Articles | Volume 23, issue 18
https://doi.org/10.5194/acp-23-10517-2023
© Author(s) 2023. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
https://doi.org/10.5194/acp-23-10517-2023
© Author(s) 2023. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
25 Sep 2023
Research article |
| 25 Sep 2023
| 25 Sep 2023
An aldehyde as a rapid source of secondary aerosol precursors: theoretical and experimental study of hexanal autoxidation
Aerosol Physics Laboratory, Physics Unit, Faculty of Engineering and Natural Sciences, Tampere University, 33720 Tampere, Finland
Siddharth Iyer
Aerosol Physics Laboratory, Physics Unit, Faculty of Engineering and Natural Sciences, Tampere University, 33720 Tampere, Finland
Avinash Kumar
Aerosol Physics Laboratory, Physics Unit, Faculty of Engineering and Natural Sciences, Tampere University, 33720 Tampere, Finland
Prasenjit Seal
Aerosol Physics Laboratory, Physics Unit, Faculty of Engineering and Natural Sciences, Tampere University, 33720 Tampere, Finland
Aerosol Physics Laboratory, Physics Unit, Faculty of Engineering and Natural Sciences, Tampere University, 33720 Tampere, Finland
Department of Chemistry, University of Helsinki, PO Box 55, 00014, Helsinki, Finland
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Neil M. Donahue, Victoria Hofbauer, Henning Finkenzeller, Dominik Stolzenburg, Paulus S. Bauer, Randall Chiu, Lubna Dada, Jonathan Duplissy, Xu-Cheng He, Martin Heinritzi, Christopher R. Hoyle, Andreas Kürten, Aleksandr Kvashnin, Katrianne Lehtipalo, Naser Mahfouz, Vladimir Makhmutov, Roy L. Mauldin III, Ugo Molteni, Lauriane L. J. Quéléver, Matti Rissanen, Siegfried Schobesberger, Mario Simon, Andrea C. Wagner, Mingyi Wang, Chao Yan, Penglin Ye, Ilona Riipinen, Hamish Gordon, Joachim Curtius, Armin Hansel, Imad El Haddad, Markku Kulmala, Douglas R. Worsnop, Rainer Volkamer, Paul M. Winkler, Jasper Kirkby, and Richard Flagan
EGUsphere, https://doi.org/10.5194/egusphere-2025-2412, https://doi.org/10.5194/egusphere-2025-2412, 2025
This preprint is open for discussion and under review for Atmospheric Measurement Techniques (AMT).
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We describe accurate measurement of particle formation and growth in the CERN CLOUD chamber, using a suite of gas- and particle-phase instruments. The interconnected measurements establish high accuracy in key particle properties and critically important gas-phase sulfuric acid. This is a template for accurate calibration of similar experiments and thus accurate determination of aerosol nucleation and growth rates, which are an important source of uncertainty in climate science.
Mojtaba Bezaatpour, Miikka Dal Maso, and Matti Rissanen
EGUsphere, https://doi.org/10.5194/egusphere-2025-2564, https://doi.org/10.5194/egusphere-2025-2564, 2025
This preprint is open for discussion and under review for Geoscientific Model Development (GMD).
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We developed a computer program that can read chemical formulas and identify key features in thousands of organic compounds. This helps scientists estimate how easily these compounds evaporate, which is important for understanding air pollution and climate. We tested the program using real-world data and found it to be highly accurate. Our work makes it faster and easier to study the behavior of many complex chemicals in the atmosphere.
Dominika Pasik, Thomas Golin Almeida, Emelda Ahongshangbam, Siddharth Iyer, and Nanna Myllys
Atmos. Chem. Phys., 25, 4313–4331, https://doi.org/10.5194/acp-25-4313-2025, https://doi.org/10.5194/acp-25-4313-2025, 2025
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We used quantum chemistry methods to investigate the oxidation mechanisms of acyl peroxy radicals (APRs) with various monoterpenes. Our findings reveal unique oxidation pathways for different monoterpenes, leading to either chain-terminating products or highly reactive intermediates that can contribute to particle formation in the atmosphere. This research highlights APRs as potentially significant but underexplored atmospheric oxidants that may influence future approaches to modelling climate.
Federica Bortolussi, Hilda Sandström, Fariba Partovi, Joona Mikkilä, Patrick Rinke, and Matti Rissanen
Atmos. Chem. Phys., 25, 685–704, https://doi.org/10.5194/acp-25-685-2025, https://doi.org/10.5194/acp-25-685-2025, 2025
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Chemical ionization mass spectrometry (CIMS) is widely used in atmospheric chemistry studies. We still have a limited understanding of the complex functioning of the instrument; therefore, we applied machine learning to provide insights from CIMS analyses. We were able to predict both detection and signal intensity with a fair error, and we found out the most important structural fragments for negative ionization schemes (NH and OH) and positive ones (nitrogen-containing groups).
Henning Finkenzeller, Jyri Mikkilä, Cecilia Righi, Paxton Juuti, Mikko Sipilä, Matti Rissanen, Douglas Worsnop, Aleksei Shcherbinin, Nina Sarnela, and Juha Kangasluoma
Atmos. Meas. Tech., 17, 5989–6001, https://doi.org/10.5194/amt-17-5989-2024, https://doi.org/10.5194/amt-17-5989-2024, 2024
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Chemical ionisation mass spectrometry is used in the atmospheric sciences to measure trace gas concentrations. Neutral gases require charging in inlets before the mass-to-charge ratio of the resulting ions can be analysed. This study uses multiphysics modelling to investigate how the MION2 and Eisele type inlets work and shows the effect of tuning parameters and their current limitations. The findings are helpful for inlet users and are expected to aid in developing improved inlets.
Alex Rowell, James Brean, David C. S. Beddows, Zongbo Shi, Avinash Kumar, Matti Rissanen, Miikka Dal Maso, Peter Mettke, Kay Weinhold, Maik Merkel, and Roy M. Harrison
Atmos. Chem. Phys., 24, 10349–10361, https://doi.org/10.5194/acp-24-10349-2024, https://doi.org/10.5194/acp-24-10349-2024, 2024
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Ions enhance the formation and growth rates of new particles, affecting the Earth's radiation budget. Despite these effects, there is little published data exploring the sources of ions in the urban environment and their role in new particle formation (NPF). Here we show that natural ion sources dominate in urban environments, while traffic is a secondary source. Ions contribute up to 12.7 % of the formation rate of particles, indicating that they are important for forming urban PM.
Stéphanie Alage, Vincent Michoud, Sergio Harb, Bénédicte Picquet-Varrault, Manuela Cirtog, Avinash Kumar, Matti Rissanen, and Christopher Cantrell
Atmos. Meas. Tech., 17, 4709–4724, https://doi.org/10.5194/amt-17-4709-2024, https://doi.org/10.5194/amt-17-4709-2024, 2024
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Calibration exercises are essential for determining the accuracy of instruments. We performed calibrations on a NO3¯ ToFCIMS instrument to determine its sensitivity and linearity for detecting various organic compounds. Our findings revealed significant variability, over several orders of magnitude, in the calibration factors obtained. The results suggest that relying on a single calibration factor from H2SO4 for the quantification of all compounds detected by this technique is not appropriate.
Romain Salignat, Matti Rissanen, Siddharth Iyer, Jean-Luc Baray, Pierre Tulet, Jean-Marc Metzger, Jérôme Brioude, Karine Sellegri, and Clémence Rose
Atmos. Chem. Phys., 24, 3785–3812, https://doi.org/10.5194/acp-24-3785-2024, https://doi.org/10.5194/acp-24-3785-2024, 2024
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Using mass spectrometry data collected at the Maïdo Observatory (2160 m a.s.l., Réunion), we provide the first detailed analysis of molecular cluster chemical composition specifically in the marine free troposphere. The abundance of the identified species is related both to in situ meteorological parameters and air mass history, which also provide insight into their origin. Our work makes an important contribution to documenting the chemistry and physics of the marine free troposphere.
Xu-Cheng He, Jiali Shen, Siddharth Iyer, Paxton Juuti, Jiangyi Zhang, Mrisha Koirala, Mikko M. Kytökari, Douglas R. Worsnop, Matti Rissanen, Markku Kulmala, Norbert M. Maier, Jyri Mikkilä, Mikko Sipilä, and Juha Kangasluoma
Atmos. Meas. Tech., 16, 4461–4487, https://doi.org/10.5194/amt-16-4461-2023, https://doi.org/10.5194/amt-16-4461-2023, 2023
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In this study, the upgraded multi-scheme chemical ionisation inlet 2 is presented. Sulfuric acid, hypoiodous acid, iodine, sulfur dioxide, and hydroperoxyl radicals are calibrated, and the improved ion optics allow us to detect sulfuric acid and iodine-containing molecules at as low as a few parts per quadrillion by volume. Additionally, we confirm the reliable detection of iodic acid using both the nitrate and bromide chemical ionisation methods under atmospherically relevant conditions.
Lukas Pichelstorfer, Pontus Roldin, Matti Rissanen, Noora Hyttinen, Olga Garmash, Carlton Xavier, Putian Zhou, Petri Clusius, Benjamin Foreback, Thomas Golin Almeida, Chenjuan Deng, Metin Baykara, Theo Kurten, and Michael Boy
EGUsphere, https://doi.org/10.5194/egusphere-2023-1415, https://doi.org/10.5194/egusphere-2023-1415, 2023
Preprint archived
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Secondary organic aerosols (SOA) form effectively from gaseous precursors via a process called autoxidation. While key chemical reaction types seem to be known, no general description of autoxidation chemistry exists. In the present work, we present a method to create autoxidation chemistry schemes for any atmospherically relevant hydrocarbon. We exemplarily investigate benzene and its potential to form aerosols. We found that autoxidation, under some conditions, can dominate the SOA formation.
Melissa Meder, Otso Peräkylä, Jonathan G. Varelas, Jingyi Luo, Runlong Cai, Yanjun Zhang, Theo Kurtén, Matthieu Riva, Matti Rissanen, Franz M. Geiger, Regan J. Thomson, and Mikael Ehn
Atmos. Chem. Phys., 23, 4373–4390, https://doi.org/10.5194/acp-23-4373-2023, https://doi.org/10.5194/acp-23-4373-2023, 2023
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We discuss and show the viability of a method where multiple isotopically labelled precursors are used for probing the formation pathways of highly oxygenated organic molecules (HOMs) from the oxidation of the monoterpene a-pinene. HOMs are very important for secondary organic aerosol (SOA) formation in forested regions, and monoterpenes are the single largest source of SOA globally. The fast reactions forming HOMs have thus far remained elusive despite considerable efforts over the last decade.
