Articles | Volume 23, issue 13
https://doi.org/10.5194/acp-23-7297-2023
© Author(s) 2023. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
https://doi.org/10.5194/acp-23-7297-2023
© Author(s) 2023. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
04 Jul 2023
Research article |
| 04 Jul 2023
| 04 Jul 2023
Formation of highly oxygenated organic molecules from the oxidation of limonene by OH radical: significant contribution of H-abstraction pathway
Hao Luo
Department of Atmospheric and Oceanic Sciences & Institute of
Atmospheric Sciences, Fudan University, Shanghai 200438, China
National Observations and Research Station for Wetland Ecosystems of the Yangtze Estuary, Fudan University, Shanghai 200438, China
Luc Vereecken
Institute of Energy and Climate Research, IEK-8: Troposphere,
Forschungszentrum Jülich, 52425 Jülich, Germany
Hongru Shen
Department of Atmospheric and Oceanic Sciences & Institute of
Atmospheric Sciences, Fudan University, Shanghai 200438, China
National Observations and Research Station for Wetland Ecosystems of the Yangtze Estuary, Fudan University, Shanghai 200438, China
Sungah Kang
Institute of Energy and Climate Research, IEK-8: Troposphere,
Forschungszentrum Jülich, 52425 Jülich, Germany
Iida Pullinen
Institute of Energy and Climate Research, IEK-8: Troposphere,
Forschungszentrum Jülich, 52425 Jülich, Germany
now at: Department of Applied Physics, University of Eastern Finland, 70210 Kuopio, Finland
Mattias Hallquist
Department of Chemistry and Molecular biology, University of
Gothenburg, 41258 Gothenburg, Sweden
Hendrik Fuchs
Institute of Energy and Climate Research, IEK-8: Troposphere,
Forschungszentrum Jülich, 52425 Jülich, Germany
Fachgruppe Physik, Universität zu Köln, 50932 Cologne,
Germany
Andreas Wahner
Institute of Energy and Climate Research, IEK-8: Troposphere,
Forschungszentrum Jülich, 52425 Jülich, Germany
Astrid Kiendler-Scharr
Institute of Energy and Climate Research, IEK-8: Troposphere,
Forschungszentrum Jülich, 52425 Jülich, Germany
deceased, 6 February 2023
Institute of Energy and Climate Research, IEK-8: Troposphere,
Forschungszentrum Jülich, 52425 Jülich, Germany
Department of Atmospheric and Oceanic Sciences & Institute of
Atmospheric Sciences, Fudan University, Shanghai 200438, China
National Observations and Research Station for Wetland Ecosystems of the Yangtze Estuary, Fudan University, Shanghai 200438, China
Shanghai Frontiers Science Center of Atmosphere–Ocean Interaction,
Fudan University, Shanghai 200438, China
Institute of Eco-Chongming (IEC), 20 Cuiniao Rd., Chongming, Shanghai 202162, China
CMA-FDU Joint Laboratory of Marine Meteorology, Fudan University,
Shanghai 200438, China
Related authors
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
Short summary
Short summary
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.
Lu Liu, Thorsten Hohaus, Andreas Hofzumahaus, Frank Holland, Hendrik Fuchs, Ralf Tillmann, Birger Bohn, Stefanie Andres, Zhaofeng Tan, Franz Rohrer, Vlassis A. Karydis, Vaishali Vardhan, Philipp Franke, Anne C. Lange, Anna Novelli, Benjamin Winter, Changmin Cho, Iulia Gensch, Sergej Wedel, Andreas Wahner, and Astrid Kiendler-Scharr
EGUsphere, https://doi.org/10.5194/egusphere-2025-3074, https://doi.org/10.5194/egusphere-2025-3074, 2025
Short summary
Short summary
We measured air particles at a rural site in Germany over a year to understand how their sources and properties change with the seasons. Particles from natural sources peaked in summer, especially during heatwaves, while those from burning activities like residential heating and wildfires dominated in colder months. Winds carrying air from other regions also influenced particle levels. These findings link air quality to climate change and energy transitions.
Susanne M. C. Scholz, Vlassis A. Karydis, Georgios I. Gkatzelis, Hendrik Fuchs, Spyros N. Pandis, and Alexandra P. Tsimpidi
EGUsphere, https://doi.org/10.5194/egusphere-2025-2510, https://doi.org/10.5194/egusphere-2025-2510, 2025
Short summary
Short summary
We studied how pollution from cars and trucks contributes to tiny airborne particles that affect air quality and climate. These particles, called secondary organic aerosols, were often underestimated in global models. By improving how certain overlooked emissions from fuel use are represented in our model, we found that their impact is much larger than previously thought. Our results suggest that road traffic plays a far greater role in global air pollution than earlier estimates showed.
Sungah Kang, Jürgen Wildt, Iida Pullinen, Luc Vereecken, Cheng Wu, Andreas Wahner, Sören R. Zorn, and Thomas F. Mentel
EGUsphere, https://doi.org/10.5194/egusphere-2025-2772, https://doi.org/10.5194/egusphere-2025-2772, 2025
Short summary
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.
Arttu Ylisirniö, Noora Hyttinen, Zijun Li, Mitchell Alton, Aki Nissinen, Iida Pullinen, Pasi Miettinen, Taina Yli-Juuti, and Siegfried Schobesberger
EGUsphere, https://doi.org/10.5194/egusphere-2025-2219, https://doi.org/10.5194/egusphere-2025-2219, 2025
Short summary
Short summary
This study aims to increase knowledge of the low volatility organic compouds observed in ambient aerosol particles by providing new volatility information about compounds used for calibrating volatility measurement instruments. Previously, such information has was not available and calibration of the instrument had to be extrapolated to cover the whole measurement range. Results of this study will provide the scientific community better tools for investigating the complexity of ambient aerosols.
Alexander Hermanns, Anne Caroline Lange, Julia Kowalski, Hendrik Fuchs, and Philipp Franke
EGUsphere, https://doi.org/10.5194/egusphere-2025-450, https://doi.org/10.5194/egusphere-2025-450, 2025
Short summary
Short summary
For air quality analyses, data assimilation models split available data into assimilation and validation data sets. The former is used to generate the analysis, the latter to verify the simulations. A preprocessor classifying the observations by the data characteristics is developed based on clustering algorithms. The assimilation and validation data sets are compiled by equally allocating data of each cluster. The resulting improvement of the analysis is evaluated with EURAD-IM.
Michael Rolletter, Andreas Hofzumahaus, Anna Novelli, Andreas Wahner, and Hendrik Fuchs
Atmos. Chem. Phys., 25, 3481–3502, https://doi.org/10.5194/acp-25-3481-2025, https://doi.org/10.5194/acp-25-3481-2025, 2025
Short summary
Short summary
Highly accurate rate coefficients of termolecular reactions between OH and HO2 radicals and reactive nitrogen oxides were measured for conditions in the lower troposphere, providing improved constraints on recommended values. No dependence on water vapour was found except for the HO2+NO2 reaction, which can be explained by an enhanced rate coefficient of the NO2 reaction with the water complex of the HO2 radical.
Hendrik Fuchs, Aaron Stainsby, Florian Berg, René Dubus, Michelle Färber, Andreas Hofzumahaus, Frank Holland, Kelvin H. Bates, Steven S. Brown, Matthew M. Coggon, Glenn S. Diskin, Georgios I. Gkatzelis, Christopher M. Jernigan, Jeff Peischl, Michael A. Robinson, Andrew W. Rollins, Nell B. Schafer, Rebecca H. Schwantes, Chelsea E. Stockwell, Patrick R. Veres, Carsten Warneke, Eleanor M. Waxman, Lu Xu, Kristen Zuraski, Andreas Wahner, and Anna Novelli
Atmos. Meas. Tech., 18, 881–895, https://doi.org/10.5194/amt-18-881-2025, https://doi.org/10.5194/amt-18-881-2025, 2025
Short summary
Short summary
Significant improvements have been made to the instruments used to measure OH reactivity, which is equivalent to the sum of air pollutant concentrations. Accurate and precise measurements with a high time resolution have been achieved, allowing use on aircraft, as demonstrated during flights in the USA.
