Articles | Volume 21, issue 12
https://doi.org/10.5194/acp-21-9681-2021
© Author(s) 2021. 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-21-9681-2021
© Author(s) 2021. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
29 Jun 2021
Research article |
| 29 Jun 2021
| 29 Jun 2021
Highly oxygenated organic molecule (HOM) formation in the isoprene oxidation by NO3 radical
Department of Atmospheric and Oceanic Sciences & Institute of
Atmospheric Sciences, Fudan University, Shanghai, 200438, China
Institute of Energy and Climate Research, IEK-8: Troposphere,
Forschungszentrum Jülich, 52425 Jülich, Germany
Big Data Institute for Carbon Emission and Environmental Pollution,
Fudan University, Shanghai, 200438, China
Institute of Eco-Chongming (IEC), 20 Cuiniao Rd., Chenjia Zhen,
Chongming, Shanghai, 202162, China
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,
Kuopio, 7021, Finland
Hendrik Fuchs
Institute of Energy and Climate Research, IEK-8: Troposphere,
Forschungszentrum Jülich, 52425 Jülich, Germany
Stephanie Schrade
Institute of Energy and Climate Research, IEK-8: Troposphere,
Forschungszentrum Jülich, 52425 Jülich, Germany
Rongrong Wu
Institute of Energy and Climate Research, IEK-8: Troposphere,
Forschungszentrum Jülich, 52425 Jülich, Germany
Ismail-Hakki Acir
Institute of Energy and Climate Research, IEK-8: Troposphere,
Forschungszentrum Jülich, 52425 Jülich, Germany
now at: Institute of Nutrition and Food Sciences, University of Bonn,
53115 Bonn, Germany
Ralf Tillmann
Institute of Energy and Climate Research, IEK-8: Troposphere,
Forschungszentrum Jülich, 52425 Jülich, Germany
Franz Rohrer
Institute of Energy and Climate Research, IEK-8: Troposphere,
Forschungszentrum Jülich, 52425 Jülich, Germany
Jürgen Wildt
Institute of Energy and Climate Research, IEK-8: Troposphere,
Forschungszentrum Jülich, 52425 Jülich, Germany
Yindong Guo
Department of Atmospheric and Oceanic Sciences & Institute of
Atmospheric Sciences, Fudan University, Shanghai, 200438, China
Astrid Kiendler-Scharr
Institute of Energy and Climate Research, IEK-8: Troposphere,
Forschungszentrum Jülich, 52425 Jülich, Germany
Andreas Wahner
Institute of Energy and Climate Research, IEK-8: Troposphere,
Forschungszentrum Jülich, 52425 Jülich, Germany
Sungah Kang
Institute of Energy and Climate Research, IEK-8: Troposphere,
Forschungszentrum Jülich, 52425 Jülich, Germany
Luc Vereecken
Institute of Energy and Climate Research, IEK-8: Troposphere,
Forschungszentrum Jülich, 52425 Jülich, Germany
Institute of Energy and Climate Research, IEK-8: Troposphere,
Forschungszentrum Jülich, 52425 Jülich, Germany
Related authors
Yali Jin, Hao Luo, Siqi Tang, Shuhui Xue, Chengyu Nie, Xiaocong Peng, Yan Zheng, Weiqi Xu, Guohua Zhang, Xiaole Pan, Yele Sun, Qi Chen, Lanzhong Liu, and Defeng Zhao
EGUsphere, https://doi.org/10.5194/egusphere-2025-4322, https://doi.org/10.5194/egusphere-2025-4322, 2025
This preprint is open for discussion and under review for Atmospheric Chemistry and Physics (ACP).
Short summary
Short summary
Cloud substantially changes the compositions organic aerosol. How cloud processing of organics occur on molecular level remains unclear. We found that compared with cloud free particles, organics in cloud contains more large molecules likely due to accretion reactions and has more nitrogen-containing compounds. We identify some new compounds formed in cloud. Such modifications of the organics in cloud can further change its physicochemical properties, and impact on climate and human health.
Hao Luo, Luc Vereecken, Hongru Shen, Sungah Kang, Iida Pullinen, Mattias Hallquist, Hendrik Fuchs, Andreas Wahner, Astrid Kiendler-Scharr, Thomas F. Mentel, and Defeng Zhao
Atmos. Chem. Phys., 23, 7297–7319, https://doi.org/10.5194/acp-23-7297-2023, https://doi.org/10.5194/acp-23-7297-2023, 2023
Short summary
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.
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.
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.
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.
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.