Miska Olin, Magdalena Okuljar, Matti P. Rissanen, Joni Kalliokoski, Jiali Shen, Lubna Dada, Markus Lampimäki, Yusheng Wu, Annalea Lohila, Jonathan Duplissy, Mikko Sipilä, Tuukka Petäjä, Markku Kulmala, and Miikka Dal Maso
Atmos. Chem. Phys., 22, 8097–8115, https://doi.org/10.5194/acp-22-8097-2022, https://doi.org/10.5194/acp-22-8097-2022, 2022
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Atmospheric new particle formation is an important source of the total particle number concentration in the atmosphere. Several parameters for predicting new particle formation events have been suggested before, but the results have been inconclusive. This study proposes an another predicting parameter, related to a specific type of highly oxidized organic molecules, especially for similar locations to the measurement site in this study, which was a coastal agricultural site in Finland.
Dalrin Ampritta Amaladhasan, Claudia Heyn, Christopher R. Hoyle, Imad El Haddad, Miriam Elser, Simone M. Pieber, Jay G. Slowik, Antonio Amorim, Jonathan Duplissy, Sebastian Ehrhart, Vladimir Makhmutov, Ugo Molteni, Matti Rissanen, Yuri Stozhkov, Robert Wagner, Armin Hansel, Jasper Kirkby, Neil M. Donahue, Rainer Volkamer, Urs Baltensperger, Martin Gysel-Beer, and Andreas Zuend
Atmos. Chem. Phys., 22, 215–244, https://doi.org/10.5194/acp-22-215-2022, https://doi.org/10.5194/acp-22-215-2022, 2022
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We use a combination of models for gas-phase chemical reactions and equilibrium gas–particle partitioning of isoprene-derived secondary organic aerosols (SOAs) informed by dark ozonolysis experiments conducted in the CLOUD chamber. Our predictions cover high to low relative humidities (RHs) and quantify how SOA mass yields are enhanced at high RH as well as the impact of inorganic seeds of distinct hygroscopicities and acidities on the coupled partitioning of water and semi-volatile organics.
Mao Xiao, Christopher R. Hoyle, Lubna Dada, Dominik Stolzenburg, Andreas Kürten, Mingyi Wang, Houssni Lamkaddam, Olga Garmash, Bernhard Mentler, Ugo Molteni, Andrea Baccarini, Mario Simon, Xu-Cheng He, Katrianne Lehtipalo, Lauri R. Ahonen, Rima Baalbaki, Paulus S. Bauer, Lisa Beck, David Bell, Federico Bianchi, Sophia Brilke, Dexian Chen, Randall Chiu, António Dias, Jonathan Duplissy, Henning Finkenzeller, Hamish Gordon, Victoria Hofbauer, Changhyuk Kim, Theodore K. Koenig, Janne Lampilahti, Chuan Ping Lee, Zijun Li, Huajun Mai, Vladimir Makhmutov, Hanna E. Manninen, Ruby Marten, Serge Mathot, Roy L. Mauldin, Wei Nie, Antti Onnela, Eva Partoll, Tuukka Petäjä, Joschka Pfeifer, Veronika Pospisilova, Lauriane L. J. Quéléver, Matti Rissanen, Siegfried Schobesberger, Simone Schuchmann, Yuri Stozhkov, Christian Tauber, Yee Jun Tham, António Tomé, Miguel Vazquez-Pufleau, Andrea C. Wagner, Robert Wagner, Yonghong Wang, Lena Weitz, Daniela Wimmer, Yusheng Wu, Chao Yan, Penglin Ye, Qing Ye, Qiaozhi Zha, Xueqin Zhou, Antonio Amorim, Ken Carslaw, Joachim Curtius, Armin Hansel, Rainer Volkamer, Paul M. Winkler, Richard C. Flagan, Markku Kulmala, Douglas R. Worsnop, Jasper Kirkby, Neil M. Donahue, Urs Baltensperger, Imad El Haddad, and Josef Dommen
Atmos. Chem. Phys., 21, 14275–14291, https://doi.org/10.5194/acp-21-14275-2021, https://doi.org/10.5194/acp-21-14275-2021, 2021
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Experiments at CLOUD show that in polluted environments new particle formation (NPF) is largely driven by the formation of sulfuric acid–base clusters, stabilized by amines, high ammonia concentrations or lower temperatures. While oxidation products of aromatics can nucleate, they play a minor role in urban NPF. Our experiments span 4 orders of magnitude variation of observed NPF rates in ambient conditions. We provide a framework based on NPF and growth rates to interpret ambient observations.
Mingyi Wang, Xu-Cheng He, Henning Finkenzeller, Siddharth Iyer, Dexian Chen, Jiali Shen, Mario Simon, Victoria Hofbauer, Jasper Kirkby, Joachim Curtius, Norbert Maier, Theo Kurtén, Douglas R. Worsnop, Markku Kulmala, Matti Rissanen, Rainer Volkamer, Yee Jun Tham, Neil M. Donahue, and Mikko Sipilä
Atmos. Meas. Tech., 14, 4187–4202, https://doi.org/10.5194/amt-14-4187-2021, https://doi.org/10.5194/amt-14-4187-2021, 2021
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Atmospheric iodine species are often short-lived with low abundance and have thus been challenging to measure. We show that the bromide chemical ionization mass spectrometry, compatible with both the atmospheric pressure and reduced pressure interfaces, can simultaneously detect various gas-phase iodine species. Combining calibration experiments and quantum chemical calculations, we quantify detection sensitivities to HOI, HIO3, I2, and H2SO4, giving detection limits down to < 106 molec. cm-3.
Meri Räty, Otso Peräkylä, Matthieu Riva, Lauriane Quéléver, Olga Garmash, Matti Rissanen, and Mikael Ehn
Atmos. Chem. Phys., 21, 7357–7372, https://doi.org/10.5194/acp-21-7357-2021, https://doi.org/10.5194/acp-21-7357-2021, 2021
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Cyclohexene resembles certain relatively complex compounds in the atmosphere that through oxidation produce vapours that take part in aerosol formation. We studied the highly oxygenated organic molecules (HOMs) formed in cyclohexene ozonolysis, the relationship between their chemical composition and their tendency to condense onto seed aerosol, as well as the effect of NOx pollutants on their signals. Two existing models were also tested for their ability to predict the volatility of the HOMs.
Clémence Rose, Matti P. Rissanen, Siddharth Iyer, Jonathan Duplissy, Chao Yan, John B. Nowak, Aurélie Colomb, Régis Dupuy, Xu-Cheng He, Janne Lampilahti, Yee Jun Tham, Daniela Wimmer, Jean-Marc Metzger, Pierre Tulet, Jérôme Brioude, Céline Planche, Markku Kulmala, and Karine Sellegri
Atmos. Chem. Phys., 21, 4541–4560, https://doi.org/10.5194/acp-21-4541-2021, https://doi.org/10.5194/acp-21-4541-2021, 2021
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Sulfuric acid (H2SO4) is commonly accepted as a key precursor for atmospheric new particle formation. However, direct measurements of [H2SO4] remain challenging, motivating the development of proxies. Using data collected in two different volcanic plumes, we show, under these specific conditions, the good performance of a proxy from the literature and also highlight the benefit of the newly developed proxies for the prediction of the highest [H2SO4] values.
Martin Heinritzi, Lubna Dada, Mario Simon, Dominik Stolzenburg, Andrea C. Wagner, Lukas Fischer, Lauri R. Ahonen, Stavros Amanatidis, Rima Baalbaki, Andrea Baccarini, Paulus S. Bauer, Bernhard Baumgartner, Federico Bianchi, Sophia Brilke, Dexian Chen, Randall Chiu, Antonio Dias, Josef Dommen, Jonathan Duplissy, Henning Finkenzeller, Carla Frege, Claudia Fuchs, Olga Garmash, Hamish Gordon, Manuel Granzin, Imad El Haddad, Xucheng He, Johanna Helm, Victoria Hofbauer, Christopher R. Hoyle, Juha Kangasluoma, Timo Keber, Changhyuk Kim, Andreas Kürten, Houssni Lamkaddam, Tiia M. Laurila, Janne Lampilahti, Chuan Ping Lee, Katrianne Lehtipalo, Markus Leiminger, Huajun Mai, Vladimir Makhmutov, Hanna Elina Manninen, Ruby Marten, Serge Mathot, Roy Lee Mauldin, Bernhard Mentler, Ugo Molteni, Tatjana Müller, Wei Nie, Tuomo Nieminen, Antti Onnela, Eva Partoll, Monica Passananti, Tuukka Petäjä, Joschka Pfeifer, Veronika Pospisilova, Lauriane L. J. Quéléver, Matti P. Rissanen, Clémence Rose, Siegfried Schobesberger, Wiebke Scholz, Kay Scholze, Mikko Sipilä, Gerhard Steiner, Yuri Stozhkov, Christian Tauber, Yee Jun Tham, Miguel Vazquez-Pufleau, Annele Virtanen, Alexander L. Vogel, Rainer Volkamer, Robert Wagner, Mingyi Wang, Lena Weitz, Daniela Wimmer, Mao Xiao, Chao Yan, Penglin Ye, Qiaozhi Zha, Xueqin Zhou, Antonio Amorim, Urs Baltensperger, Armin Hansel, Markku Kulmala, António Tomé, Paul M. Winkler, Douglas R. Worsnop, Neil M. Donahue, Jasper Kirkby, and Joachim Curtius
Atmos. Chem. Phys., 20, 11809–11821, https://doi.org/10.5194/acp-20-11809-2020, https://doi.org/10.5194/acp-20-11809-2020, 2020
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With experiments performed at CLOUD, we show how isoprene interferes in monoterpene oxidation via RO2 termination at atmospherically relevant concentrations. This interference shifts the distribution of highly oxygenated organic molecules (HOMs) away from C20 class dimers towards C15 class dimers, which subsequently reduces both biogenic nucleation and early growth rates. Our results may help to understand the absence of new-particle formation in isoprene-rich environments.
Mario Simon, Lubna Dada, Martin Heinritzi, Wiebke Scholz, Dominik Stolzenburg, Lukas Fischer, Andrea C. Wagner, Andreas Kürten, Birte Rörup, Xu-Cheng He, João Almeida, Rima Baalbaki, Andrea Baccarini, Paulus S. Bauer, Lisa Beck, Anton Bergen, Federico Bianchi, Steffen Bräkling, Sophia Brilke, Lucia Caudillo, Dexian Chen, Biwu Chu, António Dias, Danielle C. Draper, Jonathan Duplissy, Imad El-Haddad, Henning Finkenzeller, Carla Frege, Loic Gonzalez-Carracedo, Hamish Gordon, Manuel Granzin, Jani Hakala, Victoria Hofbauer, Christopher R. Hoyle, Changhyuk Kim, Weimeng Kong, Houssni Lamkaddam, Chuan P. Lee, Katrianne Lehtipalo, Markus Leiminger, Huajun Mai, Hanna E. Manninen, Guillaume Marie, Ruby Marten, Bernhard Mentler, Ugo Molteni, Leonid Nichman, Wei Nie, Andrea Ojdanic, Antti Onnela, Eva Partoll, Tuukka Petäjä, Joschka Pfeifer, Maxim Philippov, Lauriane L. J. Quéléver, Ananth Ranjithkumar, Matti P. Rissanen, Simon Schallhart, Siegfried Schobesberger, Simone Schuchmann, Jiali Shen, Mikko Sipilä, Gerhard Steiner, Yuri Stozhkov, Christian Tauber, Yee J. Tham, António R. Tomé, Miguel Vazquez-Pufleau, Alexander L. Vogel, Robert Wagner, Mingyi Wang, Dongyu S. Wang, Yonghong Wang, Stefan K. Weber, Yusheng Wu, Mao Xiao, Chao Yan, Penglin Ye, Qing Ye, Marcel Zauner-Wieczorek, Xueqin Zhou, Urs Baltensperger, Josef Dommen, Richard C. Flagan, Armin Hansel, Markku Kulmala, Rainer Volkamer, Paul M. Winkler, Douglas R. Worsnop, Neil M. Donahue, Jasper Kirkby, and Joachim Curtius
Atmos. Chem. Phys., 20, 9183–9207, https://doi.org/10.5194/acp-20-9183-2020, https://doi.org/10.5194/acp-20-9183-2020, 2020
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Highly oxygenated organic compounds (HOMs) have been identified as key vapors involved in atmospheric new-particle formation (NPF). The molecular distribution, HOM yield, and NPF from α-pinene oxidation experiments were measured at the CLOUD chamber over a wide tropospheric-temperature range. This study shows on a molecular scale that despite the sharp reduction in HOM yield at lower temperatures, the reduced volatility counteracts this effect and leads to an overall increase in the NPF rate.
