrometry (CIMS) measurements of gas-phase sulfuric acid, Atmos. Chem. Phys., 11, 3007–3019, https://doi.org/10.5194/acp-11-3007-2011, 2011.
Lamarque, J.-F., Bond, T. C., Eyring, V., Granier, C., Heil, A., Klimont, Z., Lee, D., Liousse, C., Mieville, A., Owen, B., Schultz, M. G., Shindell, D., Smith, S. J., Stehfest, E., Van Aardenne, J., Cooper, O. R., Kainuma, M., Mahowald, N., McConnell, J. R., Naik, V., Riahi, K., and van Vuuren, D. P.: Historical (1850–2000) gridded anthropogenic and biomass burning emissions of reactive gases and aerosols: methodology and application, Atmos. Chem. Phys., 10, 7017–7039, https://doi.org/10.5194/acp-10-7017-2010, 2010.
Lee, B. H., Mohr, C., Lopez-Hilfiker, F. D., Lutz, A., Hallquist, M., Lee, L., Romer, P., Cohen, R. C., Iyer, S., Kurten, T., Hu, W., Day, D. A., Campuzano-Jost, P., Jimenez, J. L., Xu, L., Ng, N. L., Guo, H., Weber, R. J., Wild, R. J., Brown, S. S., Koss, A., de Gouw, J., Olson, K., Goldstein, A. H., Seco, R., Kim, S., McAvey, K., Shepson, P. B., Starn, T., Baumann, K., Edgerton, E. S., Liu, J., Shilling, J. E., Miller, D. O., Brune, W., Schobesberger, S., D'Ambro, E. L., and Thornton, J. A.: Highly functionalized organic nitrates in the southeast United States: Contribution to secondary organic aerosol and reactive nitrogen budgets, P. Natl. Acad. Sci. USA, 113, 1516–1521, 2016.
Lee, B. H., Iyer, S., Kurtén, T., Varelas, J. G., Luo, J. Y., Thomson, R. J., and Thornton, J. A.: Ring-opening yields and auto-oxidation rates of the resulting peroxy radicals from OH-oxidation of α-pinene and β-pinene (vol 3, pg 399, 2023), Environmental Science-Atmospheres, 3, 1847–1847, https://doi.org/10.1039/d3ea90045b, 2023.
Luo, H., Vereecken, L., Shen, H., Kang, S., Pullinen, I., Hallquist, M., Fuchs, H., Wahner, A., Kiendler-Scharr, A., Mentel, T. F., and Zhao, D.: Formation of highly oxygenated organic molecules from the oxidation of limonene by OH radical: significant contribution of H-abstraction pathway, Atmos. Chem. Phys., 23, 7297–7319, https://doi.org/10.5194/acp-23-7297-2023, 2023.
McFiggans, G., Mentel, T. F., Wildt, J., Pullinen, I., Kang, S., Kleist, E., Schmitt, S., Springer, M., Tillmann, R., Wu, C., Zhao, D., Hallquist, M., Faxon, C., Le Breton, M., Hallquist, Å. M., Simpson, D., Bergström, R., Jenkin, M. E., Ehn, M., Thornton, J. A., Alfarra, M. R., Bannan, T. J., Percival, C. J., Priestley, M., Topping, D., and Kiendler-Scharr, A.: Secondary organic aerosol reduced by mixture of atmospheric vapours, Nature, 565, 587–593, https://doi.org/10.1038/s41586-018-0871-y, 2019.
Meder, M., Peräkylä, O., Varelas, J. G., Luo, J., Cai, R., Zhang, Y., Kurtén, T., Riva, M., Rissanen, M., Geiger, F. M., Thomson, R. J., and Ehn, M.: Selective deuteration as a tool for resolving autoxidation mechanisms in α-pinene ozonolysis, Atmos. Chem. Phys., 23, 4373–4390, https://doi.org/10.5194/acp-23-4373-2023, 2023.
Meder, M., Graeffe, F., Luo, Y. Y., Luo, J. Y., Iyer, S., Valiev, R., Cai, R. L., Rissanen, M., Kurtén, T., Varelas, J. G., Geiger, F. M., Thomson, R. J., and Ehn, M.: Selective Deuteration Reveals the Importance of Multiple Branching Pathways in α-Pinene Autoxidation, J. Am. Chem. Soc., 147, 14131–14138, https://doi.org/10.1021/jacs.4c14462, 2025.