Alexandros Milousis, Susanne M. C. Scholz, Hendrik Fuchs, Alexandra P. Tsimpidi, and Vlassis A. Karydis
EGUsphere, https://doi.org/10.5194/egusphere-2025-313, https://doi.org/10.5194/egusphere-2025-313, 2025
Short summary
Short summary
Nitrate aerosol has become a dominant atmospheric component, surpassing sulfate in aerosol composition. However, its simulation remains challenging due to complex formation processes and regional variability. We use the EMAC model to assess key factors in nitrate aerosol predictions. Increasing grid resolution, reducing N2O5 hydrolysis uptake, and refined emissions improve PM2.5 predictions, but PM1 remains underestimated. Seasonal & diurnal discrepancies persist, requiring further refinements.
Hassnae Erraji, Philipp Franke, Astrid Lampert, Tobias Schuldt, Ralf Tillmann, Andreas Wahner, and Anne Caroline Lange
Atmos. Chem. Phys., 24, 13913–13934, https://doi.org/10.5194/acp-24-13913-2024, https://doi.org/10.5194/acp-24-13913-2024, 2024
Short summary
Short summary
Four-dimensional variational data assimilation allows for the simultaneous optimisation of initial values and emission rates by using trace-gas profiles from drone observations in a regional air quality model. Assimilated profiles positively impact the representation of air pollutants in the model by improving their vertical distribution and ground-level concentrations. This case study highlights the potential of drone data to enhance air quality analyses including local emission evaluation.
Florian Berg, Anna Novelli, René Dubus, Andreas Hofzumahaus, Frank Holland, Andreas Wahner, and Hendrik Fuchs
Atmos. Chem. Phys., 24, 13715–13731, https://doi.org/10.5194/acp-24-13715-2024, https://doi.org/10.5194/acp-24-13715-2024, 2024
Short summary
Short summary
This study reports temperature-dependent rate coefficients of the reaction of atmospherically relevant hydrocarbons from biogenic sources (methyl vinyl ketones and monoterpenes) and anthropogenic sources (alkanes and aromatics). Measurements were done at atmospheric conditions (ambient pressure and temperature range) in air.
Barbara Ervens, Andrew Rickard, Bernard Aumont, William P. L. Carter, Max McGillen, Abdelwahid Mellouki, John Orlando, Bénédicte Picquet-Varrault, Paul Seakins, William R. Stockwell, Luc Vereecken, and Timothy J. Wallington
Atmos. Chem. Phys., 24, 13317–13339, https://doi.org/10.5194/acp-24-13317-2024, https://doi.org/10.5194/acp-24-13317-2024, 2024
Short summary
Short summary
Chemical mechanisms describe the chemical processes in atmospheric models that are used to describe the changes in the atmospheric composition. Therefore, accurate chemical mechanisms are necessary to predict the evolution of air pollution and climate change. The article describes all steps that are needed to build chemical mechanisms and discusses the advances and needs of experimental and theoretical research activities needed to build reliable chemical mechanisms.
Kuo-Ying Wang, Philippe Nedelec, Valerie Thouret, Hannah Clark, Andreas Wahner, and Andreas Petzold
EGUsphere, https://doi.org/10.5194/egusphere-2024-2414, https://doi.org/10.5194/egusphere-2024-2414, 2024
Short summary
Short summary
We use routine in-service commercial passenger airplanes Airbus A340 and A330 to collect air pollutants in the upper troposphere. The beauty in using commercial airplanes is that these commercial airplanes, like taxi on the ground, keep flying all the time. We find that short-lived air pollutants are very sensitive to ground-level emissions. Effective regulation in ground-level emissions can help to reduce air pollution in the upper troposphere.
Felix Wieser, Rolf Sander, Changmin Cho, Hendrik Fuchs, Thorsten Hohaus, Anna Novelli, Ralf Tillmann, and Domenico Taraborrelli
Geosci. Model Dev., 17, 4311–4330, https://doi.org/10.5194/gmd-17-4311-2024, https://doi.org/10.5194/gmd-17-4311-2024, 2024
Short summary
Short summary
The chemistry scheme of the atmospheric box model CAABA/MECCA is expanded to achieve an improved aerosol formation from emitted organic compounds. In addition to newly added reactions, temperature-dependent partitioning of all new species between the gas and aqueous phases is estimated and included in the pre-existing scheme. Sensitivity runs show an overestimation of key compounds from isoprene, which can be explained by a lack of aqueous-phase degradation reactions and box model limitations.
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.
Rongrong Wu, Sören R. Zorn, Sungah Kang, Astrid Kiendler-Scharr, Andreas Wahner, and Thomas F. Mentel
Atmos. Meas. Tech., 17, 1811–1835, https://doi.org/10.5194/amt-17-1811-2024, https://doi.org/10.5194/amt-17-1811-2024, 2024
Short summary
Short summary
Recent advances in high-resolution time-of-flight chemical ionization mass spectrometry (CIMS) enable the detection of highly oxygenated organic molecules, which efficiently contribute to secondary organic aerosol. Here we present an application of fuzzy c-means (FCM) clustering to deconvolve CIMS data. FCM not only reduces the complexity of mass spectrometric data but also the chemical and kinetic information retrieved by clustering gives insights into the chemical processes involved.
Ernst-Peter Röth and Luc Vereecken
Atmos. Chem. Phys., 24, 2625–2638, https://doi.org/10.5194/acp-24-2625-2024, https://doi.org/10.5194/acp-24-2625-2024, 2024
Short summary
Short summary
The paper presents the radical and molecular product quantum yields in the photolysis reaction of CHDO at wavelengths above 300 nm. Two different approaches based on literature data are used, with results falling within both approaches' uncertainty ranges. Simple functional forms are presented for use in photochemical models of the atmosphere.
Jacky Y. S. Pang, Florian Berg, Anna Novelli, Birger Bohn, Michelle Färber, Philip T. M. Carlsson, René Dubus, Georgios I. Gkatzelis, Franz Rohrer, Sergej Wedel, Andreas Wahner, and Hendrik Fuchs
Atmos. Chem. Phys., 23, 12631–12649, https://doi.org/10.5194/acp-23-12631-2023, https://doi.org/10.5194/acp-23-12631-2023, 2023
Short summary
Short summary
In this study, the oxidations of sabinene by OH radicals and ozone were investigated with an atmospheric simulation chamber. Reaction rate coefficients of the OH-oxidation reaction at temperatures between 284 to 340 K were determined for the first time in the laboratory by measuring the OH reactivity. Product yields determined in chamber experiments had good agreement with literature values, but discrepancies were found between experimental yields and expected yields from oxidation mechanisms.
Marc von Hobe, Domenico Taraborrelli, Sascha Alber, Birger Bohn, Hans-Peter Dorn, Hendrik Fuchs, Yun Li, Chenxi Qiu, Franz Rohrer, Roberto Sommariva, Fred Stroh, Zhaofeng Tan, Sergej Wedel, and Anna Novelli
Atmos. Chem. Phys., 23, 10609–10623, https://doi.org/10.5194/acp-23-10609-2023, https://doi.org/10.5194/acp-23-10609-2023, 2023
Short summary
Short summary
The trace gas carbonyl sulfide (OCS) transports sulfur from the troposphere to the stratosphere, where sulfate aerosols are formed that influence climate and stratospheric chemistry. An uncertain OCS source in the troposphere is chemical production form dimethyl sulfide (DMS), a gas released in large quantities from the oceans. We carried out experiments in a large atmospheric simulation chamber to further elucidate the chemical mechanism of OCS production from DMS.
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
Short summary
Short summary
The investigation of the night-time oxidation of the most abundant hydrocarbon, isoprene, in chamber experiments shows the importance of reaction pathways leading to epoxy products, which could enhance particle formation, that have so far not been accounted for. The chemical lifetime of organic nitrates from isoprene is long enough for the majority to be further oxidized the next day by daytime oxidants.
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
Short summary
Short summary
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.
