Articles | Volume 25, issue 6
https://doi.org/10.5194/acp-25-3481-2025
© Author(s) 2025. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
https://doi.org/10.5194/acp-25-3481-2025
© Author(s) 2025. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
25 Mar 2025
Research article |
| 25 Mar 2025
| 25 Mar 2025
Kinetics of the reactions of OH with CO, NO, and NO2 and of HO2 with NO2 in air at 1 atm pressure, room temperature, and tropospheric water vapour concentrations
Michael Rolletter
Institute of Climate and Energy Systems, ICE-3: Troposphere, Forschungszentrum Jülich GmbH, Jülich, Germany
Andreas Hofzumahaus
CORRESPONDING AUTHOR
Institute of Climate and Energy Systems, ICE-3: Troposphere, Forschungszentrum Jülich GmbH, Jülich, Germany
Anna Novelli
Institute of Climate and Energy Systems, ICE-3: Troposphere, Forschungszentrum Jülich GmbH, Jülich, Germany
Andreas Wahner
Institute of Climate and Energy Systems, ICE-3: Troposphere, Forschungszentrum Jülich GmbH, Jülich, Germany
Institute of Climate and Energy Systems, ICE-3: Troposphere, Forschungszentrum Jülich GmbH, Jülich, Germany
Department of Physics, University of Cologne, Cologne, Germany
Related authors
No articles found.
Sungah Kang, Jürgen Wildt, Iida Pullinen, Luc Vereecken, Cheng Wu, Andreas Wahner, Sören R. Zorn, and Thomas F. Mentel
Atmos. Chem. Phys., 25, 15715–15740, https://doi.org/10.5194/acp-25-15715-2025, https://doi.org/10.5194/acp-25-15715-2025, 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.
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.
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.
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
Preprint archived
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.
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
Preprint archived
Short summary
Short summary
We use routine in-service commercial passenger airplanes Airbus A340 and A330 to collect air pollutants in the upper troposphere. The beauty in using commercial airplanes is that these commercial airplanes, like taxi on the ground, keep flying all the time. We find that short-lived air pollutants are very sensitive to ground-level emissions. Effective regulation in ground-level emissions can help to reduce air pollution in the upper troposphere.
Felix Wieser, Rolf Sander, Changmin Cho, Hendrik Fuchs, Thorsten Hohaus, Anna Novelli, Ralf Tillmann, and Domenico Taraborrelli
Geosci. Model Dev., 17, 4311–4330, https://doi.org/10.5194/gmd-17-4311-2024, https://doi.org/10.5194/gmd-17-4311-2024, 2024
Short summary
Short summary
The chemistry scheme of the atmospheric box model CAABA/MECCA is expanded to achieve an improved aerosol formation from emitted organic compounds. In addition to newly added reactions, temperature-dependent partitioning of all new species between the gas and aqueous phases is estimated and included in the pre-existing scheme. Sensitivity runs show an overestimation of key compounds from isoprene, which can be explained by a lack of aqueous-phase degradation reactions and box model limitations.
Yarê Baker, Sungah Kang, Hui Wang, Rongrong Wu, Jian Xu, Annika Zanders, Quanfu He, Thorsten Hohaus, Till Ziehm, Veronica Geretti, Thomas J. Bannan, Simon P. O'Meara, Aristeidis Voliotis, Mattias Hallquist, Gordon McFiggans, Sören R. Zorn, Andreas Wahner, and Thomas F. Mentel
Atmos. Chem. Phys., 24, 4789–4807, https://doi.org/10.5194/acp-24-4789-2024, https://doi.org/10.5194/acp-24-4789-2024, 2024
Short summary
Short summary
Highly oxygenated organic molecules are important contributors to secondary organic aerosol. Their yield depends on detailed atmospheric chemical composition. One important parameter is the ratio of hydroperoxy radicals to organic peroxy radicals (HO2/RO2), and we show that higher HO2/RO2 ratios lower the secondary organic aerosol yield. This is of importance as laboratory studies are often biased towards organic peroxy radicals.