Yali Jin, Hao Luo, Siqi Tang, Shuhui Xue, Chengyu Nie, Xiaocong Peng, Yan Zheng, Weiqi Xu, Guohua Zhang, Xiaole Pan, Yele Sun, Qi Chen, Lanzhong Liu, and Defeng Zhao
EGUsphere, https://doi.org/10.5194/egusphere-2025-4322, https://doi.org/10.5194/egusphere-2025-4322, 2025
This preprint is open for discussion and under review for Atmospheric Chemistry and Physics (ACP).
Short summary
Short summary
Cloud substantially changes the compositions organic aerosol. How cloud processing of organics occur on molecular level remains unclear. We found that compared with cloud free particles, organics in cloud contains more large molecules likely due to accretion reactions and has more nitrogen-containing compounds. We identify some new compounds formed in cloud. Such modifications of the organics in cloud can further change its physicochemical properties, and impact on climate and human health.
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.
Junwei Song, Georgios I. Gkatzelis, Ralf Tillmann, Nicolas Brüggemann, Thomas Leisner, and Harald Saathoff
Atmos. Chem. Phys., 24, 13199–13217, https://doi.org/10.5194/acp-24-13199-2024, https://doi.org/10.5194/acp-24-13199-2024, 2024
Short summary
Short summary
Biogenic volatile organic compounds (BVOCs) and organic aerosol (OA) particles were measured online in a stressed spruce-dominated forest. OA was mainly attributed to the monoterpene oxidation products. The mixing ratios of BVOCs were higher than the values previously measured in other temperate forests. The results demonstrate that BVOCs are influenced not only by meteorology and biogenic emissions but also by local anthropogenic emissions and subsequent chemical transformation processes.
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.
Hengheng Zhang, Christian Rolf, Ralf Tillmann, Christian Wesolek, Frank Gunther Wienhold, Thomas Leisner, and Harald Saathoff
Aerosol Research, 2, 135–151, https://doi.org/10.5194/ar-2-135-2024, https://doi.org/10.5194/ar-2-135-2024, 2024
Short summary
Short summary
Our study employs advanced tools, including scanning lidar, balloons, and UAVs, to explore aerosol particles in the atmosphere. The scanning lidar offers distinctive near-ground-level insights, enriching our comprehension of aerosol distribution from ground level to the free troposphere. This research provides valuable data for comparing remote sensing and in situ aerosol measurements, advancing our understanding of aerosol impacts on radiative transfer, clouds, and air quality.
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.
Hao Luo, Luc Vereecken, Hongru Shen, Sungah Kang, Iida Pullinen, Mattias Hallquist, Hendrik Fuchs, Andreas Wahner, Astrid Kiendler-Scharr, Thomas F. Mentel, and Defeng Zhao
Atmos. Chem. Phys., 23, 7297–7319, https://doi.org/10.5194/acp-23-7297-2023, https://doi.org/10.5194/acp-23-7297-2023, 2023
Short summary
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.
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.
Sophie Dixneuf, Albert A. Ruth, Rolf Häseler, Theo Brauers, Franz Rohrer, and Hans-Peter Dorn
Atmos. Meas. Tech., 15, 945–964, https://doi.org/10.5194/amt-15-945-2022, https://doi.org/10.5194/amt-15-945-2022, 2022
Short summary
Short summary
Atmospheric chambers, like SAPHIR in Jülich (Germany), are used to experimentally simulate specific atmospheric scenarios to improve our understanding of the complex chemical reactions occurring in our atmospheres. These facilities hence require cutting-edge gas-sensing capabilities to detect trace gases at the lowest level and in a short time. One important trace gas is HONO, for which we custom-built an optical sensing setup, capable of detecting one HONO molecule in ~40 billion in 1 min.
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.
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.
Cited articles
Atkinson, R., Baulch, D. L., Cox, R. A., Crowley, J. N., Hampson, R. F., Hynes, R. G., Jenkin, M. E., Rossi, M. J., Troe, J., and IUPAC Subcommittee: Evaluated kinetic and photochemical data for atmospheric chemistry: Volume II – gas phase reactions of organic species, Atmos. Chem. Phys., 6, 3625–4055, https://doi.org/10.5194/acp-6-3625-2006, 2006.
Ayres, B. R., Allen, H. M., Draper, D. C., Brown, S. S., Wild, R. J., Jimenez, J. L., Day, D. A., Campuzano-Jost, P., Hu, W., de Gouw, J., Koss, A., Cohen, R. C., Duffey, K. C., Romer, P., Baumann, K., Edgerton, E., Takahama, S., Thornton, J. A., Lee, B. H., Lopez-Hilfiker, F. D., Mohr, C., Wennberg, P. O., Nguyen, T. B., Teng, A., Goldstein, A. H., Olson, K., and Fry, J. L.: Organic nitrate aerosol formation via NO3 + biogenic volatile organic compounds in the southeastern United States, Atmos. Chem. Phys., 15, 13377–13392, https://doi.org/10.5194/acp-15-13377-2015, 2015.