Tobias Schuldt, Georgios I. Gkatzelis, Christian Wesolek, Franz Rohrer, Benjamin Winter, Thomas A. J. Kuhlbusch, Astrid Kiendler-Scharr, and Ralf Tillmann
Atmos. Meas. Tech., 16, 373–386, https://doi.org/10.5194/amt-16-373-2023, https://doi.org/10.5194/amt-16-373-2023, 2023
Short summary
Short summary
We report in situ measurements of air pollutant concentrations within the planetary boundary layer on board a Zeppelin NT in Germany. We highlight the in-flight evaluation of electrochemical sensors that were installed inside a hatch box located on the bottom of the Zeppelin. Results from this work emphasize the potential of these sensors for other in situ airborne applications, e.g., on board unmanned aerial vehicles (UAVs).
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
Short summary
Short summary
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
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.
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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.
Ralf Tillmann, Georgios I. Gkatzelis, Franz Rohrer, Benjamin Winter, Christian Wesolek, Tobias Schuldt, Anne C. Lange, Philipp Franke, Elmar Friese, Michael Decker, Robert Wegener, Morten Hundt, Oleg Aseev, and Astrid Kiendler-Scharr
Atmos. Meas. Tech., 15, 3827–3842, https://doi.org/10.5194/amt-15-3827-2022, https://doi.org/10.5194/amt-15-3827-2022, 2022
Short summary
Short summary
We report in situ measurements of air pollutant concentrations within the planetary boundary layer on board a Zeppelin in Germany. The low costs of commercial flights provide an affordable and efficient method to improve our understanding of changes in emissions in space and time. The experimental setup expands the capabilities of this platform and provides insights into primary and secondary pollution observations and planetary boundary layer dynamics which determine air quality significantly.
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
Short summary
Short summary
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.
Andrea Pozzer, Simon F. Reifenberg, Vinod Kumar, Bruno Franco, Matthias Kohl, Domenico Taraborrelli, Sergey Gromov, Sebastian Ehrhart, Patrick Jöckel, Rolf Sander, Veronica Fall, Simon Rosanka, Vlassis Karydis, Dimitris Akritidis, Tamara Emmerichs, Monica Crippa, Diego Guizzardi, Johannes W. Kaiser, Lieven Clarisse, Astrid Kiendler-Scharr, Holger Tost, and Alexandra Tsimpidi
Geosci. Model Dev., 15, 2673–2710, https://doi.org/10.5194/gmd-15-2673-2022, https://doi.org/10.5194/gmd-15-2673-2022, 2022
Short summary
Short summary
A newly developed setup of the chemistry general circulation model EMAC (ECHAM5/MESSy for Atmospheric Chemistry) is evaluated here. A comprehensive organic degradation mechanism is used and coupled with a volatility base model.
The results show that the model reproduces most of the tracers and aerosols satisfactorily but shows discrepancies for oxygenated organic gases. It is also shown that this model configuration can be used for further research in atmospheric chemistry.
Zhi-Hui Zhang, Elena Hartner, Battist Utinger, Benjamin Gfeller, Andreas Paul, Martin Sklorz, Hendryk Czech, Bin Xia Yang, Xin Yi Su, Gert Jakobi, Jürgen Orasche, Jürgen Schnelle-Kreis, Seongho Jeong, Thomas Gröger, Michal Pardo, Thorsten Hohaus, Thomas Adam, Astrid Kiendler-Scharr, Yinon Rudich, Ralf Zimmermann, and Markus Kalberer
Atmos. Chem. Phys., 22, 1793–1809, https://doi.org/10.5194/acp-22-1793-2022, https://doi.org/10.5194/acp-22-1793-2022, 2022
Short summary
Short summary
Using a novel setup, we comprehensively characterized the formation of particle-bound reactive oxygen species (ROS) in anthropogenic and biogenic secondary organic aerosols (SOAs). We found that more than 90 % of all ROS components in both SOA types have a short lifetime. Our results also show that photochemical aging promotes particle-bound ROS production and enhances the oxidative potential of the aerosols. We found consistent results between chemical-based and biological-based ROS analyses.
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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.
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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.
Clara Betancourt, Christoph Küppers, Tammarat Piansawan, Uta Sager, Andrea B. Hoyer, Heinz Kaminski, Gerhard Rapp, Astrid C. John, Miriam Küpper, Ulrich Quass, Thomas Kuhlbusch, Jochen Rudolph, Astrid Kiendler-Scharr, and Iulia Gensch
Atmos. Chem. Phys., 21, 5953–5964, https://doi.org/10.5194/acp-21-5953-2021, https://doi.org/10.5194/acp-21-5953-2021, 2021
Short summary
Short summary
For the first time, we included stable isotopes in the Lagrangian particle dispersion model FLEXPART to investigate firewood home heating aerosol. This is an innovative source apportionment methodology since comparison of stable isotope ratio model predictions with observations delivers quantitative understanding of atmospheric processes. The main outcome of this study is that the home heating aerosol in residential areas was not of remote origin.
Alexander Zaytsev, Martin Breitenlechner, Anna Novelli, Hendrik Fuchs, Daniel A. Knopf, Jesse H. Kroll, and Frank N. Keutsch
Atmos. Meas. Tech., 14, 2501–2513, https://doi.org/10.5194/amt-14-2501-2021, https://doi.org/10.5194/amt-14-2501-2021, 2021
Short summary
Short summary
We have developed an online method for speciated measurements of organic peroxy radicals and stabilized Criegee intermediates using chemical derivatization combined with chemical ionization mass spectrometry. Chemical derivatization prevents secondary radical reactions and eliminates potential interferences. Comparison between our measurements and results from numeric modeling shows that the method can be used for the quantification of a wide range of atmospheric radicals and intermediates.
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.
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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.
Jiarong Li, Chao Zhu, Hui Chen, Defeng Zhao, Likun Xue, Xinfeng Wang, Hongyong Li, Pengfei Liu, Junfeng Liu, Chenglong Zhang, Yujing Mu, Wenjin Zhang, Luming Zhang, Hartmut Herrmann, Kai Li, Min Liu, and Jianmin Chen
Atmos. Chem. Phys., 20, 13735–13751, https://doi.org/10.5194/acp-20-13735-2020, https://doi.org/10.5194/acp-20-13735-2020, 2020
Short summary
Short summary
Based on a field study at Mt. Tai, China, the simultaneous variations of cloud microphysics, aerosol microphysics and their potential interactions during cloud life cycles were discussed. Results demonstrated that clouds on clean days were more susceptible to the concentrations of particle number, while clouds formed on polluted days might be more sensitive to meteorological parameters. Particles larger than 150 nm played important roles in forming cloud droplets with sizes of 5–10 μm.
Michael Rolletter, Marion Blocquet, Martin Kaminski, Birger Bohn, Hans-Peter Dorn, Andreas Hofzumahaus, Frank Holland, Xin Li, Franz Rohrer, Ralf Tillmann, Robert Wegener, Astrid Kiendler-Scharr, Andreas Wahner, and Hendrik Fuchs
Atmos. Chem. Phys., 20, 13701–13719, https://doi.org/10.5194/acp-20-13701-2020, https://doi.org/10.5194/acp-20-13701-2020, 2020
Short summary
Short summary
The photooxidation of pinonaldehyde is investigated in a chamber study under natural sunlight and low NO conditions with and without an added hydroxyl radical (OH) scavenger. The experimentally determined pinonaldehyde photolysis frequency is faster by a factor of 3.5 than currently used parameterizations in atmospheric models. Yields of degradation products are measured in the presence and absence of OH. Measurements are compared to current atmospheric models and a theory-based mechanism.
Matias Berasategui, Damien Amedro, Luc Vereecken, Jos Lelieveld, and John N. Crowley
Atmos. Chem. Phys., 20, 13541–13555, https://doi.org/10.5194/acp-20-13541-2020, https://doi.org/10.5194/acp-20-13541-2020, 2020
Short summary
Short summary
Peracetic acid is one of the most abundant organic peroxides in the atmosphere. We combine experiments and theory to show that peracetic acid reacts orders of magnitude more slowly with OH than presently accepted, which results in a significant extension of its atmospheric lifetime.