Rongrong Wu, Sören R. Zorn, Sungah Kang, Astrid Kiendler-Scharr, Andreas Wahner, and Thomas F. Mentel
Atmos. Meas. Tech., 17, 1811–1835, https://doi.org/10.5194/amt-17-1811-2024, https://doi.org/10.5194/amt-17-1811-2024, 2024
Short summary
Short summary
Recent advances in high-resolution time-of-flight chemical ionization mass spectrometry (CIMS) enable the detection of highly oxygenated organic molecules, which efficiently contribute to secondary organic aerosol. Here we present an application of fuzzy c-means (FCM) clustering to deconvolve CIMS data. FCM not only reduces the complexity of mass spectrometric data but also the chemical and kinetic information retrieved by clustering gives insights into the chemical processes involved.
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.
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.
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.
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.
Clara M. Nussbaumer, John N. Crowley, Jan Schuladen, Jonathan Williams, Sascha Hafermann, Andreas Reiffs, Raoul Axinte, Hartwig Harder, Cheryl Ernest, Anna Novelli, Katrin Sala, Monica Martinez, Chinmay Mallik, Laura Tomsche, Christian Plass-Dülmer, Birger Bohn, Jos Lelieveld, and Horst Fischer
Atmos. Chem. Phys., 21, 18413–18432, https://doi.org/10.5194/acp-21-18413-2021, https://doi.org/10.5194/acp-21-18413-2021, 2021
Short summary
Short summary
HCHO is an important atmospheric trace gas influencing the photochemical processes in the Earth’s atmosphere, including the budget of HOx and the abundance of tropospheric O3. This research presents the photochemical calculations of HCHO and O3 based on three field campaigns across Europe. We show that HCHO production via the oxidation of only four volatile organic compound precursors, i.e., CH4, CH3CHO, C5H8 and CH3OH, can balance the observed loss at all sites well.
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.
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.
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.
Rongrong Wu, Luc Vereecken, Epameinondas Tsiligiannis, Sungah Kang, Sascha R. Albrecht, Luisa Hantschke, Defeng Zhao, Anna Novelli, Hendrik Fuchs, Ralf Tillmann, Thorsten Hohaus, Philip T. M. Carlsson, Justin Shenolikar, François Bernard, John N. Crowley, Juliane L. Fry, Bellamy Brownwood, Joel A. Thornton, Steven S. Brown, Astrid Kiendler-Scharr, Andreas Wahner, Mattias Hallquist, and Thomas F. Mentel
Atmos. Chem. Phys., 21, 10799–10824, https://doi.org/10.5194/acp-21-10799-2021, https://doi.org/10.5194/acp-21-10799-2021, 2021
Short summary
Short summary
Isoprene is the biogenic volatile organic compound with the largest emissions rates. The nighttime reaction of isoprene with the NO3 radical has a large potential to contribute to SOA. We classified isoprene nitrates into generations and proposed formation pathways. Considering the potential functionalization of the isoprene nitrates we propose that mainly isoprene dimers contribute to SOA formation from the isoprene NO3 reactions with at least a 5 % mass yield.
Simon Rosanka, Rolf Sander, Andreas Wahner, and Domenico Taraborrelli
Geosci. Model Dev., 14, 4103–4115, https://doi.org/10.5194/gmd-14-4103-2021, https://doi.org/10.5194/gmd-14-4103-2021, 2021
Short summary
Short summary
The Jülich Aqueous-phase Mechanism of Organic Chemistry (JAMOC) is developed and implemented into the Module Efficiently Calculating the Chemistry of the Atmosphere (MECCA). JAMOC is an explicit in-cloud oxidation scheme for oxygenated volatile organic compounds (OVOCs), which is suitable for global model applications. Within a box-model study, we show that JAMOC yields reduced gas-phase concentrations of most OVOCs and oxidants, except for nitrogen oxides.
Simon Rosanka, Rolf Sander, Bruno Franco, Catherine Wespes, Andreas Wahner, and Domenico Taraborrelli
Atmos. Chem. Phys., 21, 9909–9930, https://doi.org/10.5194/acp-21-9909-2021, https://doi.org/10.5194/acp-21-9909-2021, 2021
Short summary
Short summary
In-cloud destruction of ozone depends on hydroperoxyl radicals in cloud droplets, where they are produced by oxygenated volatile organic compound (OVOC) oxygenation. Only rudimentary representations of these processes, if any, are currently available in global atmospheric models. By using a comprehensive atmospheric model that includes a complex in-cloud OVOC oxidation scheme, we show that atmospheric oxidants are reduced and models ignoring this process will underpredict clouds as ozone sinks.