Berndt, T. and Böge, O.: Gas-phase reaction of NO3 radicals with
isoprene: a kinetic and mechanistic study, Int. J. Chem. Kinet., 29, 755–765, https://doi.org/10.1002/(sici)1097-4601(1997)29:10<755::Aid-kin4>3.0.Co;2-l, 1997.
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 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. Edit., 57,
3820–3824, https://doi.org/10.1002/anie.201710989, 2018b.
Bernhammer, A.-K., Fischer, L., Mentler, B., Heinritzi, M., Simon, M., and Hansel, A.: Production of highly oxygenated organic molecules (HOMs) from trace contaminants during isoprene oxidation, Atmos. Meas. Tech., 11, 4763–4773, https://doi.org/10.5194/amt-11-4763-2018, 2018.
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.
Boyd, C. M., Sanchez, J., Xu, L., Eugene, A. J., Nah, T., Tuet, W. Y., Guzman, M. I., and Ng, N. L.: Secondary organic aerosol formation from the β-pinene+NO3 system: effect of humidity and peroxy radical fate, Atmos. Chem. Phys., 15, 7497–7522, https://doi.org/10.5194/acp-15-7497-2015, 2015.
Boyd, C. M., Nah, T., Xu, L., Berkemeier, T., and Ng, N. L.: Secondary
Organic Aerosol (SOA) from Nitrate Radical Oxidation of Monoterpenes:
Effects of Temperature, Dilution, and Humidity on Aerosol Formation, Mixing,
and Evaporation, Environ. Sci. Technol., 51, 7831–7841,
https://doi.org/10.1021/acs.est.7b01460, 2017.
Brown, S. S. and Stutz, J.: Nighttime radical observations and chemistry,
Chem. Soc. Rev., 41, 6405–6447, https://doi.org/10.1039/c2cs35181a, 2012.
Brown, S. S., deGouw, J. A., Warneke, C., Ryerson, T. B., Dubé, W. P., Atlas, E., Weber, R. J., Peltier, R. E., Neuman, J. A., Roberts, J. M., Swanson, A., Flocke, F., McKeen, S. A., Brioude, J., Sommariva, R., Trainer, M., Fehsenfeld, F. C., and Ravishankara, A. R.: Nocturnal isoprene oxidation over the Northeast United States in summer and its impact on reactive nitrogen partitioning and secondary organic aerosol, Atmos. Chem. Phys., 9, 3027–3042, https://doi.org/10.5194/acp-9-3027-2009, 2009.
Brown, S. S., Dube, W. P., Peischl, J., Ryerson, T. B., Atlas, E., Warneke,
C., de Gouw, J. A., Hekkert, S. t. L., Brock, C. A., Flocke, F., Trainer,
M., Parrish, D. D., Feshenfeld, F. C., and Ravishankara, A. R.: Budgets for
nocturnal VOC oxidation by nitrate radicals aloft during the 2006 Texas Air
Quality Study, J. Geophys. Res.-Atmos., 116, D24305, https://doi.org/10.1029/2011jd016544, 2011.
Chen, J., Møller, K. H., Wennberg, P. O., and Kjaergaard, H. G.:
Unimolecular Reactions Following Indoor and Outdoor Limonene Ozonolysis, J.
Phys. Chem. A, 125, 669–680, 10.1021/acs.jpca.0c09882, 2021.
Chen, Y., Takeuchi, M., Nah, T., Xu, L., Canagaratna, M. R., Stark, H., Baumann, K., Canonaco, F., Prévôt, A. S. H., Huey, L. G., Weber, R. J., and Ng, N. L.: Chemical characterization of secondary organic aerosol at a rural site in the southeastern US: insights from simultaneous high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) and FIGAERO chemical ionization mass spectrometer (CIMS) measurements, Atmos. Chem. Phys., 20, 8421–8440, https://doi.org/10.5194/acp-20-8421-2020, 2020.
Claflin, M. S. and Ziemann, P. J.: Identification and Quantitation of
Aerosol Products of the Reaction of β-Pinene with NO3 Radicals
and Implications for Gas- and Particle-Phase Reaction Mechanisms,
J. Phys. Chem. A, 122, 3640–3652, https://doi.org/10.1021/acs.jpca.8b00692,
2018.
Crounse, J. D., Knap, H. C., Ørnsø, K. B., Jørgensen, S., Paulot,
F., Kjaergaard, H. G., and Wennberg, P. O.: Atmospheric Fate of
Methacrolein. 1. Peroxy Radical Isomerization Following Addition of OH and
O2, J. Phys. Chem. A, 116, 5756–5762,
https://doi.org/10.1021/jp211560u, 2012.