Dominik Stolzenburg, Mario Simon, Ananth Ranjithkumar, Andreas Kürten, Katrianne Lehtipalo, Hamish Gordon, Sebastian Ehrhart, Henning Finkenzeller, Lukas Pichelstorfer, Tuomo Nieminen, Xu-Cheng He, Sophia Brilke, Mao Xiao, António Amorim, Rima Baalbaki, Andrea Baccarini, Lisa Beck, Steffen Bräkling, Lucía Caudillo Murillo, Dexian Chen, Biwu Chu, Lubna Dada, António Dias, Josef Dommen, Jonathan Duplissy, Imad El Haddad, Lukas Fischer, Loic Gonzalez Carracedo, Martin Heinritzi, Changhyuk Kim, Theodore K. Koenig, Weimeng Kong, Houssni Lamkaddam, Chuan Ping Lee, Markus Leiminger, Zijun Li, Vladimir Makhmutov, Hanna E. Manninen, Guillaume Marie, Ruby Marten, Tatjana Müller, Wei Nie, Eva Partoll, Tuukka Petäjä, Joschka Pfeifer, Maxim Philippov, Matti P. Rissanen, Birte Rörup, Siegfried Schobesberger, Simone Schuchmann, Jiali Shen, Mikko Sipilä, Gerhard Steiner, Yuri Stozhkov, Christian Tauber, Yee Jun Tham, António Tomé, Miguel Vazquez-Pufleau, Andrea C. Wagner, Mingyi Wang, Yonghong Wang, Stefan K. Weber, Daniela Wimmer, Peter J. Wlasits, Yusheng Wu, Qing Ye, Marcel Zauner-Wieczorek, Urs Baltensperger, Kenneth S. Carslaw, Joachim Curtius, Neil M. Donahue, Richard C. Flagan, Armin Hansel, Markku Kulmala, Jos Lelieveld, Rainer Volkamer, Jasper Kirkby, and Paul M. Winkler
Atmos. Chem. Phys., 20, 7359–7372, https://doi.org/10.5194/acp-20-7359-2020, https://doi.org/10.5194/acp-20-7359-2020, 2020
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Sulfuric acid is a major atmospheric vapour for aerosol formation. If new particles grow fast enough, they can act as cloud droplet seeds or affect air quality. In a controlled laboratory set-up, we demonstrate that van der Waals forces enhance growth from sulfuric acid. We disentangle the effects of ammonia, ions and particle hydration, presenting a complete picture of sulfuric acid growth from molecular clusters onwards. In a climate model, we show its influence on the global aerosol budget.
Dean Chen, Putian Zhou, Tuomo Nieminen, Pontus Roldin, Ximeng Qi, Petri Clusius, Carlton Xavier, Lukas Pichelstorfer, Markku Kulmala, Pekka Rantala, Juho Aalto, Nina Sarnela, Pasi Kolari, Petri Keronen, Matti P. Rissanen, Metin Baykara, and Michael Boy
Atmos. Chem. Phys. Discuss., https://doi.org/10.5194/acp-2020-128, https://doi.org/10.5194/acp-2020-128, 2020
Preprint withdrawn
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Atmospheric oxidants OH, O3 and NO3 dominate the atmospheric oxidation capacity, and sulfuric acid (H2SO4) is considered as a main driver for new particle formation events. We studied how the trends of these atmospheric oxidants and H2SO4 changed in southern Finland during the past 12 years and discussed how these trends related to decreasing emissions of air pollutants in Europe. Our results showed that OH increased by 1.56 % yr−1 at daytime and NO3 decreased by 3.92 % yr−1 at nighttime.
Olga Garmash, Matti P. Rissanen, Iida Pullinen, Sebastian Schmitt, Oskari Kausiala, Ralf Tillmann, Defeng Zhao, Carl Percival, Thomas J. Bannan, Michael Priestley, Åsa M. Hallquist, Einhard Kleist, Astrid Kiendler-Scharr, Mattias Hallquist, Torsten Berndt, Gordon McFiggans, Jürgen Wildt, Thomas F. Mentel, and Mikael Ehn
Atmos. Chem. Phys., 20, 515–537, https://doi.org/10.5194/acp-20-515-2020, https://doi.org/10.5194/acp-20-515-2020, 2020
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Highly oxygenated organic molecules (HOMs) facilitate aerosol formation in the atmosphere. Using NO3− chemical ionization mass spectrometry we investigated HOM composition and yield in oxidation of aromatic compounds at different reactant concentrations, in the presence of NOx and seed aerosol. Higher OH concentrations increased HOM yield, suggesting multiple oxidation steps, and affected HOM composition, potentially explaining in part discrepancies in published secondary organic aerosol yields.
Matti P. Rissanen, Jyri Mikkilä, Siddharth Iyer, and Jani Hakala
Atmos. Meas. Tech., 12, 6635–6646, https://doi.org/10.5194/amt-12-6635-2019, https://doi.org/10.5194/amt-12-6635-2019, 2019
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A novel chemical ionization methodology for rapid gas–phase environmental monitoring is presented. The usefulness of the new inlet design is demonstrated by measuring various aerosol precursor compounds that are present at very low concentrations by using two consecutive ionization schemes. This new inlet enables the detection of a wide range of compounds of interest with a minimum of effort and at a fast repetition rate.
Ximeng Qi, Aijun Ding, Pontus Roldin, Zhengning Xu, Putian Zhou, Nina Sarnela, Wei Nie, Xin Huang, Anton Rusanen, Mikael Ehn, Matti P. Rissanen, Tuukka Petäjä, Markku Kulmala, and Michael Boy
Atmos. Chem. Phys., 18, 11779–11791, https://doi.org/10.5194/acp-18-11779-2018, https://doi.org/10.5194/acp-18-11779-2018, 2018
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In this study we simulate the HOM concentrations and discuss their roles in NPF at a remote boreal forest site in Finland and a suburban site in eastern China. We found that sulfuric acid and HOM organonitrate concentrations in the gas phase are significantly higher but other HOM monomers and dimers from monoterpene oxidation are lower in eastern China. This study highlights the need for molecular-scale measurements in improving the understanding of NPF mechanisms in polluted areas.
Nina Sarnela, Tuija Jokinen, Jonathan Duplissy, Chao Yan, Tuomo Nieminen, Mikael Ehn, Siegfried Schobesberger, Martin Heinritzi, Sebastian Ehrhart, Katrianne Lehtipalo, Jasmin Tröstl, Mario Simon, Andreas Kürten, Markus Leiminger, Michael J. Lawler, Matti P. Rissanen, Federico Bianchi, Arnaud P. Praplan, Jani Hakala, Antonio Amorim, Marc Gonin, Armin Hansel, Jasper Kirkby, Josef Dommen, Joachim Curtius, James N. Smith, Tuukka Petäjä, Douglas R. Worsnop, Markku Kulmala, Neil M. Donahue, and Mikko Sipilä
Atmos. Chem. Phys., 18, 2363–2380, https://doi.org/10.5194/acp-18-2363-2018, https://doi.org/10.5194/acp-18-2363-2018, 2018
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Atmospheric trace gases can form small molecular clusters, which can grow to larger sizes through the condensation of vapours. This process is called new particle formation. In this paper we studied the formation of sulfuric acid and highly oxygenated molecules, the key compounds in atmospheric new particle formation, in chamber experiments and introduced a way to simulate these ozonolysis products of α-pinene in a simple manner.
Andreas Kürten, Chenxi Li, Federico Bianchi, Joachim Curtius, António Dias, Neil M. Donahue, Jonathan Duplissy, Richard C. Flagan, Jani Hakala, Tuija Jokinen, Jasper Kirkby, Markku Kulmala, Ari Laaksonen, Katrianne Lehtipalo, Vladimir Makhmutov, Antti Onnela, Matti P. Rissanen, Mario Simon, Mikko Sipilä, Yuri Stozhkov, Jasmin Tröstl, Penglin Ye, and Peter H. McMurry
Atmos. Chem. Phys., 18, 845–863, https://doi.org/10.5194/acp-18-845-2018, https://doi.org/10.5194/acp-18-845-2018, 2018
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A recent laboratory study (CLOUD) showed that new particles nucleate efficiently from sulfuric acid and dimethylamine (DMA). The reanalysis of previously published data reveals that the nucleation rates are even faster than previously assumed, i.e., nucleation can proceed at rates that are compatible with collision-controlled new particle formation for atmospheric conditions. This indicates that sulfuric acid–DMA nucleation is likely an important source of particles in the boundary layer.
Carla Frege, Ismael K. Ortega, Matti P. Rissanen, Arnaud P. Praplan, Gerhard Steiner, Martin Heinritzi, Lauri Ahonen, António Amorim, Anne-Kathrin Bernhammer, Federico Bianchi, Sophia Brilke, Martin Breitenlechner, Lubna Dada, António Dias, Jonathan Duplissy, Sebastian Ehrhart, Imad El-Haddad, Lukas Fischer, Claudia Fuchs, Olga Garmash, Marc Gonin, Armin Hansel, Christopher R. Hoyle, Tuija Jokinen, Heikki Junninen, Jasper Kirkby, Andreas Kürten, Katrianne Lehtipalo, Markus Leiminger, Roy Lee Mauldin, Ugo Molteni, Leonid Nichman, Tuukka Petäjä, Nina Sarnela, Siegfried Schobesberger, Mario Simon, Mikko Sipilä, Dominik Stolzenburg, António Tomé, Alexander L. Vogel, Andrea C. Wagner, Robert Wagner, Mao Xiao, Chao Yan, Penglin Ye, Joachim Curtius, Neil M. Donahue, Richard C. Flagan, Markku Kulmala, Douglas R. Worsnop, Paul M. Winkler, Josef Dommen, and Urs Baltensperger
Atmos. Chem. Phys., 18, 65–79, https://doi.org/10.5194/acp-18-65-2018, https://doi.org/10.5194/acp-18-65-2018, 2018
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It was recently shown that biogenic highly oxygenated molecules (HOMs) form particles in the absence of sulfuric acid and ions enhance the nucleation rate. Here we compare the molecular composition of positive and negative HOM clusters at 25, 5 and −25 °C. At lower temperatures the HOM average oxygen-to-carbon ratio decreases indicating a reduction in the rate of autoxidation due to rather high activation energy. The experimental findings are supported by quantum chemical calculations.