Defeng Zhao, Iida Pullinen, Hendrik Fuchs, Stephanie Schrade, Rongrong Wu, Ismail-Hakki Acir, Ralf Tillmann, Franz Rohrer, Jürgen Wildt, Yindong Guo, Astrid Kiendler-Scharr, Andreas Wahner, Sungah Kang, Luc Vereecken, and Thomas F. Mentel
Atmos. Chem. Phys., 21, 9681–9704, https://doi.org/10.5194/acp-21-9681-2021, https://doi.org/10.5194/acp-21-9681-2021, 2021
Short summary
Short summary
The reaction of isoprene, a biogenic volatile organic compound with the globally largest emission rates, with NO3, an nighttime oxidant influenced heavily by anthropogenic emissions, forms a large number of highly oxygenated organic molecules (HOM). These HOM are formed via one or multiple oxidation steps, followed by autoxidation. Their total yield is much higher than that in the daytime oxidation of isoprene. They may play an important role in nighttime organic aerosol formation and growth.
Marvin Glowania, Franz Rohrer, Hans-Peter Dorn, Andreas Hofzumahaus, Frank Holland, Astrid Kiendler-Scharr, Andreas Wahner, and Hendrik Fuchs
Atmos. Meas. Tech., 14, 4239–4253, https://doi.org/10.5194/amt-14-4239-2021, https://doi.org/10.5194/amt-14-4239-2021, 2021
Short summary
Short summary
Three instruments that use different techniques to measure gaseous formaldehyde concentrations were compared in experiments in the atmospheric simulation chamber SAPHIR at Forschungszentrum Jülich. The results demonstrated the need to correct the baseline in measurements by instruments that use the Hantzsch reaction or make use of cavity ring-down spectroscopy. After applying corrections, all three methods gave accurate and precise measurements within their specifications.
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.
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.
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.
Cited articles
Aloisio, S. and Francisco, J. S.: A density functional study of the H2O−-HOCO complex, J. Phys. Chem. A, 104, 404–407, https://doi.org/10.1021/jp9928356, 2000. a
Aloisio, S., Francisco, J. S., and Friedl, R. R.: Experimental evidence for the existence of the HO2–H2O complex, J. Phys. Chem. A, 104, 6597–6601, https://doi.org/10.1021/jp0006330, 2000. a, b, c, d
Amedro, D., Miyazaki, K., Parker, A., Schoemaecker, C., and Fittschen, C.: Atmospheric and kinetic studies of OH and HO2 by the FAGE technique, J. Environ. Sci., 24, 78–86, https://doi.org/10.1016/S1001-0742(11)60723-7, 2012. a
Amedro, D., Bunkan, A. J. C., Berasategui, M., and Crowley, J. N.: Kinetics of the OH + NO2 reaction: rate coefficients (217–333 K, 16–1200 mbar) and fall-off parameters for N2 and O2 bath gases, Atmos. Chem. Phys., 19, 10643–10657, https://doi.org/10.5194/acp-19-10643-2019, 2019. a, b, c, d, e, f, g, h, i
Amedro, D., Berasategui, M., Bunkan, A. J. C., Pozzer, A., Lelieveld, J., and Crowley, J. N.: Kinetics of the OH + NO2 reaction: effect of water vapour and new parameterization for global modelling, Atmos. Chem. Phys., 20, 3091–3105, https://doi.org/10.5194/acp-20-3091-2020, 2020. a, b, c, d, e, f, g, h, i
Anastasi, C. and Smith, I. W. M.: Rate measurements of reactions of OH by resonance absorption. Part 6. Rate constants for
Atkinson, R., Baulch, D. L., Cox, R. A., Crowley, J. N., Hampson, R. F., Hynes, R. G., Jenkin, M. E., Rossi, M. J., and Troe, J.: Evaluated kinetic and photochemical data for atmospheric chemistry: Volume I – gas phase reactions of Ox, HOx, NOx and SOx species, Atmos. Chem. Phys., 4, 1461–1738, https://doi.org/10.5194/acp-4-1461-2004, 2004. a, b, c, d, e, f