Mei-Tsan Kuo, Isabelle Weber, Christa Fittschen, Luc Vereecken, and Jim Jr-Min Lin
Atmos. Chem. Phys., 20, 12983–12993, https://doi.org/10.5194/acp-20-12983-2020, https://doi.org/10.5194/acp-20-12983-2020, 2020
Short summary
Short summary
Dimethyl sulfide (DMS) is the major sulfur-containing species in the troposphere. Previous work by Newland et al. (2015) reported very high reactivity of isoprene-derived Criegee intermediates (CIs) towards DMS. By monitoring CIs with direct UV absorption, we found CI + DMS reactions are very slow, in contrast to the results of Newland et al. (2015), suggesting these CIs would not oxidize atmospheric DMS at any substantial level.
Patrick Dewald, Jonathan M. Liebmann, Nils Friedrich, Justin Shenolikar, Jan Schuladen, Franz Rohrer, David Reimer, Ralf Tillmann, Anna Novelli, Changmin Cho, Kangming Xu, Rupert Holzinger, François Bernard, Li Zhou, Wahid Mellouki, Steven S. Brown, Hendrik Fuchs, Jos Lelieveld, and John N. Crowley
Atmos. Chem. Phys., 20, 10459–10475, https://doi.org/10.5194/acp-20-10459-2020, https://doi.org/10.5194/acp-20-10459-2020, 2020
Short summary
Short summary
We present direct measurements of NO3 reactivity resulting from the oxidation of isoprene by NO3 during an intensive simulation chamber study. Measurements were in excellent agreement with values calculated from measured isoprene amounts and the rate coefficient for the reaction of NO3 with isoprene. Comparison of the measurement with NO3 reactivities from non-steady-state and model calculations suggests that isoprene-derived RO2 and HO2 radicals account to ~ 50 % of overall NO3 losses.
Iida Pullinen, Sebastian Schmitt, Sungah Kang, Mehrnaz Sarrafzadeh, Patrick Schlag, Stefanie Andres, Einhard Kleist, Thomas F. Mentel, Franz Rohrer, Monika Springer, Ralf Tillmann, Jürgen Wildt, Cheng Wu, Defeng Zhao, Andreas Wahner, and Astrid Kiendler-Scharr
Atmos. Chem. Phys., 20, 10125–10147, https://doi.org/10.5194/acp-20-10125-2020, https://doi.org/10.5194/acp-20-10125-2020, 2020
Short summary
Short summary
Biogenic and anthropogenic air masses mix in the atmosphere, bringing plant-emitted monoterpenes and traffic-related nitrogen oxides together. There is debate whether the presence of nitrogen oxides reduces or increases secondary aerosol formation. This is important as secondary aerosols have cooling effects in the climate system but also constitute a health risk in populated areas. We show that the presence of NOx alone should not much affect the mass yields of secondary organic aerosols.
Cited articles
Alecu, I. M., Zheng, J., Zhao, Y., and Truhlar, D. G.: Computational thermochemistry: scale factor databases and scale factors for vibrational frequencies obtained from electronic model chemistries, J. Chem. Theor. Comput., 6, 2872–2887, https://doi.org/10.1021/ct100326h, 2010.
Bartlett, R. J. and Purvis, G. D.: Many-Body Perturbation-Theory,
Coupled-Pair Many-Electron Theory, and Importance of Quadruple Excitations for Correlation Problem, Int. J. Quant. Chem., 14, 561–581, https://doi.org/10.1002/qua.560140504, 1978.
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., Jokinen, T., Hyttinen, N., Kurtén, T.,
Otkjær, R. V., Kjaergaard, H. G., Stratmann, F., Herrmann, H., Sipilä, M., Kulmala, M., and Ehn, M.: Hydroxyl radical-induced formation
of highly oxidized organic compounds, Nat. Commun., 7, 13677,
https://doi.org/10.1038/ncomms13677, 2016.
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 alpha-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. Ed. Engl., 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.
Braure, T., Bedjanian, Y., Romanias, M. N., Morin, J., Riffault, V., Tomas,
A., and Coddeville, P.: Experimental study of the reactions of limonene with
OH and OD radicals: kinetics and products, J. Phys. Chem. A, 118, 9482–9490,
https://doi.org/10.1021/jp507180g, 2014.
Chen, X. and Hopke, P. K.: A chamber study of secondary organic aerosol
formation by limonene ozonolysis, Indoor Air, 20, 320–328,
https://doi.org/10.1111/j.1600-0668.2010.00656.x, 2010.
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.
Dash, M. R. and Rajakumar, B.: Theoretical investigations of the gas phase
reaction of limonene (C10H16) with OH radical, Mol. Phys., 113,
3202–3215, https://doi.org/10.1080/00268976.2015.1014002, 2015.
Dunning, T. H.: Gaussian basis sets for use in correlated molecular
calculations. I. The atoms boron through neon and hydrogen, J. Chem. Phys., 90, 1007–1023, https://doi.org/10.1063/1.456153, 1989.
Dunning, T. H., Peterson, K. A., and Wilson, A. K.: Gaussian basis sets for
use in correlated molecular calculations. X. The atoms aluminum through
argon revisited, J. Chem. Phys., 114, 9244–9253, https://doi.org/10.1063/1.1367373, 2001.
Eckart, C.: The Penetration of a Potential Barrier by Electrons, Phys. Rev.,
35, 1303–1309, https://doi.org/10.1103/PhysRev.35.1303, 1930.
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, 2012.
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, T. 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., 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.
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.
Finlayson-Pitts, B. J. and Pitts, J. N. J.: Chemistry of the Upper and Lower
Atmosphere: Theory, Experiments, and Applications, Academic Press, San
Diego, San Francisco, New York, Boston, London, Sydney, Tokyo, ISBN 978-0-12-257060-5
https://doi.org/10.1016/B978-0-12-257060-5.X5000-X, 2000.
Friedman, B. and Farmer, D. K.: SOA and gas phase organic acid yields from
the sequential photooxidation of seven monoterpenes, Atmos. Environ., 187,
335–345, https://doi.org/10.1016/j.atmosenv.2018.06.003, 2018.
Frisch, M. J., Trucks, G. W., Schlegel, H. B., Scuseria, G. E., Robb, M. A., Cheeseman, J. R., Scalmani, G., Barone, V., Petersson, G. A., Nakatsuji, H., Li, X., Caricato, M., Marenich, A. V., Bloino, J., Janesko, B. G., Gomperts, R., Mennucci, B., Hratchian, H. P., Ortiz, J. V., Izmaylov, A. F., Sonnenberg, J. L., Williams-Young, D., Ding, F., Lipparini, F., Egidi, F., Goings, J., Peng, B., Petrone, A., Henderson, T., Ranasinghe, D., Zakrzewski, V. G., Gao, J., Rega, N., Zheng, G., Liang, W., Hada, M., Ehara, M., Toyota, K., Fukuda, R., Hasegawa, J., Ishida, M., Nakajima, T., Honda, Y., Kitao, O., Nakai, H., Vreven, T., Throssell, K., Montgomery, J. A., Jr., Peralta, J. E., Ogliaro, F., Bearpark, M. J., Heyd, J. J., Brothers, E. N., Kudin, K. N., Staroverov, V. N., Keith, T. A., Kobayashi, R., Normand, J., Raghavachari, K., Rendell, A. P., Burant, J. C., Iyengar, S. S., Tomasi, J., Cossi, M., Millam, J. M., Klene, M., Adamo, C., Cammi, R., Ochterski, J. W., Martin, R. L., Morokuma, K., Farkas, O., Foresman, J. B., and Fox, D. J.: Gaussian 09 Revision E.01, Gaussian, Inc., Wallingford CT, [code],
https://gaussian.com/gaussian16/ (last access: 28 June 2023), 2016.
Fuchs, H., Bohn, B., Hofzumahaus, A., Holland, F., Lu, K. D., Nehr, S., Rohrer, F., and Wahner, A.: Detection of HO2 by laser-induced
fluorescence: calibration and interferences from RO2 radicals, Atmos.