Xuemeng Chen, Lauriane L. J. Quéléver, Pak L. Fung, Jutta Kesti, Matti P. Rissanen, Jaana Bäck, Petri Keronen, Heikki Junninen, Tuukka Petäjä, Veli-Matti Kerminen, and Markku Kulmala
Atmos. Chem. Phys., 18, 49–63, https://doi.org/10.5194/acp-18-49-2018, https://doi.org/10.5194/acp-18-49-2018, 2018
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We analysed a 20-year-long dataset collected in a Finnish boreal forest at SMEAR II station to investigate the frequency and strength of ozone depletion events. We could identify a number of ozone depletion events that lasted for more than 3 h, mainly in the autumn and winter months. Their occurrence was likely related to the formation of a low mixing layer under the conditions of low temperatures, low wind speeds, high relative humidities and limited intensity of solar radiation.
Robert Wagner, Chao Yan, Katrianne Lehtipalo, Jonathan Duplissy, Tuomo Nieminen, Juha Kangasluoma, Lauri R. Ahonen, Lubna Dada, Jenni Kontkanen, Hanna E. Manninen, Antonio Dias, Antonio Amorim, Paulus S. Bauer, Anton Bergen, Anne-Kathrin Bernhammer, Federico Bianchi, Sophia Brilke, Stephany Buenrostro Mazon, Xuemeng Chen, Danielle C. Draper, Lukas Fischer, Carla Frege, Claudia Fuchs, Olga Garmash, Hamish Gordon, Jani Hakala, Liine Heikkinen, Martin Heinritzi, Victoria Hofbauer, Christopher R. Hoyle, Jasper Kirkby, Andreas Kürten, Alexander N. Kvashnin, Tiia Laurila, Michael J. Lawler, Huajun Mai, Vladimir Makhmutov, Roy L. Mauldin III, Ugo Molteni, Leonid Nichman, Wei Nie, Andrea Ojdanic, Antti Onnela, Felix Piel, Lauriane L. J. Quéléver, Matti P. Rissanen, Nina Sarnela, Simon Schallhart, Kamalika Sengupta, Mario Simon, Dominik Stolzenburg, Yuri Stozhkov, Jasmin Tröstl, Yrjö Viisanen, Alexander L. Vogel, Andrea C. Wagner, Mao Xiao, Penglin Ye, Urs Baltensperger, Joachim Curtius, Neil M. Donahue, Richard C. Flagan, Martin Gallagher, Armin Hansel, James N. Smith, António Tomé, Paul M. Winkler, Douglas Worsnop, Mikael Ehn, Mikko Sipilä, Veli-Matti Kerminen, Tuukka Petäjä, and Markku Kulmala
Atmos. Chem. Phys., 17, 15181–15197, https://doi.org/10.5194/acp-17-15181-2017, https://doi.org/10.5194/acp-17-15181-2017, 2017
Putian Zhou, Laurens Ganzeveld, Ditte Taipale, Üllar Rannik, Pekka Rantala, Matti Petteri Rissanen, Dean Chen, and Michael Boy
Atmos. Chem. Phys., 17, 14309–14332, https://doi.org/10.5194/acp-17-14309-2017, https://doi.org/10.5194/acp-17-14309-2017, 2017
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In boreal forest, there is a large number of gaseous organic compounds called biogenic volatile organic compounds (BVOCs). Within the canopy, they can be emitted from vegetation and soil, react with each other and other gases, be transported in the air, and be removed from vegetation and soil surfaces. We applied a numerical model to simulate these processes and found that these BVOCs can be divided into five categories according to the significance of their sources and sinks.
Federico Bianchi, Olga Garmash, Xucheng He, Chao Yan, Siddharth Iyer, Ida Rosendahl, Zhengning Xu, Matti P. Rissanen, Matthieu Riva, Risto Taipale, Nina Sarnela, Tuukka Petäjä, Douglas R. Worsnop, Markku Kulmala, Mikael Ehn, and Heikki Junninen
Atmos. Chem. Phys., 17, 13819–13831, https://doi.org/10.5194/acp-17-13819-2017, https://doi.org/10.5194/acp-17-13819-2017, 2017
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Naturally charged highly oxidised molecules (HOMs) were characterized using advanced mass spectrometers. Two different classes of compounds, clustered with the nitrate and bisulfate ions, were identified: HOMs containing only carbon, hydrogen and oxygen and nitrogen-containing HOMs or organonitrates (ONs). They exhibit strong diurnal variations where HOMs peak during night and ONs during day. Finally, large clusters containing up to 40 carbon atoms (four oxidized
α-pinene units) were observed.
Emilie Öström, Zhou Putian, Guy Schurgers, Mikhail Mishurov, Niku Kivekäs, Heikki Lihavainen, Mikael Ehn, Matti P. Rissanen, Theo Kurtén, Michael Boy, Erik Swietlicki, and Pontus Roldin
Atmos. Chem. Phys., 17, 8887–8901, https://doi.org/10.5194/acp-17-8887-2017, https://doi.org/10.5194/acp-17-8887-2017, 2017
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We used a model to study how biogenic volatile organic compounds (BVOCs) emitted from the boreal forest contribute to the formation and growth of particles in the atmosphere. Some of these particles are important climate forcers, acting as seeds for cloud droplet fomation. We implemented a new gas chemistry mechanism that describes how the BVOCs are oxidized and form low-volatility highly oxidized organic molecules. With the new mechanism we are able to accurately predict the particle growth.
Michael J. Lawler, Paul M. Winkler, Jaeseok Kim, Lars Ahlm, Jasmin Tröstl, Arnaud P. Praplan, Siegfried Schobesberger, Andreas Kürten, Jasper Kirkby, Federico Bianchi, Jonathan Duplissy, Armin Hansel, Tuija Jokinen, Helmi Keskinen, Katrianne Lehtipalo, Markus Leiminger, Tuukka Petäjä, Matti Rissanen, Linda Rondo, Mario Simon, Mikko Sipilä, Christina Williamson, Daniela Wimmer, Ilona Riipinen, Annele Virtanen, and James N. Smith
Atmos. Chem. Phys., 16, 13601–13618, https://doi.org/10.5194/acp-16-13601-2016, https://doi.org/10.5194/acp-16-13601-2016, 2016
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We present chemical observations of newly formed particles as small as ~ 10 nm from new particle formation experiments using sulfuric acid, dimethylamine, ammonia, and water vapor as gas phase reactants. The nanoparticles were more acidic than expected based on thermodynamic expectations, particularly at the smallest measured sizes. The results suggest rapid surface conversion of SO2 to sulfate and show a marked composition change between 10 and 15 nm, possibly indicating a phase change.
Chao Yan, Wei Nie, Mikko Äijälä, Matti P. Rissanen, Manjula R. Canagaratna, Paola Massoli, Heikki Junninen, Tuija Jokinen, Nina Sarnela, Silja A. K. Häme, Siegfried Schobesberger, Francesco Canonaco, Lei Yao, André S. H. Prévôt, Tuukka Petäjä, Markku Kulmala, Mikko Sipilä, Douglas R. Worsnop, and Mikael Ehn
Atmos. Chem. Phys., 16, 12715–12731, https://doi.org/10.5194/acp-16-12715-2016, https://doi.org/10.5194/acp-16-12715-2016, 2016
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Highly oxidized multifunctional compounds (HOMs) are known to have a significant contribution to secondary aerosol formation, yet their dominating formation pathways remain unclear in the atmosphere. We apply positive matrix factorization (PMF) on HOM data, and successfully retrieve factors representing different formation pathways. The results improve our understanding of HOM formation, and provide new perspectives on using PMF to study the variation of short-lived specie.
Felipe D. Lopez-Hilfiker, Siddarth Iyer, Claudia Mohr, Ben H. Lee, Emma L. D'Ambro, Theo Kurtén, and Joel A. Thornton
Atmos. Meas. Tech., 9, 1505–1512, https://doi.org/10.5194/amt-9-1505-2016, https://doi.org/10.5194/amt-9-1505-2016, 2016
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We present the maximum sensitivity of a TOF-CIMS using the collision limit and iodide adducts. We also present an ion adduct declustering scanning procedure which determines the effective binding energies of the detected ion adducts and therefore their approximate sensitivity. The combination of declustering scanning and the collision limit provides an approximate calibration for many compounds in the mass spectrum which would otherwise be impossible to obtain by traditional methods.
J. Kim, L. Ahlm, T. Yli-Juuti, M. Lawler, H. Keskinen, J. Tröstl, S. Schobesberger, J. Duplissy, A. Amorim, F. Bianchi, N. M. Donahue, R. C. Flagan, J. Hakala, M. Heinritzi, T. Jokinen, A. Kürten, A. Laaksonen, K. Lehtipalo, P. Miettinen, T. Petäjä, M. P. Rissanen, L. Rondo, K. Sengupta, M. Simon, A. Tomé, C. Williamson, D. Wimmer, P. M. Winkler, S. Ehrhart, P. Ye, J. Kirkby, J. Curtius, U. Baltensperger, M. Kulmala, K. E. J. Lehtinen, J. N. Smith, I. Riipinen, and A. Virtanen
Atmos. Chem. Phys., 16, 293–304, https://doi.org/10.5194/acp-16-293-2016, https://doi.org/10.5194/acp-16-293-2016, 2016
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The hygroscopicity of nucleated nanoparticles was measured in the presence of sulfuric acid, sulfuric acid-dimethylamine, and sulfuric acid-organics derived from α-pinene oxidation during CLOUD7 at CERN in 2012. The hygroscopicity parameter κ decreased with increasing particle size, indicating decreasing acidity of particles.
R. L. Mauldin III, M. P. Rissanen, T. Petäjä, and M. Kulmala
Atmos. Meas. Tech. Discuss., https://doi.org/10.5194/amt-2015-398, https://doi.org/10.5194/amt-2015-398, 2016
Revised manuscript not accepted
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The manuscript describes a novel instrument for the measurement of OH, HO2+RO2, and other atmospheric species. The instrument described combines the chemical ionization techniques of nitrate CIMS, OH conversion to H2SO4, HO2+RO2 conversion to H2SO4, and high resolution time of flight mass spectroscopy into one system. By using one instrument to obtain spectra it is possible to compare spectra from the different modes and gain further chemical information towards peak identification.