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.
Mentel, Th. F., Wildt, J., Kiendler-Scharr, A., Kleist, E., Tillmann, R., Dal Maso, M., Fisseha, R., Hohaus, Th., Spahn, H., Uerlings, R., Wegener, R., Griffiths, P. T., Dinar, E., Rudich, Y., and Wahner, A.: Photochemical production of aerosols from real plant emissions, Atmos. Chem. Phys., 9, 4387–4406, https://doi.org/10.5194/acp-9-4387-2009, 2009.
Molteni, U., Simon, M., Heinritzi, M., Hoyle, C. R., Bernhammer, A. K., Bianchi, F., Breitenlechner, M., Brilke, S., Dias, A., Duplissy, J., Frege, C., Gordon, H., Heyn, C., Jokinen, T., Kurten, A., Lehtipalo, K., Makhmutov, V., Petaja, T., Pieber, S. M., Praplan, A. P., Schobesberger, S., Steiner, G., Stozhkov, Y., Tome, A., Trostl, J., Wagner, A. C., Wagner, R., Williamson, C., Yan, C., Baltensperger, U., Curtius, J., Donahue, N. M., Hansel, A., Kirkby, J., Kulmala, M., Worsnop, D. R., and Dommen, J.: Formation of Highly Oxygenated Organic Molecules from α-Pinene Ozonolysis: Chemical Characteristics, Mechanism, and Kinetic Model Development, ACS Earth and Space Chemistry, 3, 873–883, https://doi.org/10.1021/acsearthspacechem.9b00035, 2019.
Mutzel, A., Poulain, L., Berndt, T., Iinuma, Y., Rodigast, M., Boege, O., Richters, S., Spindler, G., Sipila, M., Jokinen, T., Kulmala, M., and Herrmann, H.: Highly Oxidized Multifunctional Organic Compounds Observed in Tropospheric Particles: A Field and Laboratory Study, Environ. Sci. Technol., 49, 7754–7761, https://doi.org/10.1021/acs.est.5b00885, 2015.
Ng, N. L., Chhabra, P. S., Chan, A. W. H., Surratt, J. D., Kroll, J. H., Kwan, A. J., McCabe, D. C., Wennberg, P. O., Sorooshian, A., Murphy, S. M., Dalleska, N. F., Flagan, R. C., and Seinfeld, J. H.: Effect of NOx level on secondary organic aerosol (SOA) formation from the photooxidation of terpenes, Atmos. Chem. Phys., 7, 5159–5174, https://doi.org/10.5194/acp-7-5159-2007, 2007.
Nie, W., Yan, C., Yang, L. W., Roldin, P., Liu, Y. L., Vogel, A. L., Molteni, U., Stolzenburg, D., Finkenzeller, H., Amorim, A., Bianchi, F., Curtius, J., Dada, L., Draper, D. C., Duplissy, J., Hansel, A., He, X. C., Hofbauer, V., Jokinen, T., Kim, C., Lehtipalo, K., Nichman, L., Mauldin, R. L., Makhmutov, V., Mentler, B., Mizelli-Ojdanic, A., Petäjä, T., Quéléver, L. L. J., Schallhart, S., Simon, M., Tauber, C., Tomé, A., Volkamer, R., Wagner, A. C., Wagner, R., Wang, M. Y., Ye, P. L., Li, H. Y., Huang, W., Qi, X. M., Lou, S. J., Liu, T. Y., Chi, X. G., Dommen, J., Baltensperger, U., El Haddad, I., Kirkby, J., Worsnop, D., Kulmala, M., Donahue, N. M., Ehn, M., and Ding, A. J.: NO at low concentration can enhance the formation of highly oxygenated biogenic molecules in the atmosphere, Nat. Commun., 14, https://doi.org/10.1038/s41467-023-39066-4, 2023.
Nozière, B., Barnes, I., and Becker, K. H.: Product study and mechanisms of the reactions of α-pinene and of pinonaldehyde with OH radicals, J. Geophys. Res.-Atmos., 104, 23645–23656, https://doi.org/10.1029/1999jd900778, 1999.