Meas. Tech., 4, 1209–1225, https://doi.org/10.5194/amt-4-1209-2011, 2011.
Fuchs, H., Dorn, H.-P., Bachner, M., Bohn, B., Brauers, T., Gomm, S., Hofzumahaus, A., Holland, F., Nehr, S., Rohrer, F., Tillmann, R., and Wahner, A.: Comparison of OH concentration measurements by DOAS and LIF during SAPHIR chamber experiments at high OH reactivity and low NO concentration, Atmos. Meas. Tech., 5, 1611–1626, https://doi.org/10.5194/amt-5-1611-2012, 2012.
Gkatzelis, G. I., Coggon, M. M., McDonald, B. C., Peischl, J., Gilman, J.
B., Aikin, K. C., Robinson, M. A., Canonaco, F., Prevot, A. S. H., Trainer,
M., and Warneke, C.: Observations Confirm that Volatile Chemical Products
Are a Major Source of Petrochemical Emissions in U.S. Cities, Environ. Sci.
Technol., 55, 4332–4343, https://doi.org/10.1021/acs.est.0c05471, 2021.
Goerigk, L., Hansen, A., Bauer, C., Ehrlich, S., Najibi, A., and Grimme, S.:
A look at the density functional theory zoo with the advanced GMTKN55 database for general main group thermochemistry, kinetics and noncovalent
interactions, Phys. Chem. Chem. Phys., 19, 32184–32215, https://doi.org/10.1039/c7cp04913g, 2017.
Gong, Y., Chen, Z., and Li, H.: The oxidation regime and SOA composition in
limonene ozonolysis: roles of different double bonds, radicals, and water,
Atmos. Chem. Phys., 18, 15105–15123, https://doi.org/10.5194/acp-18-15105-2018, 2018.
Griffin, R. J., Cocker, D. R., Flagan, R. C., and Seinfeld, J. H.: Organic
aerosol formation from the oxidation of biogenic hydrocarbons, J. Geophys.
Res., 104, 3555–3567, https://doi.org/10.1029/1998jd100049, 1999.
Grimme, S., Ehrlich, S., and Goerigk, L.: Effect of the damping function in
dispersion corrected density functional theory, J. Comput. Chem., 32, 1456–1465, https://doi.org/10.1002/jcc.21759, 2011.
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.
Guo, Y., Shen, H., Pullinen, I., Luo, H., Kang, S., Vereecken, L., Fuchs, H., Hallquist, M., Acir, I.-H., Tillmann, R., Rohrer, F., Wildt, J., Kiendler-Scharr, A., Wahner, A., Zhao, D., and Mentel, T. F.: Identification of highly oxygenated organic molecules and their role in aerosol formation in the reaction of limonene with nitrate radical, Atmos. Chem. Phys., 22, 11323–11346, https://doi.org/10.5194/acp-22-11323-2022, 2022.
Hakola, H., Arey, J., Aschmann, S. M., and Atkinson, R.: Product Formation
from the Gas-Phase Reactions of OH Radicals and O3 with a Series of
Monoterpenes, J. Atmos. Chem., 18, 75–102, https://doi.org/10.1007/Bf00694375, 1994.
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.
Hammes, J., Lutz, A., Mentel, T., Faxon, C., and Hallquist, M.: Carboxylic
acids from limonene oxidation by ozone and hydroxyl radicals: insights into
mechanisms derived using a FIGAERO-CIMS, Atmos. Chem. Phys., 19, 13037–13052, https://doi.org/10.5194/acp-19-13037-2019, 2019.
Huang, W., Saathoff, H., Shen, X., Ramisetty, R., Leisner, T., and Mohr, C.:
Chemical Characterization of Highly Functionalized Organonitrates Contributing to Night-Time Organic Aerosol Mass Loadings and Particle
Growth, Environ. Sci. Technol., 53, 1165–1174, https://doi.org/10.1021/acs.est.8b05826, 2019.
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.
Jaoui, M., Corse, E., Kleindienst, T. E., Offenberg, J. H., Lewandowski, M.,
and Edney, E. O.: Analysis of Secondary Organic Aerosol Compounds from the
Photooxidation of d Limonene in the Presence of NOx and their Detection
in Ambient PM2.5, Environ. Sci. Technol., 40, 3819–3828, 2006.
Jenkin, M. E., Saunders, S. M., and Pilling, M. J.: The tropospheric degradation of volatile organic compounds: a protocol for mechanism development, Atmos. Environ., 31, 81–104, 1997.
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.
Johnston, H. S. and Heicklen, J.: Tunnelling Corrections for Unsymmetrical
Eckart Potential Energy Barriers, J. Phys. Chem., 66, 532–533, 1962.
Jokinen, T., Sipilä, M., Richters, S., Kerminen, V. M., 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.
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.
Jørgensen, S., Knap, H. C., Otkjær, R. V., Jensen, A. M., Kjeldsen,
M. L., Wennberg, P. O., and Kjaergaard, H. G.: Rapid Hydrogen Shift Scrambling in Hydroperoxy-Substituted Organic Peroxy Radicals, J. Phys. Chem. A, 120, 266–275, https://doi.org/10.1021/acs.jpca.5b06768, 2016.
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.
Kenseth, C. M., Huang, Y., Zhao, R., Dalleska, N. F., Hethcox, J. C., Stoltz, B. M., and Seinfeld, J. H.: Synergistic O3+OH oxidation pathway to extremely low-volatility dimers revealed in beta-pinene secondary organic aerosol, P. Natl. Acad. Sci. USA, 115, 8301–8306, https://doi.org/10.1073/pnas.1804671115, 2018.
Kirkby, J., Duplissy, J., Sengupta, K., Frege, C., Gordon, H., Williamson,
C., Heinritzi, M., Simon, M., Yan, C., Almeida, J., Tröstl, J., Nieminen, T., Ortega, I. K., Wagner, R., Adamov, A., Amorim, A., Bernhammer, A. K., Bianchi, F., Breitenlechner, M., Brilke, S., Chen, X., Craven, J., Dias, A., Ehrhart, S., Flagan, R. C., Franchin, A., Fuchs, C., Guida, R., Hakala, J., Hoyle, C. R., Jokinen, T., Junninen, H., Kangasluoma, J., Kim, J., Krapf, M., Kürten, A., Laaksonen, A., Lehtipalo, K., Makhmutov, V., Mathot, S., Molteni, U., Onnela, A., Peräkylä, O., Piel, F., Petäjä, T., Praplan, A. P., Pringle, K., Rap, A., Richards, N. A., Riipinen, I., Rissanen, M. P., Rondo, L., Sarnela, N., Schobesberger, S., Scott, C. E., Seinfeld, J. H., Sipilä, M., Steiner, G., Stozhkov, Y., Stratmann, F., Tomé, A., Virtanen, A., Vogel, A. L., Wagner, A. C., Wagner, P. E., Weingartner, E., Wimmer, D., Winkler, P. M., Ye, P., Zhang, X., Hansel, A., Dommen, J., Donahue, N. M., Worsnop, D. R., Baltensperger, U., Kulmala, M., Carslaw, K. S., and Curtius, J.: Ion-induced nucleation of pure biogenic particles, Nature, 533, 521–526, https://doi.org/10.1038/nature17953, 2016.
Knap, H. C. and Jørgensen, S.: Rapid Hydrogen Shift Reactions in Acyl
Peroxy Radicals, J. Phys. Chem. A, 121, 1470–1479, https://doi.org/10.1021/acs.jpca.6b12787, 2017.
Koch, S., Winterhalter, R., Uherek, E., Kolloff, A., Neeb, P., and Moortgat,
G. K.: Formation of new particles in the gas-phase ozonolysis of monoterpenes, Atmos. Environ., 34, 4031–4042, 2000.
Krechmer, J. E., Coggon, M. M., Massoli, P., Nguyen, T. B., Crounse, J. D.,
Hu, W., Day, D. A., Tyndall, G. S., Henze, D. K., Rivera-Rios, J. C., Nowak,
J. B., Kimmel, J. R., Mauldin, R. L., Stark, H., Jayne, J. T., Sipilä, M., Junninen, H., Clair, J. M. S., Zhang, X., Feiner, P. A., Zhang, L., Miller, D. O., Brune, W. H., Keutsch, F. N., Wennberg, P. O., Seinfeld, J. H., Worsnop, D. R., Jimenez, J. L., and Canagaratna, M. R.: Formation of Low Volatility Organic Compounds and Secondary Organic Aerosol from Isoprene Hydroxyhydroperoxide Low-NO Oxidation, Environ. Sci. Technol., 49, 10330–10339, https://doi.org/10.1021/acs.est.5b02031, 2015.