M. Sipilä, N. Sarnela, T. Jokinen, H. Junninen, J. Hakala, M. P. Rissanen, A. Praplan, M. Simon, A. Kürten, F. Bianchi, J. Dommen, J. Curtius, T. Petäjä, and D. R. Worsnop
Atmos. Meas. Tech., 8, 4001–4011, https://doi.org/10.5194/amt-8-4001-2015, https://doi.org/10.5194/amt-8-4001-2015, 2015
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Atmospheric concentrations of amines are poorly known mainly due to challenges related to their reliable high-sensitivity detection. We have created a method and instrument that is capable for detecting amines with lowest limit of detection of around 0.01 parts per trillion. Application of the instrument in the field study indicates that concentrations of dimethyl amine in a boreal forest site are below 0.03ppt, not enough to account for the observed new particle formation rates.
T. F. Mentel, M. Springer, M. Ehn, E. Kleist, I. Pullinen, T. Kurtén, M. Rissanen, A. Wahner, and J. Wildt
Atmos. Chem. Phys., 15, 6745–6765, https://doi.org/10.5194/acp-15-6745-2015, https://doi.org/10.5194/acp-15-6745-2015, 2015
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We studied a series of cycloalkenes and methyl-substituted alkenes in order to elucidate the structural pre-requisites and chemical pathways to the recently discovered class of highly oxidized molecules ELVOC (Ehn et al., Nature, 2014). ELVOC may totally change the view on (parts of) the mechanism of SOA formation. We present results which support recent observations of H shifts from C-H to peroxy radicals, highlighting the pivotal role of peroxyradicals in organic atmospheric chemistry.
A. P. Praplan, S. Schobesberger, F. Bianchi, M. P. Rissanen, M. Ehn, T. Jokinen, H. Junninen, A. Adamov, A. Amorim, J. Dommen, J. Duplissy, J. Hakala, A. Hansel, M. Heinritzi, J. Kangasluoma, J. Kirkby, M. Krapf, A. Kürten, K. Lehtipalo, F. Riccobono, L. Rondo, N. Sarnela, M. Simon, A. Tomé, J. Tröstl, P. M. Winkler, C. Williamson, P. Ye, J. Curtius, U. Baltensperger, N. M. Donahue, M. Kulmala, and D. R. Worsnop
Atmos. Chem. Phys., 15, 4145–4159, https://doi.org/10.5194/acp-15-4145-2015, https://doi.org/10.5194/acp-15-4145-2015, 2015
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Our study shows, based on data from three atmospheric pressure interface time-of-flight mass spectrometers measuring in parallel charged and neutral molecules and molecular clusters, how oxidised organic compounds bind to inorganic ions (e.g. bisulfate, nitrate, ammonium). This ionisation is selective for compounds with lower molar mass due to their limited amount and variety of functional groups. We also found that extremely low volatile organic compounds (ELVOCs) can be formed immediately.
M. Sipilä, T. Jokinen, T. Berndt, S. Richters, R. Makkonen, N. M. Donahue, R. L. Mauldin III, T. Kurtén, P. Paasonen, N. Sarnela, M. Ehn, H. Junninen, M. P. Rissanen, J. Thornton, F. Stratmann, H. Herrmann, D. R. Worsnop, M. Kulmala, V.-M. Kerminen, and T. Petäjä
Atmos. Chem. Phys., 14, 12143–12153, https://doi.org/10.5194/acp-14-12143-2014, https://doi.org/10.5194/acp-14-12143-2014, 2014
J. Kangasluoma, C. Kuang, D. Wimmer, M. P. Rissanen, K. Lehtipalo, M. Ehn, D. R. Worsnop, J. Wang, M. Kulmala, and T. Petäjä
Atmos. Meas. Tech., 7, 689–700, https://doi.org/10.5194/amt-7-689-2014, https://doi.org/10.5194/amt-7-689-2014, 2014
Related subject area
Subject: Gases | Research Activity: Laboratory Studies | Altitude Range: Troposphere | Science Focus: Chemistry (chemical composition and reactions)
Measurement report: Insight into greenhouse gas emission characteristics of light-duty vehicles in China in the context of technological innovation
Enhancing SO3 hydrolysis and nucleation: the role of formic sulfuric anhydride
Reactivity study of 3,3-dimethylbutanal and 3,3-dimethylbutanone: kinetics, reaction products, mechanisms, and atmospheric implications
Spatially separate production of hydrogen oxides and nitric oxide in lightning
Gas-phase observations of accretion products from stabilized Criegee intermediates in terpene ozonolysis with two dicarboxylic acids
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
Atmospheric breakdown kinetics and air quality impact of potential “green” solvents the oxymethylene ethers OME3 and OME4
Chemical characterization of organic vapors from wood, straw, cow dung, and coal burning
Atmospheric Mercury: Recent advances in theoretical, computational, experimental, observational and isotopic understanding to decipher its complex redox transformations in the upper and lower atmosphere and interaction with Earth surface reservoirs
Quantifying primary oxidation products in the OH-initiated reaction of benzyl alcohol
Opinion: Improved scientific discourse and quality assurance by interactive open access publishing with community-based multi-stage open peer review in an open science landscape
Evaluating Nitrogen Oxide and α-pinene Oxidation Chemistry: Insights from Oxygen and Nitrogen Stable Isotopes
Temperature-dependent rate coefficients for the reactions of OH radicals with selected alkanes, aromatic compounds, and monoterpenes
Exploring HONO production from particulate nitrate photolysis in representative regions of China: characteristics, influencing factors, and environmental implications
Formation of reactive nitrogen species promoted by iron ions through the photochemistry of a neonicotinoid insecticide
Rate coefficients for the reactions of OH radicals with C3–C11 alkanes determined by the relative-rate technique
Formation and temperature dependence of highly oxygenated organic molecules (HOMs) from Δ3-carene ozonolysis
Mechanistic insight into the kinetic fragmentation of norpinonic acid in the gas phase: an experimental and density functional theory (DFT) study
Secondary reactions of aromatics-derived oxygenated organic molecules lead to plentiful highly oxygenated organic molecules within an intraday OH exposure
Impact of HO2∕RO2 ratio on highly oxygenated α-pinene photooxidation products and secondary organic aerosol formation potential
Negligible temperature dependence of the ozone–iodide reaction and implications for oceanic emissions of iodine
Extension, development, and evaluation of the representation of the OH-initiated dimethyl sulfide (DMS) oxidation mechanism in the Master Chemical Mechanism (MCM) v3.3.1 framework
On the potential use of highly oxygenated organic molecules (HOMs) as indicators for ozone formation sensitivity
Oxygenated organic molecules produced by low-NOx photooxidation of aromatic compounds: contributions to secondary organic aerosol and steric hindrance
Impact of temperature on the role of Criegee intermediates and peroxy radicals in dimer formation from β-pinene ozonolysis
Atmospheric impact of 2-methylpentanal emissions: kinetics, photochemistry, and formation of secondary pollutants
Technical note: Gas-phase nitrate radical generation via irradiation of aerated ceric ammonium nitrate mixtures
Direct probing of acylperoxy radicals during ozonolysis of α-pinene: constraints on radical chemistry and production of highly oxygenated organic molecules
Atmospheric photooxidation and ozonolysis of sabinene: reaction rate coefficients, product yields, and chemical budget of radicals
Compilation of Henry's law constants (version 5.0.0) for water as solvent
Measurement report: Carbonyl sulfide production during dimethyl sulfide oxidation in the atmospheric simulation chamber SAPHIR
Measuring and modeling investigation of the net photochemical ozone production rate via an improved dual-channel reaction chamber technique
Evolution of organic carbon in the laboratory oxidation of biomass-burning emissions
Atmospheric oxidation of new “green” solvents – Part 2: methyl pivalate and pinacolone
On the formation of highly oxidized pollutants by autoxidation of terpenes under low-temperature-combustion conditions: the case of limonene and α-pinene
Selective deuteration as a tool for resolving autoxidation mechanisms in α-pinene ozonolysis
Comparison of isoprene chemical mechanisms under atmospheric night-time conditions in chamber experiments: evidence of hydroperoxy aldehydes and epoxy products from NO3 oxidation
Measurement of Henry's law and liquid-phase loss rate constants of peroxypropionic nitric anhydride (PPN) in deionized water and in n-octanol
Product distribution, kinetics, and aerosol formation from the OH oxidation of dimethyl sulfide under different RO2 regimes
Atmospheric breakdown chemistry of the new “green” solvent 2,2,5,5-tetramethyloxolane via gas-phase reactions with OH and Cl radicals
Impact of cooking style and oil on semi-volatile and intermediate volatility organic compound emissions from Chinese domestic cooking
Observations of gas-phase products from the nitrate-radical-initiated oxidation of four monoterpenes
Investigation of the limonene photooxidation by OH at different NO concentrations in the atmospheric simulation chamber SAPHIR (Simulation of Atmospheric PHotochemistry In a large Reaction Chamber)
Kinetic study of the atmospheric oxidation of a series of epoxy compounds by OH radicals
An experimental study of the reactivity of terpinolene and β-caryophyllene with the nitrate radical
Oxidation product characterization from ozonolysis of the diterpene ent-kaurene
Kinetics of OH + SO2 + M: temperature-dependent rate coefficients in the fall-off regime and the influence of water vapour
Formation of organic sulfur compounds through SO2-initiated photochemistry of PAHs and dimethylsulfoxide at the air-water interface
Stable carbon isotopic composition of biomass burning emissions – implications for estimating the contribution of C3 and C4 plants
Evaluation of the daytime tropospheric loss of 2-methylbutanal
Xinping Yang, Jia Ke, Zhihui Huang, Yi Wen, Dailin Yin, Zhen Jiang, Zhigang Yue, Yunjing Wang, Songdi Liao, Hang Yin, and Yan Ding
Atmos. Chem. Phys., 25, 7669–7682, https://doi.org/10.5194/acp-25-7669-2025, https://doi.org/10.5194/acp-25-7669-2025, 2025
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Given the limitation of insufficient research on greenhouse gas emission characteristics of light-duty vehicles in China against a dual-carbon background, we conducted chassis dynamometer tests on over 10 vehicles and elaborated in detail on the characteristics of greenhouse gas emissions from vehicles in the context of technological updates.
Rui Wang, Rongrong Li, Shasha Chen, Ruxue Mu, Changming Zhang, Xiaohui Ma, Majid Khan, and Tianlei Zhang
Atmos. Chem. Phys., 25, 5695–5709, https://doi.org/10.5194/acp-25-5695-2025, https://doi.org/10.5194/acp-25-5695-2025, 2025
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Gaseous results indicated that SO3 hydrolysis with formic sulfuric anhydride (FSA) has a Gibbs free energy barrier as low as 1.5 kcal mol-1 and can effectively compete with other SO3 hydrolysis. Interfacial BOMD (Born–Oppenheimer molecular dynamics) simulations illustrated that FSA-mediated SO3 hydrolysis at the gas–liquid interface occurs through a stepwise mechanism and can be completed within a few picoseconds. ACDC (Atmospheric Clusters Dynamics Code) kinetic simulations indicated that FSA significantly enhances cluster formation rates in the H2SO4–NH3 system.