Paulson, S. E., Chung, M., Sen, A. D., and Orzechowska, G.: Measurement of OH radical formation from the reaction of ozone with several biogenic alkenes, J. Geophys. Res.-Atmos., 103, 25533–25539, 1998.
Peeters, J., Vereecken, L., and Fantechi, G.: The detailed mechanism of the OH-initiated atmospheric oxidation of α-pinene: a theoretical study, Phys. Chem. Chem. Phys., 3, 5489–5504, https://doi.org/10.1039/b106555f, 2001.
Peräkylä, O., Berndt, T., Franzon, L., Hasan, G., Meder, M., Valiev, R. R., Daub, C. D., Varelas, J. G., Geiger, F. M., Thomson, R. J., Rissanen, M., Kurtén, T., and Ehn, M.: Large Gas-Phase Source of Esters and Other Accretion Products in the Atmosphere, J. Am. Chem. Soc., 145, 7780–7790, https://doi.org/10.1021/jacs.2c10398, 2023.
Piletic, I. R. and Kleindienst, T. E.: Rates and Yields of Unimolecular Reactions Producing Highly Oxidized Peroxy Radicals in the OH-Induced Autoxidation of α-Pinene, β-Pinene, and Limonene, J. Phys. Chem. A, 126, 88–100, https://doi.org/10.1021/acs.jpca.1c07961, 2022.
Praske, E., Otkjaer, 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.
Pullinen, I., Schmitt, S., Kang, S., Sarrafzadeh, M., Schlag, P., Andres, S., Kleist, E., Mentel, T. F., Rohrer, F., Springer, M., Tillmann, R., Wildt, J., Wu, C., Zhao, D., Wahner, A., and Kiendler-Scharr, A.: Impact of NOx on secondary organic aerosol (SOA) formation from α-pinene and β-pinene photooxidation: the role of highly oxygenated organic nitrates, Atmos. Chem. Phys., 20, 10125–10147, https://doi.org/10.5194/acp-20-10125-2020, 2020.
Pye, H. O. T., Chan, A. W. H., Barkley, M. P., and Seinfeld, J. H.: Global modeling of organic aerosol: the importance of reactive nitrogen (NOx and NO3), Atmos. Chem. Phys., 10, 11261–11276, https://doi.org/10.5194/acp-10-11261-2010, 2010.
Rissanen, M. P.: NO2 Suppression of Autoxidation-Inhibition of Gas-Phase Highly Oxidized Dimer Product Formation, ACS Earth and Space Chemistry, 2, 1211–1219, https://doi.org/10.1021/acsearthspacechem.8b00123, 2018.
Rissanen, M. P., Kurten, T., Sipila, M., Thornton, J. A., Kangasluoma, J., Sarnela, N., Junninen, H., Jorgensen, S., Schallhart, S., Kajos, M. K., Taipale, R., Springer, M., Mentel, T. F., Ruuskanen, T., Petaja, 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.
Roldin, P., Ehn, M., Kurten, T., Olenius, T., Rissanen, M. P., Sarnela, N., Elm, J., Rantala, P., Hao, L. Q., Hyttinen, N., Heikkinen, L., Worsnop, D. R., Pichelstorfer, L., Xavier, C., Clusius, P., Ostrom, E., Petaja, T., Kulmala, M., Vehkamaki, 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, https://doi.org/10.1038/s41467-019-12338-8, 2019.
Rollins, A. W., Smith, J. D., Wilson, K. R., and Cohen, R. C.: Real Time In Situ Detection of Organic Nitrates in Atmospheric Aerosols, Environ. Sci. Technol., 44, 5540–5545, https://doi.org/10.1021/es100926x, 2010.
Sarrafzadeh, M., Wildt, J., Pullinen, I., Springer, M., Kleist, E., Tillmann, R., Schmitt, S. H., Wu, C., Mentel, T. F., Zhao, D., Hastie, D. R., and Kiendler-Scharr, A.: Impact of NOx and OH on secondary organic aerosol formation from β-pinene photooxidation, Atmos. Chem. Phys., 16, 11237–11248, https://doi.org/10.5194/acp-16-11237-2016, 2016.
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.