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. a
Bacak, A., Cooke, M. C., Bardwell, M. W., McGillen, M. R., Archibald, A. T., Huey, L. G., Tanner, D., Utembe, S. R., Jenkin, M. E., Derwent, R. G., Shallcross, D. E., and Percival, C. J.: Kinetics of the HO2+NO2 reaction: On the impact of new gas-phase kinetic data for the formation of HO2NO2 on HOX, NOX and HO2NO2 levels in the troposphere, Atmos. Environ., 45, 6414–6422, https://doi.org/10.1016/j.atmosenv.2011.08.008, 2011. a, b, c, d
Barker, J. R., Stanton, J. F., and Nguyen, T. L.: Semiclassical transition state theory/master equation kinetics of HO+CO: Performance evaluation, Int. J. Chem. Kin., 52, 1022–1045, https://doi.org/10.1002/kin.21420, 2020. a
Beno, M. F., Jonah, C. D., and Mulac, W. A.: Rate constants for the reaction OH+CO as functions of temperature and water concentration, Int. J. Chem. Kin., 17, 1091–1101, https://doi.org/10.1002/kin.550171006, 1985. a
Berg, F., Novelli, A., Dubus, R., Hofzumahaus, A., Holland, F., Wahner, A., and Fuchs, H.: Temperature-dependent rate coefficients for the reactions of OH radicals with selected alkanes, aromatic compounds, and monoterpenes, Atmos. Chem. Phys., 24, 13715–13731, https://doi.org/10.5194/acp-24-13715-2024, 2024. a, b
Bohn, B. and Zetzsch, C.: Rate Constants of HO2+NO Covering Atmospheric Conditions. 1. HO2 Formed by OH+H2O2, J. Phys. Chem. A, 101, 1488–1493, https://doi.org/10.1021/jp961396x, 1997. a, b, c
Bohn, B. and Zetzsch, C.: Gas-phase reaction of the OH–benzene adduct with O2: reversibility and secondary formation of HO2, Phys. Chem. Chem. Phys., 1, 5097–5107, https://doi.org/10.1039/A904887A, 1999. a, b, c
Burkholder, J. B., Abbatt, J. P. D., Barnes, I., Roberts, J. M., Melamed, M. L., Ammann, M., Bertram, A. K., Cappa, C. D., Carlton, A. G., Carpenter, L. J., Crowley, J. N., Dubowski, Y., George, C., Heard, D. E., Herrmann, H., Keutsch, F. N., Kroll, J. H., McNeill, V. F., Ng, N. L., Nizkorodov, S. A., Orlando, J. J., Percival, C. J., Picquet-Varrault, B., Rudich, Y., Seakins, P. W., Surratt, J. D., Tanimoto, H., Thornton, J. A., Tong, Z., Tyndall, G. S., Wahner, A., Weschler, C. J., Wilson, K. R., and Ziemann, P. J.: The essential role for laboratory studies in atmospheric chemistry, Environ. Sci. Technol., 51, 2519–2528, https://doi.org/10.1021/acs.est.6b04947, 2017. a, b
Burkholder, J. B., Sander, S. P., Abbatt, J. P. D., Barker, J. R., Huie, R. E., Kolb, C. E., Kurylo, M. J., Orkin, V. L., Wilmouth, D. M., and Wine, P. H.: Chemical kinetics and photochemical data for use in atmospheric studies–evaluation number 19, Nasa panel for data evaluation technical report, 19-5, 1–1610, https://jpldataeval.jpl.nasa.gov/pdf/NASA-JPL Evaluation 19-5.pdf (last access: 25 October 2024), 2020. a, b, c, d, e, f, g, h, i, j, k, l, m, n, o, p, q, r, s, t
Buszek, R. J., Francisco, J. S., and Anglada, J. M.: Water effects on atmospheric reactions, Int. Rev. Phys. Chem., 30, 335–369, https://doi.org/10.1080/0144235X.2011.634128, 2011. a, b
Chao, W., Jr-Min Lin, J., Takahashi, K., Tomas, A., Yu, L., Kajii, Y., Batut, S., Schoemaecker, C., and Fittschen, C.: Water vapor does not catalyze the reaction between methanol and OH radicals, Angew. Chem. Int. Ed., 58, 5013–5017, https://doi.org/10.1002/anie.201900711, 2019. a