Inmaculada Aranda, Sagrario Salgado, Beatriz Cabañas, Florentina Villanueva, and Pilar Martín
Atmos. Chem. Phys., 25, 5445–5468, https://doi.org/10.5194/acp-25-5445-2025, https://doi.org/10.5194/acp-25-5445-2025, 2025
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3,3-dimethylbutanal and 3,3-dimethylbutanone are compounds that might play a big role in the chemistry of the atmosphere. To better understand their effects, the rate at which these reactions happen was measured and the reaction products were identified. The results of this study show that these compounds degrade near their sources, so they do not have a direct impact on climate. However, they can contribute to the formation of tropospheric O3 and secondary organic aerosols affecting our health.
Jena M. Jenkins and William H. Brune
Atmos. Chem. Phys., 25, 5041–5052, https://doi.org/10.5194/acp-25-5041-2025, https://doi.org/10.5194/acp-25-5041-2025, 2025
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Both the atmosphere's primary cleaner, the hydroxyl radical, and nitric oxide are generated in extreme amounts by lightning, and laboratory and modeling experiments demonstrate that these molecules are generated in different places in lightning flashes. Thus the hydroxyl radical is not immediately consumed by the nitric oxide and instead is available to remove other pollutants in the atmosphere. Additionally, substantial nitrous acid is also likely generated by lightning.
Yuanyuan Luo, Lauri Franzon, Jiangyi Zhang, Nina Sarnela, Neil M. Donahue, Theo Kurtén, and Mikael Ehn
Atmos. Chem. Phys., 25, 4655–4664, https://doi.org/10.5194/acp-25-4655-2025, https://doi.org/10.5194/acp-25-4655-2025, 2025
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This study explores the formation of accretion products from reactions involving highly reactive compounds, Criegee intermediates. We focused on three types of terpenes, common in nature, and their reactions with specific acids. Our findings reveal that these reactions efficiently produce expected compounds. This research enhances our understanding of how these reactions affect air quality and climate by contributing to aerosol formation, crucial for atmospheric chemistry.
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
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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.
James D. D'Souza Metcalf, Ruth K. Winkless, Caterina Mapelli, C. Rob McElroy, Claudiu Roman, Cecilia Arsene, Romeo I. Olariu, Iustinian G. Bejan, and Terry J. Dillon
EGUsphere, https://doi.org/10.5194/egusphere-2025-866, https://doi.org/10.5194/egusphere-2025-866, 2025
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Oxymethylene ethers are a class of sustainable compounds that could be used to replace harmful organic solvents in a range of applications. In this work we used lab-based experiments to identify the main breakdown routes of these compounds in the atmosphere. We have determined that they likely contribute less to air pollution than the compounds that they replace.
Tiantian Wang, Jun Zhang, Houssni Lamkaddam, Kun Li, Ka Yuen Cheung, Lisa Kattner, Erlend Gammelsæter, Michael Bauer, Zachary C. J. Decker, Deepika Bhattu, Rujin Huang, Rob L. Modini, Jay G. Slowik, Imad El Haddad, Andre S. H. Prevot, and David M. Bell
Atmos. Chem. Phys., 25, 2707–2724, https://doi.org/10.5194/acp-25-2707-2025, https://doi.org/10.5194/acp-25-2707-2025, 2025
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Our study analyzes real-time emissions of organic vapors from solid fuel combustion. Using the mass spectrometer, we tested various fuels, finding higher emission factors for organic vapors from wood burning. Intermediate-volatility organic compounds constituted a significant fraction of emissions in solid fuel combustion. Statistical tests identified unique potential markers. Our insights benefit air quality, climate, and health, aiding accurate emission assessments.
Jonas O. Sommar, Xueling Tang, Xinyu Shi, Guangyi Sun, Che-Jen Lin, and Xinbin Feng
EGUsphere, https://doi.org/10.5194/egusphere-2024-4190, https://doi.org/10.5194/egusphere-2024-4190, 2025
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A more thorough understanding of the complex processes involved in the atmospheric Hg cycle has been achieved. The dynamics of the cycle are influenced by a rapid redox chemistry with several oxidation states and effects of multiphase interactions. This review provides a detailed analysis of the atmospheric chemistry of Hg in both the lower and upper atmosphere, together with a synthesis of the latest kinetic, thermochemical, photochemical, and isotopic fractionation data.
Reina S. Buenconsejo, Sophia M. Charan, John H. Seinfeld, and Paul O. Wennberg
Atmos. Chem. Phys., 25, 1883–1897, https://doi.org/10.5194/acp-25-1883-2025, https://doi.org/10.5194/acp-25-1883-2025, 2025
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We look at the atmospheric chemistry of a volatile chemical product (VCP), benzyl alcohol. Benzyl alcohol and other VCPs may play a significant role in the formation of urban smog. By better understanding the chemistry of VCPs like benzyl alcohol, we may better understand observed data and how VCPs affect air quality. We identify products formed from benzyl alcohol chemistry and use this chemistry to understand how benzyl alcohol forms a key component of smog, secondary organic aerosol.
Barbara Ervens, Ken S. Carslaw, Thomas Koop, and Ulrich Pöschl
EGUsphere, https://doi.org/10.5194/egusphere-2025-419, https://doi.org/10.5194/egusphere-2025-419, 2025
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Over the past two decades, the European Geosciences Union (EGU) has demonstrated the success, viability and benefits of interactive open access (OA) publishing with public peer review in its journals, its publishing platform EGUsphere and virtual compilations. The article summarizes the evolution of the EGU/Copernicus publications and of OA publishing with interactive public peer review at large by placing the EGU/Copernicus publications in the context of current and future global open science.
Wendell W. Walters, Masayuki Takeuchi, Danielle E. Blum, Gamze Eris, David Tanner, Weiqi Xu, Jean Rivera-Rios, Fobang Liu, Tianchang Xu, Greg Huey, Justin B. Min, Rodney Weber, Nga L. Ng, and Meredith G. Hastings
EGUsphere, https://doi.org/10.5194/egusphere-2024-3860, https://doi.org/10.5194/egusphere-2024-3860, 2024
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We studied how chemicals released from plants and pollution interact in the atmosphere, affecting air quality and climate. By combining laboratory experiments and chemistry models, we tracked unique chemical fingerprints to understand how nitrogen compounds transform to form particles in the air. Our findings help explain the role of these reactions in pollution and provide tools to improve predictions for cleaner air and better climate policies.
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
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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.
Bowen Li, Jian Gao, Chun Chen, Liang Wen, Yuechong Zhang, Junling Li, Yuzhe Zhang, Xiaohui Du, Kai Zhang, and Jiaqi Wang
Atmos. Chem. Phys., 24, 13183–13198, https://doi.org/10.5194/acp-24-13183-2024, https://doi.org/10.5194/acp-24-13183-2024, 2024
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The photolysis rate constant of particulate nitrate for HONO production (JNO3−–HONO), derived from PM2.5 samples collected at five representative sites in China, exhibited a wide range of variation. A parameterization equation relating JNO3−–HONO to OC/NO3− has been established and can be used to estimate JNO3−–HONO in different environments. Our work provides an important reference for research in other regions of the world where aerosol samples have a high proportion of organic components.
Zhu Ran, Yanan Hu, Yuanzhe Li, Xiaoya Gao, Can Ye, Shuai Li, Xiao Lu, Yongming Luo, Sasho Gligorovski, and Jiangping Liu
Atmos. Chem. Phys., 24, 11943–11954, https://doi.org/10.5194/acp-24-11943-2024, https://doi.org/10.5194/acp-24-11943-2024, 2024
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We report enhanced formation of nitrous acid (HONO) and NOx (NO + NO2) triggered by iron ions during photolysis of neonicotinoid insecticides at the air–water interface. This novel previously overlooked source of atmospheric HONO and NOx may be an important contribution to the global nitrogen cycle and affects atmospheric oxidizing capacity and climate change.
Yanyan Xin, Chengtang Liu, Xiaoxiu Lun, Shuyang Xie, Junfeng Liu, and Yujing Mu
Atmos. Chem. Phys., 24, 11409–11429, https://doi.org/10.5194/acp-24-11409-2024, https://doi.org/10.5194/acp-24-11409-2024, 2024
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Rate coefficients for the reactions of OH radicals with C3–C11 alkanes were determined using the multivariate relative-rate technique. A total of 25 relative-rate coefficients at room temperature and 24 Arrhenius expressions in the temperature range of 273–323 K were obtained, which expanded the data available.
Yuanyuan Luo, Ditte Thomsen, Emil Mark Iversen, Pontus Roldin, Jane Tygesen Skønager, Linjie Li, Michael Priestley, Henrik B. Pedersen, Mattias Hallquist, Merete Bilde, Marianne Glasius, and Mikael Ehn
Atmos. Chem. Phys., 24, 9459–9473, https://doi.org/10.5194/acp-24-9459-2024, https://doi.org/10.5194/acp-24-9459-2024, 2024
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∆3-carene is abundantly emitted from vegetation, but its atmospheric oxidation chemistry has received limited attention. We explored highly oxygenated organic molecule (HOM) formation from ∆3-carene ozonolysis in chambers and investigated the impact of temperature and relative humidity on HOM formation. Our findings provide new insights into ∆3-carene oxidation pathways and their potential to impact atmospheric aerosols.
Izabela Kurzydym, Agata Błaziak, Kinga Podgórniak, Karol Kułacz, and Kacper Błaziak
Atmos. Chem. Phys., 24, 9309–9322, https://doi.org/10.5194/acp-24-9309-2024, https://doi.org/10.5194/acp-24-9309-2024, 2024
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This paper outlines a unique scientific strategy for studying the reactivity of atmospherically relevant norpinonic acid (NA). The publication offers a new toolbox, illustrating NA's fragmentation and pattern of kinetic degradation leading to the formation of new small molecules. Furthermore, the research strategy presented here demonstrates how a mass spectrometer can function as a gas-phase reactor and the quantum chemistry method can serve as a reaction model builder.
Yuwei Wang, Chuang Li, Ying Zhang, Yueyang Li, Gan Yang, Xueyan Yang, Yizhen Wu, Lei Yao, Hefeng Zhang, and Lin Wang
Atmos. Chem. Phys., 24, 7961–7981, https://doi.org/10.5194/acp-24-7961-2024, https://doi.org/10.5194/acp-24-7961-2024, 2024
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The formation and evolution mechanisms of aromatics-derived highly oxygenated organic molecules (HOMs) are essential to understand the formation of secondary organic aerosol pollution. Our conclusion highlights an underappreciated formation pathway of aromatics-derived HOMs and elucidates detailed formation mechanisms of certain HOMs, which advances our understanding of HOMs and potentially explains the existing gap between model prediction and ambient measurement of the HOMs' concentrations.
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
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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.