Shen, H., Vereecken, L., Kang, S., Pullinen, I., Fuchs, H., Zhao, D., and Mentel, T. F.: Unexpected significance of a minor reaction pathway in daytime formation of biogenic highly oxygenated organic compounds, Science Advances, 8, eabp8702, https://doi.org/10.1126/sciadv.abp8702, 2022.
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.
Stolzenburg, D., Fischer, L., Vogel, A. L., Heinritzi, M., Schervish, M., Simon, M., Wagner, A. C., Dada, L., Ahonen, L. R., Amorim, A., Baccarini, A., Bauer, P. S., Baumgartner, B., Bergen, A., Bianchi, F., Breitenlechner, M., Brilke, S., Mazon, S. B., Chen, D. X., Dias, A., Draper, D. C., Duplissy, J., Haddad, I., Finkenzeller, H., Frege, C., Fuchs, C., Garmash, O., Gordon, H., He, X., Helm, J., Hofbauer, V., Hoyle, C. R., Kim, C., Kirkby, J., Kontkanen, J., Kuerten, A., Lampilahti, J., Lawler, M., Lehtipalo, K., Leiminger, M., Mai, H., Mathot, S., Mentler, B., Molteni, U., Nie, W., Nieminen, T., Nowak, J. B., Ojdanic, A., Onnela, A., Passananti, M., Petaja, T., Quelever, L. L. J., Rissanen, M. P., Sarnela, N., Schallhart, S., Tauber, C., Tome, A., Wagner, R., Wang, M., Weitz, L., Wimmer, D., Xiao, M., Yan, C., Ye, P., Zha, Q., Baltensperger, U., Curtius, J., Dommen, J., Flagan, R. C., Kulmala, M., Smith, J. N., Worsnop, D. R., Hansel, A., Donahue, N. M., and Winkler, P. M.: Rapid growth of organic aerosol nanoparticles over a wide tropospheric temperature range, P. Natl. Acad. Sci. USA, 115, 9122–9127, https://doi.org/10.1073/pnas.1807604115, 2018.
Tröstl, J., Chuang, W. K., Gordon, H., Heinritzi, M., Yan, C., Molteni, U., Ahlm, L., Frege, C., Bianchi, F., Wagner, R., Simon, M., Lehtipalo, K., Williamson, C., Craven, J. S., Duplissy, J., Adamov, A., Almeida, J., Bernhammer, A. K., Breitenlechner, M., Brilke, S., Dias, A., Ehrhart, S., Flagan, R. C., Franchin, A., Fuchs, C., Guida, R., Gysel, M., Hansel, A., Hoyle, C. R., Jokinen, T., Junninen, H., Kangasluoma, J., Keskinen, H., Kim, J., Krapf, M., Kurten, A., Laaksonen, A., Lawler, M., Leiminger, M., Mathot, S., Mohler, O., Nieminen, T., Onnela, A., Petaja, T., Piel, F. M., Miettinen, P., Rissanen, M. P., Rondo, L., Sarnela, N., Schobesberger, S., Sengupta, K., Sipila, M., Smith, J. N., Steiner, G., Tome, A., Virtanen, A., Wagner, A. C., Weingartner, E., Wimmer, D., Winkler, P. M., Ye, P. L., Carslaw, K. S., Curtius, J., Dommen, J., Kirkby, J., Kulmala, M., Riipinen, I., Worsnop, D. R., Donahue, N. M., and Baltensperger, U.: The role of low-volatility organic compounds in initial particle growth in the atmosphere, Nature, 533, 527–531, https://doi.org/10.1038/nature18271, 2016.
Valiev, R. R., Hasan, G., Salo, V. T., Kubecka, J., and Kurten, T.: Intersystem Crossings Drive Atmospheric Gas-Phase Dimer Formation, J. Phys. Chem. A, 123, 6596–6604, https://doi.org/10.1021/acs.jpca.9b02559, 2019.
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.: Nontraditional (per)oxy ring-closure paths in the atmospheric oxidation of isoprene and monoterpenes, J. Phys. Chem. A, 108, 5197–5204, https://doi.org/10.1021/jp049219g, 2004.