Christensen, L. E., Okumura, M., Sander, S. P., Friedl, R. R., Miller, C. E., and Sloan, J. J.: Measurements of the rate constant of
Cox, R. A. and Burrows, J. P.: Kinetics and mechanism of the disproportionation of HO2 in the gas phase, J. Chem. Phys., 20, 2560–2588, https://doi.org/10.1021/j100483a002, 1979. a, b, c, d
Ehhalt, D. H.: Photooxidation of trace gases in the troposphere, Phys. Chem. Chem. Phys., 1, 5401–5408, https://doi.org/10.1039/a905097c, 1999. a
Ervens, B., Rickard, A., Aumont, B., Carter, W. P. L., McGillen, M., Mellouki, A., Orlando, J., Picquet-Varrault, B., Seakins, P., Stockwell, W. R., Vereecken, L., and Wallington, T. J.: Opinion: Challenges and needs of tropospheric chemical mechanism development, Atmos. Chem. Phys., 24, 13317–13339, https://doi.org/10.5194/acp-24-13317-2024, 2024. a
Fiore, A. M., Mickley, L. J., Zhu, Q., and Baublitz, C. B.: Climate and tropospheric oxidizing capacity, Annu. Rev. Earth Planet. Sci., 52, 321–349, https://doi.org/10.1146/annurev-earth-032320-090307, 2024. a, b
Fuchs, H., Bohn, B., Hofzumahaus, A., Holland, F., Lu, K. D., Nehr, S., Rohrer, F., and Wahner, A.: Detection of HO2 by laser-induced fluorescence: calibration and interferences from RO2 radicals, Atmos. Meas. Tech., 4, 1209–1225, https://doi.org/10.5194/amt-4-1209-2011, 2011. a, b
Fuchs, H., Hofzumahaus, A., Rohrer, F., Bohn, B., Brauers, T., Dorn, H.-P., Häseler, R., Holland, F., Kaminski, M., Li, X., Lu, K., Nehr, S., Tillmann, R., Wegener, R., and Wahner, A.: Experimental evidence for efficient hydroxyl radical regeneration in isoprene oxidation, Nat. Geosci., 6, 1023–1026, https://doi.org/10.1038/NGEO1964, 2013. a
Fuchs, H., Acir, I.-H., Bohn, B., Brauers, T., Dorn, H.-P., Häseler, R., Hofzumahaus, A., Holland, F., Kaminski, M., Li, X., Lu, K., Lutz, A., Nehr, S., Rohrer, F., Tillmann, R., Wegener, R., and Wahner, A.: OH regeneration from methacrolein oxidation investigated in the atmosphere simulation chamber SAPHIR, Atmos. Chem. Phys., 14, 7895–7908, https://doi.org/10.5194/acp-14-7895-2014, 2014. a
Fulle, D., Hamann, H. F., Hippler, H., and Troe, J.: High pressure range of addition reactions of HO. II. Temperature and pressure dependence of the reaction
Gierczak, T., Jiménez, E., Riffault, V., Burkholder, J. B., and Ravishankara, A. R.: Thermal decomposition of HO2NO2 (peroxynitric acid, PNA): Rate coefficient and determination of the enthalpy of formation, J. Phys. Chem. A, 109, 586–596, https://doi.org/10.1021/jp046632f, 2005. a, b
Griffith, S. M., Hansen, R. F., Dusanter, S., Michoud, V., Gilman, J. B., Kuster, W. C., Veres, P. R., Graus, M., de Gouw, J. A., Roberts, J., Young, C., Washenfelder, R., Brown, S. S., Thalman, R., Waxman, E., Volkamer, R., Tsai, C., Stutz, J., Flynn, J. H., Grossberg, N., Lefer, B., Alvarez, S. L., Rappenglueck, B., Mielke, L. H., Osthoff, H. D., and Stevens, P. S.: Measurements of hydroxyl and hydroperoxy radicals during CalNex-LA: Model comparisons and radical budgets, J. Geophys. Res., 121, 4211–4232, https://doi.org/10.1002/2015JD024358, 2016. a
Heard, D. E. and Henderson, D. A.: Quenching of OH(A
Hofzumahaus, A. and Stuhl, F.: Rate constant of the reaction HO+CO in the presence of N2 and O2, Ber. Bunsenges. Phys. Chem., 88, 557–561, https://doi.org/10.1002/bbpc.19840880612, 1984. a, b