Lucy V. Brown, Ryan J. Pound, Lyndsay S. Ives, Matthew R. Jones, Stephen J. Andrews, and Lucy J. Carpenter
Atmos. Chem. Phys., 24, 3905–3923, https://doi.org/10.5194/acp-24-3905-2024, https://doi.org/10.5194/acp-24-3905-2024, 2024
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Ozone is deposited from the lower atmosphere to the surface of the ocean; however, the chemical reactions which drive this deposition are currently not well understood. Of particular importance is the reaction between ozone and iodide, and this work measures the kinetics of this reaction and its temperature dependence, which we find to be negligible. We then investigate the subsequent emissions of iodine-containing species from the surface ocean, which can further impact ozone.
Lorrie Simone Denise Jacob, Chiara Giorio, and Alexander Thomas Archibald
Atmos. Chem. Phys., 24, 3329–3347, https://doi.org/10.5194/acp-24-3329-2024, https://doi.org/10.5194/acp-24-3329-2024, 2024
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Recent studies on DMS have provided new challenges to our mechanistic understanding. Here we synthesise a number of recent studies to further develop and extend a state-of-the-art mechanism. Our new mechanism is shown to outperform all existing mechanisms when compared over a wide set of conditions. The development of an improved DMS mechanism will help lead the way to better the understanding the climate impacts of DMS emissions in past, present, and future atmospheric conditions.
Jiangyi Zhang, Jian Zhao, Yuanyuan Luo, Valter Mickwitz, Douglas Worsnop, and Mikael Ehn
Atmos. Chem. Phys., 24, 2885–2911, https://doi.org/10.5194/acp-24-2885-2024, https://doi.org/10.5194/acp-24-2885-2024, 2024
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Due to the intrinsic connection between the formation pathways of O3 and HOMs, the ratio of HOM dimers or non-nitrate monomers to HOM organic nitrates could be used to determine O3 formation regimes. Owing to the fast formation and short lifetimes of HOMs, HOM-based indicating ratios can describe O3 formation in real time. Despite the success of our approach in this simple laboratory system, applicability to the much more complex atmosphere remains to be determined.
Xi Cheng, Yong Jie Li, Yan Zheng, Keren Liao, Theodore K. Koenig, Yanli Ge, Tong Zhu, Chunxiang Ye, Xinghua Qiu, and Qi Chen
Atmos. Chem. Phys., 24, 2099–2112, https://doi.org/10.5194/acp-24-2099-2024, https://doi.org/10.5194/acp-24-2099-2024, 2024
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In this study we conducted laboratory measurements to investigate the formation of gas-phase oxygenated organic molecules (OOMs) from six aromatic volatile organic compounds (VOCs). We provide a thorough analysis on the effects of precursor structure (substituents and ring numbers) on product distribution and highlight from a laboratory perspective that heavy (e.g., double-ring) aromatic VOCs are important in initial particle growth during secondary organic aerosol formation.
Yiwei Gong, Feng Jiang, Yanxia Li, Thomas Leisner, and Harald Saathoff
Atmos. Chem. Phys., 24, 167–184, https://doi.org/10.5194/acp-24-167-2024, https://doi.org/10.5194/acp-24-167-2024, 2024
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This study investigates the role of the important atmospheric reactive intermediates in the formation of dimers and aerosol in monoterpene ozonolysis at different temperatures. Through conducting a series of chamber experiments and utilizing chemical kinetic and aerosol dynamic models, the SOA formation processes are better described, especially for colder regions. The results can be used to improve the chemical mechanism modeling of monoterpenes and SOA parameterization in transport models.
María Asensio, Sergio Blázquez, María Antiñolo, José Albaladejo, and Elena Jiménez
Atmos. Chem. Phys., 23, 14115–14126, https://doi.org/10.5194/acp-23-14115-2023, https://doi.org/10.5194/acp-23-14115-2023, 2023
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In this work, we focus on the atmospheric chemistry and consequences for air quality of 2-methylpentanal (2MP), which is widely used as a flavoring ingredient and as an intermediate in the synthesis of dyes, resins, and pharmaceuticals. Measurements are presented on how fast 2MP is degraded by sunlight and oxidants like hydroxyl (OH) radicals and chlorine (Cl) atoms and what products are generated. We conclude that 2MP will be degraded in a few hours, affecting local air quality.
Andrew T. Lambe, Bin Bai, Masayuki Takeuchi, Nicole Orwat, Paul M. Zimmerman, Mitchell W. Alton, Nga L. Ng, Andrew Freedman, Megan S. Claflin, Drew R. Gentner, Douglas R. Worsnop, and Pengfei Liu
Atmos. Chem. Phys., 23, 13869–13882, https://doi.org/10.5194/acp-23-13869-2023, https://doi.org/10.5194/acp-23-13869-2023, 2023
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We developed a new method to generate nitrate radicals (NO3) for atmospheric chemistry applications that works by irradiating mixtures containing ceric ammonium nitrate with a UV light at room temperature. It has several advantages over traditional NO3 sources. We characterized its performance over a range of mixture and reactor conditions as well as other irradiation products. Proof of concept was demonstrated by generating and characterizing oxidation products of the β-pinene + NO3 reaction.
Han Zang, Dandan Huang, Jiali Zhong, Ziyue Li, Chenxi Li, Huayun Xiao, and Yue Zhao
Atmos. Chem. Phys., 23, 12691–12705, https://doi.org/10.5194/acp-23-12691-2023, https://doi.org/10.5194/acp-23-12691-2023, 2023
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Acylperoxy radicals (RO2) are key intermediates in the atmospheric oxidation of organic compounds, yet our knowledge of their identities and chemistry remains poor. Using direct measurements and kinetic modeling, we identify the composition and formation pathways of acyl RO2 and quantify their contribution to highly oxygenated organic molecules during α-pinene ozonolysis, which will help to understand oxidation chemistry of monoterpenes and sources of low-volatility organics in 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
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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.
Rolf Sander
Atmos. Chem. Phys., 23, 10901–12440, https://doi.org/10.5194/acp-23-10901-2023, https://doi.org/10.5194/acp-23-10901-2023, 2023
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According to Henry's law, the equilibrium ratio between the abundances in the gas phase and in the aqueous phase is constant for a dilute solution. Henry’s law constants of trace gases of potential importance in environmental chemistry have been collected and converted into a uniform format. The compilation contains 46 434 values of Henry's law constants for 10 173 species, collected from 995 references. It is also available on the internet at https://www.henrys-law.org.
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
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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.
Yixin Hao, Jun Zhou, Jie-Ping Zhou, Yan Wang, Suxia Yang, Yibo Huangfu, Xiao-Bing Li, Chunsheng Zhang, Aiming Liu, Yanfeng Wu, Yaqing Zhou, Shuchun Yang, Yuwen Peng, Jipeng Qi, Xianjun He, Xin Song, Yubin Chen, Bin Yuan, and Min Shao
Atmos. Chem. Phys., 23, 9891–9910, https://doi.org/10.5194/acp-23-9891-2023, https://doi.org/10.5194/acp-23-9891-2023, 2023
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By employing an improved net photochemical ozone production rate (NPOPR) detection system based on the dual-channel reaction chamber technique, we measured the net photochemical ozone production rate in the Pearl River Delta in China. The photochemical ozone formation mechanisms in the reaction and reference chambers were investigated using the observation-data-constrained box model, which helped us to validate the NPOPR detection system and understand photochemical ozone formation mechanism.
Kevin J. Nihill, Matthew M. Coggon, Christopher Y. Lim, Abigail R. Koss, Bin Yuan, Jordan E. Krechmer, Kanako Sekimoto, Jose L. Jimenez, Joost de Gouw, Christopher D. Cappa, Colette L. Heald, Carsten Warneke, and Jesse H. Kroll
Atmos. Chem. Phys., 23, 7887–7899, https://doi.org/10.5194/acp-23-7887-2023, https://doi.org/10.5194/acp-23-7887-2023, 2023
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In this work, we collect emissions from controlled burns of biomass fuels that can be found in the western United States into an environmental chamber in order to simulate their oxidation as they pass through the atmosphere. These findings provide a detailed characterization of the composition of the atmosphere downwind of wildfires. In turn, this will help to explore the effects of these changing emissions on downwind populations and will also directly inform atmospheric and climate models.
Caterina Mapelli, James K. Donnelly, Úna E. Hogan, Andrew R. Rickard, Abbie T. Robinson, Fergal Byrne, Con Rob McElroy, Basile F. E. Curchod, Daniel Hollas, and Terry J. Dillon
Atmos. Chem. Phys., 23, 7767–7779, https://doi.org/10.5194/acp-23-7767-2023, https://doi.org/10.5194/acp-23-7767-2023, 2023
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Solvents are chemical compounds with countless uses in the chemical industry, and they also represent one of the main sources of pollution in the chemical sector. Scientists are trying to develop new
greensafer solvents which present favourable advantages when compared to traditional solvents. Since the assessment of these green solvents often lacks air quality considerations, this study aims to understand the behaviour of these compounds, investigating their reactivity in the troposphere.
Roland Benoit, Nesrine Belhadj, Zahraa Dbouk, Maxence Lailliau, and Philippe Dagaut
Atmos. Chem. Phys., 23, 5715–5733, https://doi.org/10.5194/acp-23-5715-2023, https://doi.org/10.5194/acp-23-5715-2023, 2023
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We observed a surprisingly similar set of oxidation product chemical formulas from limonene and α-pinene, including oligomers, formed under cool-flame (present experiments) and simulated atmospheric oxidation (literature). Data analysis indicated that a subset of chemical formulas is common to all experiments independently of experimental conditions. Also, this study indicates that many detected chemical formulas can be ascribed to an autooxidation reaction.
Melissa Meder, Otso Peräkylä, Jonathan G. Varelas, Jingyi Luo, Runlong Cai, Yanjun Zhang, Theo Kurtén, Matthieu Riva, Matti Rissanen, Franz M. Geiger, Regan J. Thomson, and Mikael Ehn
Atmos. Chem. Phys., 23, 4373–4390, https://doi.org/10.5194/acp-23-4373-2023, https://doi.org/10.5194/acp-23-4373-2023, 2023
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We discuss and show the viability of a method where multiple isotopically labelled precursors are used for probing the formation pathways of highly oxygenated organic molecules (HOMs) from the oxidation of the monoterpene a-pinene. HOMs are very important for secondary organic aerosol (SOA) formation in forested regions, and monoterpenes are the single largest source of SOA globally. The fast reactions forming HOMs have thus far remained elusive despite considerable efforts over the last decade.
Philip T. M. Carlsson, Luc Vereecken, Anna Novelli, François Bernard, Steven S. Brown, Bellamy Brownwood, Changmin Cho, John N. Crowley, Patrick Dewald, Peter M. Edwards, Nils Friedrich, Juliane L. Fry, Mattias Hallquist, Luisa Hantschke, Thorsten Hohaus, Sungah Kang, Jonathan Liebmann, Alfred W. Mayhew, Thomas Mentel, David Reimer, Franz Rohrer, Justin Shenolikar, Ralf Tillmann, Epameinondas Tsiligiannis, Rongrong Wu, Andreas Wahner, Astrid Kiendler-Scharr, and Hendrik Fuchs
Atmos. Chem. Phys., 23, 3147–3180, https://doi.org/10.5194/acp-23-3147-2023, https://doi.org/10.5194/acp-23-3147-2023, 2023
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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.