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.
Draper, D. C., Myllys, N., Hyttinen, N., Møller, K. H., Kjaergaard, H.
G., Fry, J. L., Smith, J. N., and Kurten, T.: Formation of Highly Oxidized
Molecules from NO3 Radical Initiated Oxidation of Δ-3-Carene: A
Mechanistic Study, ACS Earth and Space Chemistry, 3, 1460–1470,
https://doi.org/10.1021/acsearthspacechem.9b00143, 2019.
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.,
Jørgensen, S., Kjaergaard, H. G., Canagaratna, M., Dal Maso, M., 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.
Faxon, C., Hammes, J., Le Breton, M., Pathak, R. K., and Hallquist, M.: Characterization of organic nitrate constituents of secondary organic aerosol (SOA) from nitrate-radical-initiated oxidation of limonene using high-resolution chemical ionization mass spectrometry, Atmos. Chem. Phys., 18, 5467–5481, https://doi.org/10.5194/acp-18-5467-2018, 2018.
Finlayson-Pitts, B. and Pitts, J.: Chemistry of the upper and lower
atmosphere, Academic Press, San Diego, 2000.
Fry, J. L., Kiendler-Scharr, A., Rollins, A. W., Wooldridge, P. J., Brown, S. S., Fuchs, H., Dubé, W., Mensah, A., dal Maso, M., Tillmann, R., Dorn, H.-P., Brauers, T., and Cohen, R. C.: Organic nitrate and secondary organic aerosol yield from NO3 oxidation of β-pinene evaluated using a gas-phase kinetics/aerosol partitioning model, Atmos. Chem. Phys., 9, 1431–1449, https://doi.org/10.5194/acp-9-1431-2009, 2009.
Fry, J. L., Kiendler-Scharr, A., Rollins, A. W., Brauers, T., Brown, S. S., Dorn, H.-P., Dubé, W. P., Fuchs, H., Mensah, A., Rohrer, F., Tillmann, R., Wahner, A., Wooldridge, P. J., and Cohen, R. C.: SOA from limonene: role of NO3 in its generation and degradation, Atmos. Chem. Phys., 11, 3879–3894, https://doi.org/10.5194/acp-11-3879-2011, 2011.
Fry, J. L., Draper, D. C., Barsanti, K. C., Smith, J. N., Ortega, J.,
Winkle, P. M., Lawler, M. J., Brown, S. S., Edwards, P. M., Cohen, R. C.,
and Lee, L.: Secondary Organic Aerosol Formation and Organic Nitrate Yield
from NO3 Oxidation of Biogenic Hydrocarbons, Environ. Sci. Technol.,
48, 11944–11953, https://doi.org/10.1021/es502204x, 2014.
Fry, J. L., Brown, S. S., Middlebrook, A. M., Edwards, P. M., Campuzano-Jost, P., Day, D. A., Jimenez, J. L., Allen, H. M., Ryerson, T. B., Pollack, I., Graus, M., Warneke, C., de Gouw, J. A., Brock, C. A., Gilman, J., Lerner, B. M., Dubé, W. P., Liao, J., and Welti, A.: Secondary organic aerosol (SOA) yields from NO3 radical + isoprene based on nighttime aircraft power plant plume transects, Atmos. Chem. Phys., 18, 11663–11682, https://doi.org/10.5194/acp-18-11663-2018, 2018.
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.
Garmash, O., Rissanen, M. P., Pullinen, I., Schmitt, S., Kausiala, O., Tillmann, R., Zhao, D., Percival, C., Bannan, T. J., Priestley, M., Hallquist, Å. M., Kleist, E., Kiendler-Scharr, A., Hallquist, M., Berndt, T., McFiggans, G., Wildt, J., Mentel, T. F., and Ehn, M.: Multi-generation OH oxidation as a source for highly oxygenated organic molecules from aromatics, Atmos. Chem. Phys., 20, 515–537, https://doi.org/10.5194/acp-20-515-2020, 2020.
Geyer, A., Alicke, B., Konrad, S., Schmitz, T., Stutz, J., and Platt, U.:
Chemistry and oxidation capacity of the nitrate radical in the continental
boundary layer near Berlin, J. Geophys. Res.-Atmos., 106, 8013–8025,
https://doi.org/10.1029/2000jd900681, 2001.