Larsen, B. R., Di Bella, D., Glasius, M., Winterhalter, R., Jensen, N. R.,
and Hjorth, J.: Gas-phase OH oxidation of monoterpenes: Gaseous and
particulate products, J. Atmos. Chem., 38, 231–276, https://doi.org/10.1023/A:1006487530903, 2001.
Lee, A., Goldstein, A. H., Kroll, J. H., Ng, N. L., Varutbangkul, V., Flagan, R. C., and Seinfeld, J. H.: Gas-phase products and secondary aerosol yields from the photooxidation of 16 different terpenes, J. Geophys. Res., 111, D17305, https://doi.org/10.1029/2006jd007050, 2006a.
Lee, A., Goldstein, A. H., Keywood, M. D., Gao, S., Varutbangkul, V., Bahreini, R., Ng, N. L., Flagan, R. C., and Seinfeld, J. H.: Gas-phase
products and secondary aerosol yields from the ozonolysis of ten different
terpenes, J. Geophys. Res., 111, D07302, https://doi.org/10.1029/2005jd006437, 2006b.
Lee, B. H., Mohr, C., Lopez-Hilfiker, F. D., Lutz, A., Hallquist, M., Lee,
L., Romer, P., Cohen, R. C., Iyer, S., Kurtén, 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, https://doi.org/10.1073/pnas.1508108113, 2016.
Lelieveld, J., Butler, T. M., Crowley, J. N., Dillon, T. J., Fischer, H.,
Ganzeveld, L., Harder, H., Lawrence, M. G., Martinez, M., Taraborrelli, D.,
and Williams, J.: Atmospheric oxidation capacity sustained by a tropical
forest, Nature, 452, 737–740, https://doi.org/10.1038/nature06870, 2008.
Massoli, P., Stark, H., Canagaratna, M. R., Krechmer, J. E., Xu, L., Ng, N.
L., Mauldin, Ó., Roy L., Yan, C., Kimmel, J., Misztal, P. K., Jimenez, J. L., Jayne, J. T., and Worsnop, D. R.: Ambient Measurements of Highly Oxidized Gas-Phase Molecules during the Southern Oxidant and Aerosol Study (SOAS) 2013, ACS Earth Space Chem., 2, 653–672, https://doi.org/10.1021/acsearthspacechem.8b00028, 2018.
Mayorga, R., Xia, Y., Zhao, Z., Long, B., and Zhang, H.: Peroxy Radical
Autoxidation and Sequential Oxidation in Organic Nitrate Formation during
Limonene Nighttime Oxidation, Environ. Sci. Technol., 56, 15337–15346,
https://doi.org/10.1021/acs.est.2c04030, 2022.
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.
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.
Miller, J. A., Pilling, M. J., and Troe, J.: Unravelling combustion
mechanisms through a quantitative understanding of elementary reactions, P.
Combust. Inst., 30, 43–88, https://doi.org/10.1016/j.proci.2004.08.281, 2005.
Moiseenko, K. B., Vasileva, A. V., Skorokhod, A. I., Belikov, I. B., Repin,
A. Y., and Shtabkin, Y. A.: Regional Impact of Ozone Precursor Emissions on
NOx and O3 Levels at ZOTTO Tall Tower in Central Siberia, Earth
Space Sci., 8, e2021EA001762, https://doi.org/10.1029/2021ea001762, 2021.
Møller, K. H., Bates, K. H., and Kjaergaard, H. G.: The Importance of
Peroxy Radical Hydrogen-Shift Reactions in Atmospheric Isoprene Oxidation, J.
Phys. Chem. A, 123, 920–932, https://doi.org/10.1021/acs.jpca.8b10432, 2019.
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., Kürten, A., Lehtipalo, K.,
Makhmutov, V., Petäjä, T., Pieber, S. M., Praplan, A. P., Schobesberger, S., Steiner, G., Stozhkov, Y., Tomé, A., Tröstl, 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 Space Chem., 3, 873–883,
https://doi.org/10.1021/acsearthspacechem.9b00035, 2019.
Nazaroff, W. W. and Weschler, C. J.: Cleaning products and air fresheners:
exposure to primary and secondary air pollutants, Atmos. Environ., 38,
2841–2865, https://doi.org/10.1016/j.atmosenv.2004.02.040, 2004.
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.
Ng, N. L., Brown, S. S., Archibald, A. T., Atlas, E., Cohen, R. C., Crowley,
J. N., Day, D. A., Donahue, N. M., Fry, J. L., Fuchs, H., Griffin, R. J., Guzman, M. I., Herrmann, H., Hodzic, A., Iinuma, Y., Jimenez, J. L.,
Kiendler-Scharr, A., Lee, B. H., Luecken, D. J., Mao, J., McLaren, R., Mutzel, A., Osthoff, H. D., Ouyang, B., Picquet-Varrault, B., Platt, U.,
Pye, H. O. T., Rudich, Y., Schwantes, R. H., Shiraiwa, M., Stutz, J.,
Thornton, J. A., Tilgner, A., Williams, B. J., and Zaveri, R. A.: Nitrate
radicals and biogenic volatile organic compounds: oxidation, mechanisms, and
organic aerosol, Atmos. Chem. Phys., 17, 2103–2162, https://doi.org/10.5194/acp-17-2103-2017, 2017.
Novelli, A., Cho, C., Fuchs, H., Hofzumahaus, A., Rohrer, F., Tillmann, R.,
Kiendler-Scharr, A., Wahner, A., and Vereecken, L.: Experimental and theoretical study on the impact of a nitrate group on the chemistry of
alkoxy radicals, Phys. Chem. Chem. Phys., 23, 5474–5495, https://doi.org/10.1039/d0cp05555g, 2021.
Nozière, B. and Vereecken, L.: Direct Observation of Aliphatic Peroxy
Radical Autoxidation and Water Effects: An Experimental and Theoretical
Study, Angew. Chem. Int. Ed., 58, 13976–13982, https://doi.org/10.1002/anie.201907981, 2019.
Pang, J. Y. S., Novelli, A., Kaminski, M., Acir, I.-H., Bohn, B., Carlsson, P. T. M., Cho, C., Dorn, H.-P., Hofzumahaus, A., Li, X., Lutz, A., Nehr, S., Reimer, D., Rohrer, F., Tillmann, R., Wegener, R., Kiendler-Scharr, A., Wahner, A., and Fuchs, H.: Investigation of the limonene photooxidation by OH at different NO concentrations in the atmospheric simulation chamber SAPHIR (Simulation of Atmospheric PHotochemistry In a large Reaction Chamber), Atmos. Chem. Phys., 22, 8497–8527, https://doi.org/10.5194/acp-22-8497-2022, 2022.
Peeters, J., Vandenberk, S., Piessens, E., and Pultau, V.: H-atom abstraction in reactions of cyclic polyalkenes with OH, Chemosphere, 38, 1189–1195, 1999.
Perraud, V., Bruns, E. A., Ezell, M. J., Johnson, S. N., Yu, Y., Alexander, M. L., Zelenyuk, A., Imre, D., Chang, W. L., Dabdub, D., Pankow, J. F., and
Finlayson-Pitts, B. J.: Nonequilibrium atmospheric secondary organic aerosol
formation and growth, P. Natl. Acad. Sci. USA, 109, 2836–2841,
https://doi.org/10.1073/pnas.1119909109, 2012.