Kevin D. Easterbrook, Mitchell A. Vona, Kiana Nayebi-Astaneh, Amanda M. Miller, and Hans D. Osthoff
Atmos. Chem. Phys., 23, 311–322, https://doi.org/10.5194/acp-23-311-2023, https://doi.org/10.5194/acp-23-311-2023, 2023
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The trace gas peroxypropionyl nitrate (PPN) is generated in photochemical smog, phytotoxic, a strong eye irritant, and possibly mutagenic. Here, its solubility and reactivity in water and in octanol were investigated using a bubble flow apparatus, yielding its Henry's law constant and octanol–water partition coefficient (Kow). The results allow the fate of PPN to be more accurately constrained in atmospheric chemical transport models, including its uptake on clouds, organic aerosol, and leaves.
Qing Ye, Matthew B. Goss, Jordan E. Krechmer, Francesca Majluf, Alexander Zaytsev, Yaowei Li, Joseph R. Roscioli, Manjula Canagaratna, Frank N. Keutsch, Colette L. Heald, and Jesse H. Kroll
Atmos. Chem. Phys., 22, 16003–16015, https://doi.org/10.5194/acp-22-16003-2022, https://doi.org/10.5194/acp-22-16003-2022, 2022
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The atmospheric oxidation of dimethyl sulfide (DMS) is a major natural source of sulfate particles in the atmosphere. However, its mechanism is poorly constrained. In our work, laboratory measurements and mechanistic modeling were conducted to comprehensively investigate DMS oxidation products and key reaction rates. We find that the peroxy radical (RO2) has a controlling effect on product distribution and aerosol yield, with the isomerization of RO2 leading to the suppression of aerosol yield.
Caterina Mapelli, Juliette V. Schleicher, Alex Hawtin, Conor D. Rankine, Fiona C. Whiting, Fergal Byrne, C. Rob McElroy, Claudiu Roman, Cecilia Arsene, Romeo I. Olariu, Iustinian G. Bejan, and Terry J. Dillon
Atmos. Chem. Phys., 22, 14589–14602, https://doi.org/10.5194/acp-22-14589-2022, https://doi.org/10.5194/acp-22-14589-2022, 2022
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Solvents represent an important source of pollution from the chemical industry. New "green" solvents aim to replace toxic solvents with new molecules made from renewable sources and designed to be less harmful. Whilst these new molecules are selected according to toxicity and other characteristics, no consideration has yet been included on air quality. Studying the solvent breakdown in air, we found that TMO has a lower impact on air quality than traditional solvents with similar properties.
Kai Song, Song Guo, Yuanzheng Gong, Daqi Lv, Yuan Zhang, Zichao Wan, Tianyu Li, Wenfei Zhu, Hui Wang, Ying Yu, Rui Tan, Ruizhe Shen, Sihua Lu, Shuangde Li, Yunfa Chen, and Min Hu
Atmos. Chem. Phys., 22, 9827–9841, https://doi.org/10.5194/acp-22-9827-2022, https://doi.org/10.5194/acp-22-9827-2022, 2022
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Emissions from four typical Chinese domestic cooking and fried chicken using four kinds of oils were investigated to illustrate the impact of cooking style and oil. Of the estimated SOA, 10.2 %–32.0 % could be explained by S/IVOC oxidation. Multiway principal component analysis (MPCA) emphasizes the importance of the unsaturated fatty acid-alkadienal volatile product mechanism (oil autoxidation) accelerated by the cooking and heating procedure.
Michelia Dam, Danielle C. Draper, Andrey Marsavin, Juliane L. Fry, and James N. Smith
Atmos. Chem. Phys., 22, 9017–9031, https://doi.org/10.5194/acp-22-9017-2022, https://doi.org/10.5194/acp-22-9017-2022, 2022
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We performed chamber experiments to measure the composition of the gas-phase reaction products of nitrate-radical-initiated oxidation of four monoterpenes. The total organic yield, effective oxygen-to-carbon ratio, and dimer-to-monomer ratio were correlated with the observed particle formation for the monoterpene systems with some exceptions. The Δ-carene system produced the most particles, followed by β-pinene, with the α-pinene and α-thujene systems producing no particles.
Jacky Yat Sing Pang, Anna Novelli, Martin Kaminski, Ismail-Hakki Acir, Birger Bohn, Philip T. M. Carlsson, Changmin Cho, Hans-Peter Dorn, Andreas Hofzumahaus, Xin Li, Anna Lutz, Sascha Nehr, David Reimer, Franz Rohrer, Ralf Tillmann, Robert Wegener, Astrid Kiendler-Scharr, Andreas Wahner, and Hendrik Fuchs
Atmos. Chem. Phys., 22, 8497–8527, https://doi.org/10.5194/acp-22-8497-2022, https://doi.org/10.5194/acp-22-8497-2022, 2022
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This study investigates the radical chemical budget during the limonene oxidation at different atmospheric-relevant NO concentrations in chamber experiments under atmospheric conditions. It is found that the model–measurement discrepancies of HO2 and RO2 are very large at low NO concentrations that are typical for forested environments. Possible additional processes impacting HO2 and RO2 concentrations are discussed.
Carmen Maria Tovar, Ian Barnes, Iustinian Gabriel Bejan, and Peter Wiesen
Atmos. Chem. Phys., 22, 6989–7004, https://doi.org/10.5194/acp-22-6989-2022, https://doi.org/10.5194/acp-22-6989-2022, 2022
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This work explores the kinetics and reactivity of epoxides towards the OH radical using two different simulation chambers. Estimation of the rate coefficients has also been made using different structure–activity relationship (SAR) approaches. The results indicate a direct influence of the structural and geometric properties of the epoxides not considered in SAR estimations, influencing the reactivity of these compounds. The outcomes of this work are in very good agreement with previous studies.
Axel Fouqueau, Manuela Cirtog, Mathieu Cazaunau, Edouard Pangui, Jean-François Doussin, and Bénédicte Picquet-Varrault
Atmos. Chem. Phys., 22, 6411–6434, https://doi.org/10.5194/acp-22-6411-2022, https://doi.org/10.5194/acp-22-6411-2022, 2022
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Biogenic volatile organic compounds are intensely emitted by forests and crops and react with the nitrate radical during the nighttime to form functionalized products. The purpose of this study is to furnish kinetic and mechanistic data for terpinolene and β-caryophyllene, using simulation chamber experiments. Rate constants have been measured using both relative and absolute methods, and mechanistic studies have been conducted in order to identify and quantify the main reaction products.
Yuanyuan Luo, Olga Garmash, Haiyan Li, Frans Graeffe, Arnaud P. Praplan, Anssi Liikanen, Yanjun Zhang, Melissa Meder, Otso Peräkylä, Josep Peñuelas, Ana María Yáñez-Serrano, and Mikael Ehn
Atmos. Chem. Phys., 22, 5619–5637, https://doi.org/10.5194/acp-22-5619-2022, https://doi.org/10.5194/acp-22-5619-2022, 2022
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Diterpenes were only recently observed in the atmosphere, and little is known of their atmospheric fates. We explored the ozonolysis of the diterpene kaurene in a chamber, and we characterized the oxidation products for the first time using chemical ionization mass spectrometry. Our findings highlight similarities and differences between diterpenes and smaller terpenes during their atmospheric oxidation.
Wenyu Sun, Matias Berasategui, Andrea Pozzer, Jos Lelieveld, and John N. Crowley
Atmos. Chem. Phys., 22, 4969–4984, https://doi.org/10.5194/acp-22-4969-2022, https://doi.org/10.5194/acp-22-4969-2022, 2022
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The reaction between OH and SO2 is a termolecular process that in the atmosphere results in the formation of H2SO4 and thus aerosols. We present the first temperature- and pressure-dependent measurements of the rate coefficients in N2. This is also the first study to examine the effects of water vapour on the kinetics of this reaction. Our results indicate the rate coefficient is larger than that recommended by evaluation panels, with deviations of up to 30 % in some parts of the atmosphere.
Haoyu Jiang, Yingyao He, Yiqun Wang, Sheng Li, Bin Jiang, Luca Carena, Xue Li, Lihua Yang, Tiangang Luan, Davide Vione, and Sasho Gligorovski
Atmos. Chem. Phys., 22, 4237–4252, https://doi.org/10.5194/acp-22-4237-2022, https://doi.org/10.5194/acp-22-4237-2022, 2022
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Heterogeneous oxidation of SO2 is suggested to be one of the most important pathways for sulfate formation during extreme haze events in China, yet the exact mechanism remains highly uncertain. Our study reveals that ubiquitous compounds at the sea surface PAHS and DMSO, when exposed to SO2 under simulated sunlight irradiation, generate abundant organic sulfur compounds, providing implications for air-sea interaction and secondary organic aerosols formation processes.
Roland Vernooij, Ulrike Dusek, Maria Elena Popa, Peng Yao, Anupam Shaikat, Chenxi Qiu, Patrik Winiger, Carina van der Veen, Thomas Callum Eames, Natasha Ribeiro, and Guido R. van der Werf
Atmos. Chem. Phys., 22, 2871–2890, https://doi.org/10.5194/acp-22-2871-2022, https://doi.org/10.5194/acp-22-2871-2022, 2022
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Landscape fires are a major source of greenhouse gases and aerosols, particularly in sub-tropical savannas. Stable carbon isotopes in emissions can be used to trace the contribution of C3 plants (e.g. trees or shrubs) and C4 plants (e.g. savanna grasses) to greenhouse gases and aerosols if the process is well understood. This helps us to link individual vegetation types to emissions, identify biomass burning emissions in the atmosphere, and improve the reconstruction of historic fire regimes.
María Asensio, María Antiñolo, Sergio Blázquez, José Albaladejo, and Elena Jiménez
Atmos. Chem. Phys., 22, 2689–2701, https://doi.org/10.5194/acp-22-2689-2022, https://doi.org/10.5194/acp-22-2689-2022, 2022
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The diurnal atmospheric degradation of 2-methylbutanal, 2 MB, emitted by sources like vegetation or the poultry industry is evaluated in this work. Sunlight and oxidants like hydroxyl (OH) radicals and chlorine (Cl) atoms initiate this degradation. Measurements of how fast 2 MB is degraded and what products are generated are presented. The lifetime of 2 MB is around 1 h at noon, when the OH reaction dominates. Thus, 2 MB will not be transported far, affecting only local air quality.
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Short summary
This work illustrates how a common volatile hydrocarbon, hexanal, has the potential to undergo atmospheric autoxidation that leads to prompt formation of condensable material that subsequently contributes to aerosol formation, deteriorating the air quality of urban atmospheres. We used the combined state-of-the-art quantum chemical modeling and experimental flow reactor experiments under atmospheric conditions to resolve the autoxidation mechanism of hexanal initiated by a common oxidant.
This work illustrates how a common volatile hydrocarbon, hexanal, has the potential to undergo...
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