Hamilton, J. F., Bryant, D. J., Edwards, P. M., Ouyang, B., Bannan, T. J.,
Mehra, A., Mayhew, A. W., Hopkins, J. R., Dunmore, R. E., Squires, F. A.,
Lee, J. D., Newland, M. J., Worrall, S. D., Bacak, A., Coe, H., Percival,
C., Whalley, L. K., Heard, D. E., Slater, E. J., Jones, R. L., Cui, T.,
Surratt, J. D., Reeves, C. E., Mills, G. P., Grimmond, S., Sun, Y., Xu, W.,
Shi, Z., and Rickard, A. R.: Key Role of NO3 Radicals in the Production
of Isoprene Nitrates and Nitrooxyorganosulfates in Beijing, Environ. Sci.
Technol., 55, 842–853, https://doi.org/10.1021/acs.est.0c05689, 2021.
Huang, W., Saathoff, H., Shen, X. L., 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., Kupiainen-Määttä, O., Rissanen, M. P., Muuronen,
M., Ehn, M., and Kurtén, T.: Modeling the Charging of Highly Oxidized
Cyclohexene Ozonolysis Products Using Nitrate-Based Chemical Ionization,
J. Phys. Chem. A, 119, 6339–6345, https://doi.org/10.1021/acs.jpca.5b01818,
2015.
Japar, S. M. and Niki, H.: Gas-phase reactions of the nitrate radical with
olefins, J. Phys. Chem., 79, 1629–1632,
https://doi.org/10.1021/j100583a002, 1975.
Jenkin, M. E., Saunders, S. M., and Pilling, M. J.: The tropospheric
degradation of volatile organic compounds: A protocol for mechanism
development, Atmos. Environ., 31, 81–104, https://doi.org/10.1016/s1352-2310(96)00105-7,
1997.
Jenkin, M. E., Boyd, A. A., and Lesclaux, R.: Peroxy Radical Kinetics
Resulting from the OH-Initiated Oxidation of 1,3-Butadiene,
2,3-Dimethyl-1,3-Butadiene and Isoprene, J. Atmos. Chem., 29, 267–298,
https://doi.org/10.1023/A:1005940332441, 1998.
Jenkin, M. E., Saunders, S. M., Wagner, V., and Pilling, M. J.: Protocol for the development of the Master Chemical Mechanism, MCM v3 (Part B): tropospheric degradation of aromatic volatile organic compounds, Atmos. Chem. Phys., 3, 181–193, https://doi.org/10.5194/acp-3-181-2003, 2003.
Jenkin, M. E., Young, J. C., and Rickard, A. R.: The MCM v3.3.1 degradation scheme for isoprene, Atmos. Chem. Phys., 15, 11433–11459, https://doi.org/10.5194/acp-15-11433-2015, 2015.
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., Sipila, 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. Edit., 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 Sipila, 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.
Kaminski, M., Fuchs, H., Acir, I.-H., Bohn, B., Brauers, T., Dorn, H.-P., Häseler, R., Hofzumahaus, A., Li, X., Lutz, A., Nehr, S., Rohrer, F., Tillmann, R., Vereecken, L., Wegener, R., and Wahner, A.: Investigation of the β-pinene photooxidation by OH in the atmosphere simulation chamber SAPHIR, Atmos. Chem. Phys., 17, 6631–6650, https://doi.org/10.5194/acp-17-6631-2017, 2017.
Kenseth, C. M., Huang, Y. L., Zhao, R., Dalleska, N. F., Hethcox, 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.
D., 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.
Krechmer, J. E., Coggon, M. M., Massoli, P., Nguyen, T. B., Crounse, J. D.,
Hu, W. 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.,
Sipila, M., Junninen, H., St Clair, J. M., 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.
Kwan, A. J., Chan, A. W. H., Ng, N. L., Kjaergaard, H. G., Seinfeld, J. H., and Wennberg, P. O.: Peroxy radical chemistry and OH radical production during the NO3-initiated oxidation of isoprene, Atmos. Chem. Phys., 12, 7499–7515, https://doi.org/10.5194/acp-12-7499-2012, 2012.
Lai, C. C. and Finlayson-Pitts, B. J.: Reactions of dinitrogen pentoxide
and nitrogen-dioxide with 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine,
Lipids, 26, 306–314, https://doi.org/10.1007/bf02537142, 1991.
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, https://doi.org/10.1073/pnas.1508108113, 2016.
Lu, K. D., Rohrer, F., Holland, F., Fuchs, H., Brauers, T., Oebel, A., Dlugi, R., Hu, M., Li, X., Lou, S. R., Shao, M., Zhu, T., Wahner, A., Zhang, Y. H., and Hofzumahaus, A.: Nighttime observation and chemistry of HOx in the Pearl River Delta and Beijing in summer 2006, Atmos. Chem. Phys., 14, 4979–4999, https://doi.org/10.5194/acp-14-4979-2014, 2014.