Hofzumahaus, A., Rohrer, F., Lu, K., Bohn, B., Brauers, T., Chang, C.-C., Fuchs, H., Holland, F., Kita, K., Kondo, Y., Li, X., Lou, S., Shao, M., Zeng, L., Wahner, A., and Zhang, Y.: Amplified trace gas removal in the troposphere, Science, 324, 1702–1704, https://doi.org/10.1126/science.1164566, 2009. a, b, c, d
Hynes, A. J., Wine, P. H., and Ravishankara, A. R.: Kinetics of the OH+CO reaction under atmospheric conditions, J. Geophys. Res., 91, 11815–11820, https://doi.org/10.1029/JD091iD11p11815, 1986. a, b, c, d
Ivanov, A. V., Trakhtenberg, S., Bertram, A. K., Gershenzon, Y. M., and Molina, M. J.: OH, HO2, and ozone gaseous diffusion coefficients, J. Phys. Chem. A, 111, 1632–1637, https://doi.org/10.1021/jp066558w, 2007. a
Johnson, C. J., Otto, R., and Continetti, R. E.: Spectroscopy and dynamics of the HOCO radical: insights into the
Khan, M. A. H., Cooke, M. C., Utembe, S. R., Archibald, A. T., Derwent, R. G., Jenkin, M. E., Morris, W. C., South, N., Hansen, J. C., Francisco, J. S., Percival, C. J., and Shallcross, D. E.: Global analysis of peroxy radicals and peroxy radical-water complexation using the STOCHEM-CRI global chemistry and transport model, Atmos. Environ., 106, 278–287, https://doi.org/10.1016/j.atmosenv.2015.02.020, 2015. a
Kim, S., Huey, L. G., Stickel, R. E., Tanner, D. J., Crawford, J. H., Olson, J. R., Chen, G., Brune, W. H., Ren, X., Lesher, R., Wooldridge, P. J., Bertram, T. H., Perring, A., Cohen, R. C., Lefer, B. L., Shetter, R. E., Avery, M., Diskin, G., and Sokolik, I.: Measurement of HO2NO2 in the free troposphere during the Intercontinental Chemical Transport Experiment–North America 2004, J. Geophys. Res., 112, D12S01, https://doi.org/10.1029/2006JD007676, 2007. a
Kircher, C. C. and Sander, S. P.: Kinetics and mechanism of HO2 and DO2 disproportionations, J. Phys. Chem., 88, 2082–2091, https://doi.org/10.1021/j150654a029, 1984. a, b
Kleffmann, J., Gavriloaiei, T., Hofzumahaus, A., Holland, F., Koppmann, R., Rupp, L., Schlosser, E., Siese, M., and Wahner, A.: Daytime formation of nitrous acid: A major source of OH radicals in a forest, Geophys. Res. Lett., 32, L05818, https://doi.org/10.1029/2005GL022524, 2005. a
Kovacs, T. A. and Brune, W. H.: Total OH loss rate measurement, J. Atmos. Chem., 39, 105–122, 2001. a
Kurylo, M. J. and Ouellette, P. A.: Pressure dependence of the rate constant for the reaction
Liessmann, M., Miller, Y., Gerber, B., and B., A.: Reaction of OH and NO at Low Temperatures in the Presence of Water: the Role of Clusters, Zeitschrift für physikalische Chemie, 225, 1129–1144, https://doi.org/10.1524/zpch.2011.0181, 2011. a
Lii, R.-R., Sauer, Myran C., J., and Gordon, S.: Temperature dependence of the gas-phase self-reaction of hydroperoxo in the presence of water, J. Phys. Chem., 85, 2833–2834, https://doi.org/10.1021/j150619a027, 1981. a, b, c
Liu, Y. and Sander, S. P.: Rate constant for the OH+CO reaction at low temperatures, J. Chem. Phys. A, 119, 10060–10066, https://doi.org/10.1021/acs.jpca.5b07220, 2015. a, b
Lou, S., Holland, F., Rohrer, F., Lu, K., Bohn, B., Brauers, T., Chang, C. C., Fuchs, H., Häseler, R., Kita, K., Kondo, Y., Li, X., Shao, M., Zeng, L., Wahner, A., Zhang, Y., Wang, W., and Hofzumahaus, A.: Atmospheric OH reactivities in the Pearl River Delta – China in summer 2006: measurement and model results, Atmos. Chem. Phys., 10, 11243–11260, https://doi.org/10.5194/acp-10-11243-2010, 2010. a, b, c, d