Vereecken, L. and Peeters, J.: Decomposition of substituted alkoxy radicals – part I: a generalized structure-activity relationship for reaction barrier heights, Phys. Chem. Chem. Phys., 11, 9062–9074, https://doi.org/10.1039/b909712k, 2009.
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, 12608–12620, https://doi.org/10.1039/c0cp00387e, 2010.
Vereecken, L., Mueller, J. F., and Peeters, J.: Low-volatility poly-oxygenates in the OH-initiated atmospheric oxidation of α-pinene: impact of non-traditional peroxyl radical chemistry, Phys. Chem. Chem. Phys., 9, 5241–5248, https://doi.org/10.1039/b708023a, 2007.
Vereecken, L., Vu, G., Wahner, A., Kiendler-Scharr, A., and Nguyen, H. M. T.: A structure activity relationship for ring closure reactions in unsaturated alkylperoxy radicals, Phys. Chem. Chem. Phys., 23, 16564–16576, https://doi.org/10.1039/d1cp02758a, 2021.
von Schneidemesser, E., Monks, P. S., Allan, J. D., Bruhwiler, L., Forster, P., Fowler, D., Lauer, A., Morgan, W. T., Paasonen, P., Righi, M., Sindelarova, K., and Sutton, M. A.: Chemistry and the Linkages between Air Quality and Climate Change, Chem. Rev., 115, 3856–3897, https://doi.org/10.1021/acs.chemrev.5b00089, 2015.
Wang, Z. D., Ehn, M., Rissanen, M. P., Garmash, O., Quéléver, L., Xing, L. L., Monge-Palacios, M., Rantala, P., Donahue, N. M., Berndt, T., and Sarathy, S. M.: Efficient alkane oxidation under combustion engine and atmospheric conditions, Communications Chemistry, 4, https://doi.org/10.1038/s42004-020-00445-3, 2021.
Wildt, J., Mentel, T. F., Kiendler-Scharr, A., Hoffmann, T., Andres, S., Ehn, M., Kleist, E., Müsgen, P., Rohrer, F., Rudich, Y., Springer, M., Tillmann, R., and Wahner, A.: Suppression of new particle formation from monoterpene oxidation by NOx, Atmos. Chem. Phys., 14, 2789–2804, https://doi.org/10.5194/acp-14-2789-2014, 2014.
Xu, L., Moller, K. H., Crounse, J. D., Otkjwr, R. V., Kjaergaard, H. G., and Wennberg, P. O.: Unimolecular Reactions of Peroxy Radicals Formed in the Oxidation of α-Pinene and β-Pinene by Hydroxyl Radicals, J. Phys. Chem. A, 123, 1661–1674, https://doi.org/10.1021/acs.jpca.8b11726, 2019.
Yang, H., Raucci, U., Iyer, S., Hasan, G., Almeida, T. G., Barua, S., Savolainen, A., Kangasluoma, J., Rissanen, M., Vehkamäki, H., and Kurtén, T.: Molecular dynamics-guided reaction discovery reveals endoperoxide-to-alkoxy radical isomerization as key branching point in α-pinene ozonolysis, Nat. Commun., 16, https://doi.org/10.1038/s41467-025-55985-w, 2025.
Zhao, D., Schmitt, S. H., Wang, M., Acir, I.-H., Tillmann, R., Tan, Z., Novelli, A., Fuchs, H., Pullinen, I., Wegener, R., Rohrer, F., Wildt, J., Kiendler-Scharr, A., Wahner, A., and Mentel, T. F.: Effects of NOx and SO2 on the secondary organic aerosol formation from photooxidation of α-pinene and limonene, Atmos. Chem. Phys., 18, 1611–1628, https://doi.org/10.5194/acp-18-1611-2018, 2018.
Short summary
Highly oxygenated organic molecules by atmospheric oxidation of plant emitted monoterpenes are important components in secondary organic aerosol formation. Autoxidation of organic peroxy radicals is one important pathway of their formation. We show that isomerization of highly oxygenated alkoxy radicals leads to highly oxygenated peroxy radicals that continue the autoxidation chain. Alkoxy-peroxy steps may dominate the formation of highly oxygenated molecules at high nitrogen oxide levels.
Highly oxygenated organic molecules by atmospheric oxidation of plant emitted monoterpenes are...
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