Malkin, T. L., Goddard, A., Heard, D. E., and Seakins, P. W.: Measurements of OH and HO2 yields from the gas phase ozonolysis of isoprene, Atmos. Chem. Phys., 10, 1441–1459, https://doi.org/10.5194/acp-10-1441-2010, 2010.
Massoli, P., Stark, H., Canagaratna, M. R., Krechmer, J. E., Xu, L., Ng, N.
L., Mauldin, R. 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 and Space Chemistry, 2, 653–672,
https://doi.org/10.1021/acsearthspacechem.8b00028, 2018.
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.
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., Bianchi, F., Klein, F., El Haddad, I., Frege, C., Rossi, M. J., Dommen, J., and Baltensperger, U.: Formation of highly oxygenated organic molecules from aromatic compounds, Atmos. Chem. Phys., 18, 1909–1921, https://doi.org/10.5194/acp-18-1909-2018, 2018.
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 alpha-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.
Nah, T., Sanchez, J., Boyd, C. M., and Ng, N. L.: Photochemical Aging of
alpha-pinene and beta-pinene Secondary Organic Aerosol formed from Nitrate
Radical Oxidation, Environ. Sci. Technol., 50, 222–231,
https://doi.org/10.1021/acs.est.5b04594, 2016.
Ng, N. L., Kwan, A. J., Surratt, J. D., Chan, A. W. H., Chhabra, P. S., Sorooshian, A., Pye, H. O. T., Crounse, J. D., Wennberg, P. O., Flagan, R. C., and Seinfeld, J. H.: Secondary organic aerosol (SOA) formation from reaction of isoprene with nitrate radicals (NO3), Atmos. Chem. Phys., 8, 4117–4140, https://doi.org/10.5194/acp-8-4117-2008, 2008.
Nguyen, T. B., Tyndall, G. S., Crounse, J. D., Teng, A. P., Bates, K. H.,
Schwantes, R. H., Coggon, M. M., Zhang, L., Feiner, P., Milller, D. O.,
Skog, K. M., Rivera-Rios, J. C., Dorris, M., Olson, K. F., Koss, A., Wild,
R. J., Brown, S. S., Goldstein, A. H., de Gouw, J. A., Brune, W. H.,
Keutsch, F. N., Seinfeld, J. H., and Wennberg, P. O.: Atmospheric fates of
Criegee intermediates in the ozonolysis of isoprene, Phys. Chem. Chem.
Phys., 18, 10241–10254, https://doi.org/10.1039/c6cp00053c, 2016.
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. Edit., 58, 13976–13982, https://doi.org/10.1002/anie.201907981,
2019.
Perring, A. E., Wisthaler, A., Graus, M., Wooldridge, P. J., Lockwood, A. L., Mielke, L. H., Shepson, P. B., Hansel, A., and Cohen, R. C.: A product study of the isoprene+NO3 reaction, Atmos. Chem. Phys., 9, 4945–4956, https://doi.org/10.5194/acp-9-4945-2009, 2009.
Pfrang, C., Martin, R. S., Canosa-Mas, C. E., and Wayne, R. P.: Gas-phase
reactions of NO3 and N2O5 with (Z)-hex-4-en-1-ol,
(Z)-hex-3-en-1-ol (`leaf alcohol'), (E)-hex-3-en-1-ol, (Z)-hex-2-en-1-ol and
(E)-hex-2-en-1-ol, Phys. Chem. Chem. Phys., 8, 354–363, https://doi.org/10.1039/b510835g,
2006.
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.
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.
Richters, S., Pfeifle, M., Olzmann, M., and Berndt, T.: endo-Cyclization of
unsaturated RO2 radicals from the gas-phase ozonolysis of
cyclohexadienes, Chem. Commun., 53, 4132–4135, https://doi.org/10.1039/c7cc01350g, 2017.
Rissanen, M. P., Kurten, T., Sipila, 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., 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.
Rissanen, M. P., Kurten, T., Sipila, M., Thornton, J. A., Kausiala, O.,
Garmash, O., Kjaergaard, H. G., Petaja, T., Worsnop, D. R., Ehn, M., and
Kulmala, M.: Effects of Chemical Complexity on the Autoxidation Mechanisms
of Endocyclic Alkene Ozonolysis Products: From Methylcyclohexenes toward
Understanding alpha-Pinene, J. Phys. Chem. A, 119, 4633–4650,
https://doi.org/10.1021/jp510966g, 2015.