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., Otkjær, R. V., Crounse, J. D., Hethcox, J. C., Stoltz, B. M., Kjaergaard, H. G., and Wennberg, P. O.: Intramolecular Hydrogen Shift Chemistry of Hydroperoxy-Substituted Peroxy Radicals, J. Phys. Chem. A, 123,
590–600, https://doi.org/10.1021/acs.jpca.8b09745, 2019.
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., D'Ambro, E. L., Lee, B., Schobesberger, S., Takeuchi, M.,
Zhao, Y., Lopez-Hilfiker, F., Liu, J. M., Shilling, J. E., Xing, J., Mathur,
R., Middlebrook, A. M., Liao, J., Welti, A., Graus, M., Warneke, C., de
Gouw, J. A., Holloway, J. S., Ryerson, T. B., Pollack, I. B., and Thornton,
J. A.: Anthropogenic enhancements to production of highly oxygenated
molecules from autoxidation, P. Natl. Acad. Sci. USA, 116, 6641–6646,
https://doi.org/10.1073/pnas.1810774116, 2019.
Quéléver, L. L. J., Kristensen, K., Normann Jensen, L., Rosati, B.,
Teiwes, R., Daellenbach, K. R., Peräkylä, O., Roldin, P., Bossi, R.,
Pedersen, H. B., Glasius, M., Bilde, M., and Ehn, M.: Effect of temperature
on the formation of highly oxygenated organic molecules (HOMs) from
alpha-pinene ozonolysis, Atmos. Chem. Phys., 19, 7609–7625,
https://doi.org/10.5194/acp-19-7609-2019, 2019.
Rio, C., Flaud, P. M., Loison, J. C., and Villenave, E.: Experimental revaluation of the importance of the abstraction channel in the reactions of
monoterpenes with OH radicals, Chem. Phys. Chem., 11, 3962–3970,
https://doi.org/10.1002/cphc.201000518, 2010.
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.
Rohrer, F., Bruning, D., Grobler, E. S., Weber, M., Ehhalt, D. H., Neubert,
R., Schussler, W., and Levin, I.: Mixing ratios and photostationary state of
NO and NO2 observed during the POPCORN field campaign at a rural site
in Germany, J. Atmos. Chem., 31, 119–137, https://doi.org/10.1023/A:1006166116242, 1998.
Rohrer, F., Bohn, B., Brauers, T., Brüning, D., Johnen, F.-J., Wahner, A., and Kleffmann, J.: Characterisation of the photolytic HONO-source in the atmosphere simulation chamber SAPHIR, Atmos. Chem. Phys., 5, 2189–2201, https://doi.org/10.5194/acp-5-2189-2005, 2005.
Romonosky, D. E., Laskin, A., Laskin, J., and Nizkorodov, S. A.:
High-resolution mass spectrometry and molecular characterization of aqueous
photochemistry products of common types of secondary organic aerosols, J.
Phys. Chem. A, 119, 2594–2606, https://doi.org/10.1021/jp509476r, 2015.
Rossignol, S., Rio, C., Ustache, A., Fable, S., Nicolle, J., Même, A.,
D'Anna, B., Nicolas, M., Leoz, E., and Chiappini, L.: The use of a housecleaning product in an indoor environment leading to oxygenated polar
compounds and SOA formation: Gas and particulate phase chemical
characterization, Atmos. Environ., 75, 196–205,
https://doi.org/10.1016/j.atmosenv.2013.03.045, 2013.
Saathoff, H., Naumann, K.-H., Möhler, O., Jonsson, Å. M., Hallquist, M., Kiendler-Scharr, A., Mentel, Th. F., Tillmann, R., and Schurath, U.: Temperature dependence of yields of secondary organic aerosols from the ozonolysis of α-pinene and limonene, Atmos. Chem. Phys., 9, 1551–1577, https://doi.org/10.5194/acp-9-1551-2009, 2009.
Shen, H., Zhao, D., Pullinen, I., Kang, S., Vereecken, L., Fuchs, H., Acir,
I. H., Tillmann, R., Rohrer, F., Wildt, J., Kiendler-Scharr, A., Wahner, A.,
and Mentel, T. F.: Highly Oxygenated Organic Nitrates Formed from NO3
Radical-Initiated Oxidation of β-Pinene, Environ. Sci. Technol., 55,
15658–15671, https://doi.org/10.1021/acs.est.1c03978, 2021.
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, Sci. Adv., 8, 1–11, 2022.
Taatjes, C. A.: Uncovering the Fundamental Chemistry of Alkyl + O2
Reactions via Measurements of Product Formation, J. Phys. Chem. A, 110,
4299–4312, 2006.
Tomaz, S., Wang, D., Zabalegui, N., Li, D., Lamkaddam, H., Bachmeier, F.,
Vogel, A., Monge, M. E., Perrier, S., Baltensperger, U., George, C., Rissanen, M., Ehn, M., El Haddad, I., and Riva, M.: Structures and
reactivity of peroxy radicals and dimeric products revealed by online tandem
mass spectrometry, Nat. Commun., 12, 300, https://doi.org/10.1038/s41467-020-20532-2, 2021.
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., Kürten, A., Laaksonen, A., Lawler, M., Leiminger, M.,
Mathot, S., Möhler, O., Nieminen, T., Onnela, A., Petäjä, T.,
Piel, F. M., Miettinen, P., Rissanen, M. P., Rondo, L., Sarnela, N., Schobesberger, S., Sengupta, K., Sipilä, M., Smith, J. N., Steiner, G.,
Tomè, A., Virtanen, A., Wagner, A. C., Weingartner, E., Wimmer, D.,
Winkler, P. M., Ye, P., 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., Kubeèka, 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.: Replication Data for: Formation of highly oxygenated organic molecules from the oxidation of limonene by OH radical: significant contribution of H-abstraction pathway, Jülich DATA [data set], https://doi.org/10.26165/JUELICH-DATA/9JVHEK, 2023.
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.: Theoretical Study of the Formation of Acetone
in the OH-Initiated Atmospheric Oxidation of α-Pinene, J. Phys. Chem. A, 104, 11140–11146, 2000.
Vereecken, L. and Peeters, J.: The 1,5-H-shift in 1-butoxy: A case study in
the rigorous implementation of transition state theory for a multirotamer
system, J. Chem. Phys., 119, 5159–5170, https://doi.org/10.1063/1.1597479, 2003.
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. and Peeters, J.: A theoretical study of the OH-initiated
gas-phase oxidation mechanism of β-pinene (C10H16): first
generation products, Phys. Chem. Chem. Phys., 14, 3802–3815, https://doi.org/10.1039/c2cp23711c, 2012.
Vereecken, L., Müller, J. F., and Peeters, J.: Low-volatility
poly-oxygenates in the OH-initiated atmospheric oxidation of á-pinene:
impact of non-traditional peroxyl radical chemistry, Phys Chem Chem Phys, 9,
5241-5248, 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.
Waring, M. S.: Secondary organic aerosol formation by limonene ozonolysis:
Parameterizing multi-generational chemistry in ozone- and residence time-limited indoor environments, Atmos. Environ., 144, 79–86,
https://doi.org/10.1016/j.atmosenv.2016.08.051, 2016.
Wei, D., Fuentes, J. D., Gerken, T., Trowbridge, A. M., Stoy, P. C., and Chamecki, M.: Influences of nitrogen oxides and isoprene on ozone-temperature relationships in the Amazon rain forest, Atmos. Environ., 206, 280–292, https://doi.org/10.1016/j.atmosenv.2019.02.044, 2019.
Whalley, L. K., Edwards, P. M., Furneaux, K. L., Goddard, A., Ingham, T.,
Evans, M. J., Stone, D., Hopkins, J. R., Jones, C. E., Karunaharan, A., Lee,
J. D., Lewis, A. C., Monks, P. S., Moller, S. J., and Heard, D. E.: Quantifying the magnitude of a missing hydroxyl radical source in a tropical
rainforest, Atmos. Chem. Phys., 11, 7223–7233, https://doi.org/10.5194/acp-11-7223-2011, 2011.
Williams, P. J. H., Boustead, G. A., Heard, D. E., Seakins, P. W., Rickard, A. R., and Chechik, V.: New Approach to the Detection of Short-Lived Radical
Intermediates, J. Am. Chem. Soc., 144, 15969–15976, https://doi.org/10.1021/jacs.2c03618, 2022.