Martinez, M., Harder, H., Kovacs, T. A., Simpas, J. B., Bassis, J., Lesher, R., Brune, W. H., Frost, G. J., Williams, E. J., Stroud, C. A., Jobson, B. T., Roberts, J. M., Hall, S. R., Shetter, R. E., Wert, B., Fried, A., Alicke, B., Stutz, J., Young, V. L., White, A. B., and Zamora, R. J.: OH and HO2 concentrations, sources, and loss rates during the Southern Oxidants Study in Nashville, Tennessee, summer 1999, J. Geophys. Res., 108, 4617, https://doi.org/10.1029/2003JD003551, 2003. a
McKee, K., Blitz, M. A., Shannon, R. J., and Pilling, M. J.: HO2+NO2: Kinetics, Thermochemistry, and evidence for a bimolecular product channel, J. Phys. Chem. A, 126, 7514–7522, https://doi.org/10.1021/acs.jpca.2c04601, 2022. a
Miyazaki, K., Nakashima, Y., Schoemaecker, C., Fittschen, C., and Kajii, Y.: Note: A laser-flash photolysis and laser-induced fluorescence detection technique for measuring total HO2 reactivity in ambient air, Rev. Sci. Instrum., 84, 076106, https://doi.org/10.1063/1.4812634, 2013. a
Miyoshi, A., Matsui, H., and Washida, N.: Detection and reactions of the HOCO radical in gas phase, J. Chem. Phys., 100, 3532–3539, https://doi.org/10.1063/1.466395, 1994. a
Mollner, A. K., Valluvadasan, S., Feng, L., Sprague, M. K., Okumura, M., Milligan, D. B., Bloss, W. J., Sander, S. P., Martien, P. T., Harley, R. A., McCoy, A. B., and Carter, W. P. L.: Rate of gas phase association of hydroxyl radical and nitrogen dioxide, Science, 330, 646–649, https://doi.org/10.1126/science.1193030, 2010. a, b, c, d, e, f, g, h, i
Nakashima, Y., Tsurumaru, H., Imamura, T., Bejan, I., Wenger, J. C., and Kajii, Y.: Total OH reactivity measurements in laboratory studies of the photooxidation of isoprene, Atmos. Environ., 62, 243–247, https://doi.org/10.1016/j.atmosenv.2012.08.033, 2012. a
Nehr, S., Bohn, B., Fuchs, H., Hofzumahaus, A., and Wahner, A.: HO2 formation from the OH+benzene reaction in the presence of O2, Phys. Chem. Chem. Phys., 13, 10699–10708, https://doi.org/10.1039/C1CP20334G, 2011. a, b
Nehr, S., Bohn, B., and Wahner, A.: Prompt HO2 formation following the reaction of OH with aromatic compounds under atmospheric conditions, J. Phys. Chem. A, 116, 6015–6026, https://doi.org/10.1021/jp210946y, 2012. a, b
Newsome, B. and Evans, M.: Impact of uncertainties in inorganic chemical rate constants on tropospheric composition and ozone radiative forcing, Atmos. Chem. Phys., 17, 14333–14352, https://doi.org/10.5194/acp-17-14333-2017, 2017. a
Okabe, H.: Photochemistry of small molecules, John Wiley and Sons, https://doi.org/10.1002/nadc.19790270512, 1978. a, b
Overend, R., Paraskevopoulos, G., and Black, C.: Rates of OH radical reactions. II. The combination reaction
Paraskevopoulos, G. and Irwin, R. S.: The pressure dependence of the rate constant of the reaction of OH radicals with CO, J. Phys. Chem., 80, 259–266, https://doi.org/10.1063/1.446488, 1984. a, b, c, d
Sadanaga, Y., Yoshino, A., Kato, S., Watanaba, K., Miyakawa, Y., Hayashi, I., and Kajii, Y.: The importance of NO2 and volatile organic compounds in the urban air from the viewpoint of the OH reactivity, Geophys. Res. Lett., 31, L08102, https://doi.org/10.1029/2004GL019661, 2004a. a
Sadanaga, Y., Yoshino, A., Watanaba, K., Yoshioka, A., Wakazono, Y., Kanaya, Y., and Kajii, Y.: Development of a measurement system of peroxy radicals using a chemical amplification/laser-induced fluorescence technique, Rev. Sci. Instrum., 75, 864–872, https://doi.org/10.1063/1.1666985, 2004b. a