Riva, M., Rantala, P., Krechmer, J. E., Peräkylä, O., Zhang, Y., Heikkinen, L., Garmash, O., Yan, C., Kulmala, M., Worsnop, D., and Ehn, M.: Evaluating the performance of five different chemical ionization techniques for detecting gaseous oxygenated organic species, Atmos. Meas. Tech., 12, 2403–2421, https://doi.org/10.5194/amt-12-2403-2019, 2019.
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.
Rollins, A. W., Kiendler-Scharr, A., Fry, J. L., Brauers, T., Brown, S. S., Dorn, H.-P., Dubé, W. P., Fuchs, H., Mensah, A., Mentel, T. F., Rohrer, F., Tillmann, R., Wegener, R., Wooldridge, P. J., and Cohen, R. C.: Isoprene oxidation by nitrate radical: alkyl nitrate and secondary organic aerosol yields, Atmos. Chem. Phys., 9, 6685–6703, https://doi.org/10.5194/acp-9-6685-2009, 2009.
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.
Schwantes, R. H., Teng, A. P., Nguyen, T. B., Coggon, M. M., Crounse, J. D.,
St Clair, J. M., Zhang, X., Schilling, K. A., Seinfeld, J. H., and Wennberg,
P. O.: Isoprene NO3 Oxidation Products from the RO2+HO2
Pathway, J. Phys. Chem. A 119, 10158–10171, https://doi.org/10.1021/acs.jpca.5b06355, 2015.
Skov, H., Hjorth, J., Lohse, C., Jensen, N. R., and Restelli, G.: Products
and mechanisms of the reactions of the nitrate radical (NO3) with isoprene,
1,3-butadiene and 2,3-dimethyl-1,3-butadiene in air, Atmos.
Environ. A.-Gen., 26, 2771–2783,
https://doi.org/10.1016/0960-1686(92)90015-D, 1992.
Stark, M. S.: Epoxidation of Alkenes by Peroxyl Radicals in the Gas Phase:
Structure-Activity Relationships, J. Phys. Chem. A, 101,
8296–8301, https://doi.org/10.1021/jp972054+, 1997.
Stark, M. S.: Addition of Peroxyl Radicals to Alkenes and the Reaction of
Oxygen with Alkyl Radicals, J. Am. Chem. Soc., 122, 4162–4170,
https://doi.org/10.1021/ja993760m, 2000.
Starn, T. K., Shepson, P. B., Bertman, S. B., Riemer, D. D., Zika, R. G.,
and Olszyna, K.: Nighttime isoprene chemistry at an urban-impacted forest
site, 103, 22437–22447, https://doi.org/10.1029/98JD01201,
1998.
Stroud, C. A., Roberts, J. M., Williams, E. J., Hereid, D., Angevine, W. M.,
Fehsenfeld, F. C., Wisthaler, A., Hansel, A., Martinez-Harder, M., Harder,
H., Brune, W. H., Hoenninger, G., Stutz, J., and White, A. B.: Nighttime
isoprene trends at an urban forested site during the 1999 Southern Oxidant
Study, 107, ACH 7-1–ACH 7-14,
https://doi.org/10.1029/2001JD000959, 2002.
Takeuchi, M. and Ng, N. L.: Chemical composition and hydrolysis of organic nitrate aerosol formed from hydroxyl and nitrate radical oxidation of α-pinene and β-pinene, Atmos. Chem. Phys., 19, 12749–12766, https://doi.org/10.5194/acp-19-12749-2019, 2019.
Tan, Z., Lu, K., Hofzumahaus, A., Fuchs, H., Bohn, B., Holland, F., Liu, Y., Rohrer, F., Shao, M., Sun, K., Wu, Y., Zeng, L., Zhang, Y., Zou, Q., Kiendler-Scharr, A., Wahner, A., and Zhang, Y.: Experimental budgets of OH, HO2, and RO2 radicals and implications for ozone formation in the Pearl River Delta in China 2014, Atmos. Chem. Phys., 19, 7129–7150, https://doi.org/10.5194/acp-19-7129-2019, 2019.
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., 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 Francisco, J. S.: Theoretical studies of atmospheric
reaction mechanisms in the troposphere, Chem. Soc. Rev., 41, 6259–6293,
https://doi.org/10.1039/c2cs35070j, 2012.
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.: 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 beta-pinene (C10H16): first generation
products, Phys. Chem. Chem. Phys., 14, 3802–3815, https://doi.org/10.1039/c2cp23711c, 2012.
Vereecken, L., Mueller, J. F., and Peeters, J.: Low-volatility
poly-oxygenates in the OH-initiated atmospheric oxidation of alpha-pinene:
impact of non-traditional peroxyl radical chemistry, Phys. Chem. Chem.
Phys., 9, 5241–5248, https://doi.org/10.1039/b708023a, 2007.