Xu, L., Møller, K. H., Crounse, J. D., Otkjær, 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.
Xu, R., Thornton, J. A., Lee, B. H., Zhang, Y., Jaeglé, L., Lopez-Hilfiker, F. D., Rantala, P., and Petäjä, T.: Global simulations of monoterpene-derived peroxy radical fates and the distributions of highly oxygenated organic molecules (HOMs) and accretion products, Atmos. Chem. Phys., 22, 5477–5494, https://doi.org/10.5194/acp-22-5477-2022, 2022.
Yan, C., Nie, W., Äijälä, M., Rissanen, M. P., Canagaratna, M.
R., Massoli, P., Junninen, H., Jokinen, T., Sarnela, N., Häme, S. A. K.,
Schobesberger, S., Canonaco, F., Yao, L., Prévôt, A. S. H., Petäjä, T., Kulmala, M., Sipilä, M., Worsnop, D. R., and Ehn,
M.: Source characterization of highly oxidized multifunctional compounds in
a boreal forest environment using positive matrix factorization, Atmos. Chem.
Phys., 16, 12715–12731, https://doi.org/10.5194/acp-16-12715-2016, 2016.
Yan, C., Nie, W., Vogel, A. L., Dada, L., Lehtipalo, K., Stolzenburg, D.,
Wagner, R., Rissanen, M. P., Xiao, M., Ahonen, L., Fischer, L., Rose, C.,
Bianchi, F., Gordon, H., Simon, M., Heinritzi, M., Garmash, O., Roldin, P.,
Dias, A., Ye, P., Hofbauer, V., Amorim, A., Bauer, P. S., Bergen, A.,
Bernhammer, A. K., Breitenlechner, M., Brilke, S., Buchholz, A., Mazon, S.
B., Canagaratna, M. R., Chen, X., Ding, A., Dommen, J., Draper, D. C.,
Duplissy, J., Frege, C., Heyn, C., Guida, R., Hakala, J., Heikkinen, L.,
Hoyle, C. R., Jokinen, T., Kangasluoma, J., Kirkby, J., Kontkanen, J.,
Kurten, A., Lawler, M. J., Mai, H., Mathot, S., Mauldin, R. L., Molteni, U.,
Nichman, L., Nieminen, T., Nowak, J., Ojdanic, A., Onnela, A., Pajunoja, A.,
Petaja, T., Piel, F., Quelever, L. L. J., Sarnela, N., Schallhart, S.,
Sengupta, K., Sipila, M., Tome, A., Trostl, J., Vaisanen, O., Wagner, A. C.,
Ylisirnio, A., Zha, Q., Baltensperger, U., Carslaw, K. S., Curtius, J.,
Flagan, R. C., Hansel, A., Riipinen, I., Smith, J. N., Virtanen, A., Winkler, P. M., Donahue, N. M., Kerminen, V. M., Kulmala, M., Ehn, M., and Worsnop, D. R.: Size-dependent influence of NOx on the growth rates of organic aerosol particles, Sci. Adv., 6, eaay4945, https://doi.org/10.1126/sciadv.aay4945, 2020.
Yu, J., Cocker, D. R., Griffin, R. J., Flagan, R. C., and Seinfeld, J. H.: Gas-phase ozone oxidation of monoterpenes: Gaseous and particulate products, J. Atmos. Chem., 34, 207–258, https://doi.org/10.1023/A:1006254930583, 1999.
Zhang, H., Yee, L. D., Lee, B. H., Curtis, M. P., Worton, D. R., Isaacman-VanWertz, G., Offenberg, J. H., Lewandowski, M., Kleindienst, T.
E., Beaver, M. R., Holder, A. L., Lonneman, W. A., Docherty, K. S., Jaoui, M., Pye, H. O. T., Hu, W., Day, D. A., Campuzano-Jost, P., Jimenez, J. L., Guo, H., Weber, R. J., de Gouw, J., Koss, A. R., Edgerton, E. S., Brune, W.,
Mohr, C., Lopez-Hilfiker, F. D., Lutz, A., Kreisberg, N. M., Spielman, S. R., Hering, S. V., Wilson, K. R., Thornton, J. A., and Goldstein, A. H.: Monoterpenes are the largest source of summertime organic aerosol in the
southeastern United States, P. Natl. Acad. Sci. USA, 115, 2038–2043,
https://doi.org/10.1073/pnas.1717513115, 2018.
Zhao, B., Shrivastava, M., Donahue, N. M., Gordon, H., Schervish, M., Shilling, J. E., Zaveri, R. A., Wang, J., Andreae, M. O., Zhao, C., Gaudet,
B., Liu, Y., Fan, J., and Fast, J. D.: High concentration of ultrafine
particles in the Amazon free troposphere produced by organic new particle
formation, P. Natl. Acad. Sci. USA, 117, 25344–25351, https://doi.org/10.1073/pnas.2006716117, 2020.
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.
Zhao, D., Pullinen, I., Fuchs, H., Schrade, S., Wu, R., Acir, I.-H.,
Tillmann, R., Rohrer, F., Wildt, J., Guo, Y., Kiendler-Scharr, A., Wahner,
A., Kang, S., Vereecken, L., and Mentel, T. F.: Highly oxygenated organic
molecule (HOM) formation in the isoprene oxidation by NO3 radical,
Atmos. Chem. Phys., 21, 9681–9704, https://doi.org/10.5194/acp-21-9681-2021, 2021.
Zhao, D. F., Buchholz, A., Kortner, B., Schlag, P., Rubach, F.,
Kiendler-Scharr, A., Tillmann, R., Wahner, A., Flores, J. M., Rudich, Y.,
Watne, Å. K., Hallquist, M., Wildt, J., and Mentel, T. F.: Size-dependent hygroscopicity parameter (κ) and chemical composition of secondary organic cloud condensation nuclei, Geophys. Res. Lett., 42, 10920–10928, https://doi.org/10.1002/2015gl066497, 2015a.
Zhao, D. F., Kaminski, M., Schlag, P., Fuchs, H., Acir, I. H., Bohn, B.,
Häseler, R., Kiendler-Scharr, A., Rohrer, F., Tillmann, R., Wang, M. J.,
Wegener, R., Wildt, J., Wahner, A., and Mentel, T. F.: Secondary organic
aerosol formation from hydroxyl radical oxidation and ozonolysis of
monoterpenes, Atmos. Chem. Phys., 15, 991–1012, https://doi.org/10.5194/acp-15-991-2015, 2015b.
Zhao, Y. and Truhlar, D. G.: The M06 suite of density functionals for main
group thermochemistry, thermochemical kinetics, noncovalent interactions,
excited states, and transition elements: two new functionals and systematic
testing of four M06-class functionals and 12 other functionals, Theor. Chem.
Account., 120, 215–241, https://doi.org/10.1007/s00214-007-0310-x, 2008.
Zhao, Y., Thornton, J. A., and Pye, H. O. T.: Quantitative constraints on
autoxidation and dimer formation from direct probing of monoterpene-derived
peroxy radical chemistry, P. Natl. Acad. Sci. USA, 115, 12142–12147,
https://doi.org/10.1073/pnas.1812147115, 2018.
Ziemann, P. J. and Atkinson, R.: Kinetics, products, and mechanisms of secondary organic aerosol formation, Chem. Soc. Rev., 41, 6582–6605,
https://doi.org/10.1039/c2cs35122f, 2012.
Short summary
Oxidation of limonene, an element emitted by trees and chemical products, by OH, a daytime oxidant, forms many highly oxygenated organic molecules (HOMs), including C10-20 compounds. HOMs play an important role in new particle formation and growth. HOM formation can be explained by the chemistry of peroxy radicals. We found that a minor branching ratio initial pathway plays an unexpected, significant role. Considering this pathway enables accurate simulations of HOMs and other concentrations.
Oxidation of limonene, an element emitted by trees and chemical products, by OH, a daytime...
Altmetrics
Final-revised paper
Preprint