Sharkey, P., Sims, I. R., Smith, I. W. M., Bocherel, P., and Rowe, B. R.: Pressure and temperature dependence of the rate constants for the association reaction of OH radicals with NO between 301 and 23 K, J. Chem. Soc. Faraday Trans., 90, 3609–3616, https://doi.org/10.1039/FT9949003609, 1994. a, b
Sheps, L. and Au, K.: New instrument for time-resolved OH and HO2 quantification in high-pressure laboratory kinetics studies, J. Phys. Chem. A, 128, 3916–3925, https://doi.org/10.1021/acs.jpca.4c00994, 2024. a
Smith, I. W. M. and Zellner, R.: Rate measurements of reactions of OH by resonance absorption. Part 2. Reactions of OH with CO, C2H4 and C2H2, J. Chem. Soc., Faraday Trans. 2, 69, 1617–1627, https://doi.org/10.1039/F29736901617, 1973. a
Speak, T. H., Blitz, M. A., Stone, D., and Seakins, P. W.: A new instrument for time-resolved measurement of HO2 radicals, Atmos. Meas. Tech., 13, 839–852, https://doi.org/10.5194/amt-13-839-2020, 2020. a
Stone, D., Blitz, M., Ingham, T., Onel, L., Medeiros, D. J., and Seakins, P. W.: An instrument to measure fast gas phase radical kinetics at high temperatures and pressures, Rev. Sci. Instr., 87, 054102, https://doi.org/10.1063/1.4950906, 2016. a
Strotkamp, M., Munk, A., Jungbluth, B., Dahlhoff, K., Jansen, P., Broch, S., Gomm, S., Bachner, M., Fuchs, H., Holland, F., and Hofzumahaus, A.: Design of a rugged 308 nm tunable UV laser for airborne LIF measurements on top of Zeppelin NT, Solid State Lasers Xxii: Technology and Devices, Proceedings of SPIE, 8599, 85990L, https://doi.org/10.1117/12.2000408, 2013. a
Troe, J.: Theory of thermal unimolecular reactions in the fall-off range. I, Strong collision rate constants, Ber. Bunsen Phys. Chem., 87, 161–169, https://doi.org/10.1002/bbpc.19830870217, 1983. a
Vandaele, A. C., Hermans, C., Simon, P. C., Carleer, M., Colin, R., Fally, S., M´erienne, M. F., Jenouvrier, A., and Coquart, B.: Measurements of the NO2 absorption cross-section from 42 000 cm−1 to 10 000 cm−1 (238–1000 nm) at 220 K and 294 K, J. Quant. Spe. Rad. Trans., 59, 171–184, https://doi.org/10.1016/S0022-4073(97)00168-4, 1998. a
Whalley, L. K., Edwards, P. M., Furneaux, K. L., Goddard, A., Ingham, T., Evans, M. J., Stone, D., Hopkins, J. R., Jones, C. E., Karunaharan, A., Lee, J. D., Lewis, A. C., Monks, P. S., Moller, S. J., and Heard, D. E.: Quantifying the magnitude of a missing hydroxyl radical source in a tropical rainforest, Atmos. Chem. Phys., 11, 7223–7233, https://doi.org/10.5194/acp-11-7223-2011, 2011. a
Yang, Y., Shao, M., Wang, X., Nölscher, A. C., Kessel, S., Guenther, A., and Williams, J.: Towards a quantitative understanding of total OH reactivity: A review, Atmos. Environ., 134, 147–161, https://doi.org/10.1016/j.atmosenv.2016.03.010, 2016. a, b
Zellweger, C., Steinbacher, M., and Buchmann, B.: Evaluation of new laser spectrometer techniques for in-situ carbon monoxide measurements, Atmos. Meas. Tech., 5, 2555–2567, https://doi.org/10.5194/amt-5-2555-2012, 2012. a
Zhou, J., Murano, K., Kohno, N., Sakamoto, Y., and Kajii, Y.: Real-time quantification of the total HO2 reactivity of ambient air and HO2 uptake kinetics onto ambient aerosols in Kyoto (Japan), Atmos. Environ., 223, 117189, https://doi.org/10.1016/j.atmosenv.2019.117189, 2019. a
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.
Highly accurate rate coefficients of termolecular reactions between OH and HO2 radicals and...
Altmetrics
Final-revised paper
Preprint