Vereecken, L., Carlsson, P. T. M., Novelli, A., Bernard, F., Brown, S. S.,
Cho, C., Crowley, J. N., Fuchs, H., Mellouki, W., Reimer, D., Shenolikar,
J., Tillmann, R., Zhou, L., Kiendler-Scharr, A., and Wahner, A.: Theoretical
and experimental study of peroxy and alkoxy radicals in the
NO3-initiated oxidation of isoprene, Phys. Chem. Chem. Phys., 23,
5496–5515, https://doi.org/10.1039/d0cp06267g, 2021.
Viggiano, A. A., Seeley, J. V., Mundis, P. L., Williamson, J. S., and
Morris, R. A.: Rate Constants for the Reactions of XO3−(H2O)n
(X = C, HC, and N) and NO3−(HNO3)n with H2SO4:
Implications for Atmospheric Detection of H2SO4, J.
Phys. Chem. A, 101, 8275–8278, https://doi.org/10.1021/jp971768h, 1997.
Wagner, N. L., Dubé, W. P., Washenfelder, R. A., Young, C. J., Pollack, I. B., Ryerson, T. B., and Brown, S. S.: Diode laser-based cavity ring-down instrument for NO3, N2O5, NO, NO2 and O3 from aircraft, Atmos. Meas. Tech., 4, 1227–1240, https://doi.org/10.5194/amt-4-1227-2011, 2011.
Wang, Y., Mehra, A., Krechmer, J. E., Yang, G., Hu, X., Lu, Y., Lambe, A., Canagaratna, M., Chen, J., Worsnop, D., Coe, H., and Wang, L.: Oxygenated products formed from OH-initiated reactions of trimethylbenzene: autoxidation and accretion, Atmos. Chem. Phys., 20, 9563–9579, https://doi.org/10.5194/acp-20-9563-2020, 2020.
Wennberg, P. O., Bates, K. H., Crounse, J. D., Dodson, L. G., McVay, R. C.,
Mertens, L. A., Nguyen, T. B., Praske, E., Schwantes, R. H., Smarte, M. D.,
St Clair, J. M., Teng, A. P., Zhang, X., and Seinfeld, J. H.: Gas-Phase
Reactions of Isoprene and Its Major Oxidation Products, Chem. Rev., 118,
3337–3390, https://doi.org/10.1021/acs.chemrev.7b00439, 2018.
Wu, R., Vereecken, L., Tsiligiannis, E., Kang, S., Albrecht, S. R., Hantschke, L., Zhao, D., Novelli, A., Fuchs, H., Tillmann, R., Hohaus, T., Carlsson, P. T. M., Shenolikar, J., Bernard, F., Crowley, J. N., Fry, J. L., Brownwood, B., Thornton, J. A., Brown, S. S., Kiendler-Scharr, A., Wahner, A., Hallquist, M., and Mentel, T. F.: Molecular composition and volatility of multi-generation products formed from isoprene oxidation by nitrate radical, Atmos. Chem. Phys. Discuss. [preprint], https://doi.org/10.5194/acp-2020-1180, in review, 2020.
Xu, L., Guo, H. Y., Boyd, C. M., Klein, M., Bougiatioti, A., Cerully, K. M.,
Hite, J. R., Isaacman-VanWertz, G., Kreisberg, N. M., Knote, C., Olson, K.,
Koss, A., Goldstein, A. H., Hering, S. V., de Gouw, J., Baumann, K., Lee, S.
H., Nenes, A., Weber, R. J., and Ng, N. L.: Effects of anthropogenic
emissions on aerosol formation from isoprene and monoterpenes in the
southeastern United States, P. Natl. Acad. Sci. USA, 112, 37–42,
https://doi.org/10.1073/pnas.1417609112, 2015.
Xu, Z. N., Nie, W., Liu, Y. L., Sun, P., Huang, D. D., Yan, C., Krechmer,
J., Ye, P. L., Xu, Z., Qi, X. M., Zhu, C. J., Li, Y. Y., Wang, T. Y., Wang,
L., Huang, X., Tang, R. Z., Guo, S., Xiu, G. L., Fu, Q. Y., Worsnop, D.,
Chi, X. G., and Ding, A. J.: Multifunctional Products of Isoprene Oxidation
in Polluted Atmosphere and Their Contribution to SOA, Geophys. Res. Lett., 48, e2020GL089276,
https://doi.org/10.1029/2020GL089276, 2021.
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, Science Advances, 6, eaay4945, https://doi.org/10.1126/sciadv.aay4945,
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. 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, Th. 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.
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
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.
The reaction of isoprene, a biogenic volatile organic compound with the globally largest...
Altmetrics
Final-revised paper
Preprint