Articles | Volume 15, issue 6
https://doi.org/10.5194/amt-15-1811-2022
© Author(s) 2022. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
https://doi.org/10.5194/amt-15-1811-2022
© Author(s) 2022. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
25 Mar 2022
Research article |
| 25 Mar 2022
| 25 Mar 2022
Fragmentation inside proton-transfer-reaction-based mass spectrometers limits the detection of ROOR and ROOH peroxides
School of Civil and Environmental Engineering, Harbin Institute of
Technology, Shenzhen, 518055, China
Institute for Atmospheric and Earth System Research/Physics, Faculty of Science, University of Helsinki, Helsinki, 00014, Finland
Thomas Golin Almeida
Department of Chemistry, University of Helsinki, Helsinki, 00014,
Finland
Yuanyuan Luo
Institute for Atmospheric and Earth System Research/Physics, Faculty of Science, University of Helsinki, Helsinki, 00014, Finland
Jian Zhao
Institute for Atmospheric and Earth System Research/Physics, Faculty of Science, University of Helsinki, Helsinki, 00014, Finland
Brett B. Palm
Department of Atmospheric Science, University of Washington, Seattle, Washington, WA, 98195, USA
Christopher D. Daub
Department of Chemistry, University of Helsinki, Helsinki, 00014,
Finland
Wei Huang
Institute for Atmospheric and Earth System Research/Physics, Faculty of Science, University of Helsinki, Helsinki, 00014, Finland
Claudia Mohr
Department of Environmental Science, Stockholm University, 11418,
Stockholm, Sweden
Jordan E. Krechmer
Aerodyne Research, Inc., Billerica, MA, 01821, USA
Theo Kurtén
CORRESPONDING AUTHOR
Department of Chemistry, University of Helsinki, Helsinki, 00014,
Finland
Institute for Atmospheric and Earth System Research/Physics, Faculty of Science, University of Helsinki, Helsinki, 00014, Finland
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Hengheng Zhang, Wei Huang, Xiaoli Shen, Ramakrishna Ramisetty, Junwei Song, Olga Kiseleva, Christopher Claus Holst, Basit Khan, Thomas Leisner, and Harald Saathoff
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Liine Heikkinen, Daniel G. Partridge, Sara Blichner, Wei Huang, Rahul Ranjan, Paul Bowen, Emanuele Tovazzi, Tuukka Petäjä, Claudia Mohr, and Ilona Riipinen
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Jian Zhao, Valter Mickwitz, Yuanyuan Luo, Ella Häkkinen, Frans Graeffe, Jiangyi Zhang, Hilkka Timonen, Manjula Canagaratna, Jordan E. Krechmer, Qi Zhang, Markku Kulmala, Juha Kangasluoma, Douglas Worsnop, and Mikael Ehn
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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.
Wei Huang, Cheng Wu, Linyu Gao, Yvette Gramlich, Sophie L. Haslett, Joel Thornton, Felipe D. Lopez-Hilfiker, Ben H. Lee, Junwei Song, Harald Saathoff, Xiaoli Shen, Ramakrishna Ramisetty, Sachchida N. Tripathi, Dilip Ganguly, Feng Jiang, Magdalena Vallon, Siegfried Schobesberger, Taina Yli-Juuti, and Claudia Mohr
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Jing Cai, Juha Sulo, Yifang Gu, Sebastian Holm, Runlong Cai, Steven Thomas, Almuth Neuberger, Fredrik Mattsson, Marco Paglione, Stefano Decesari, Matteo Rinaldi, Rujing Yin, Diego Aliaga, Wei Huang, Yuanyuan Li, Yvette Gramlich, Giancarlo Ciarelli, Lauriane Quéléver, Nina Sarnela, Katrianne Lehtipalo, Nora Zannoni, Cheng Wu, Wei Nie, Juha Kangasluoma, Claudia Mohr, Markku Kulmala, Qiaozhi Zha, Dominik Stolzenburg, and Federico Bianchi
Atmos. Chem. Phys., 24, 2423–2441, https://doi.org/10.5194/acp-24-2423-2024, https://doi.org/10.5194/acp-24-2423-2024, 2024
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By combining field measurements, simulations and recent chamber experiments, we investigate new particle formation (NPF) and growth in the Po Valley, where both haze and frequent NPF occur. Our results show that sulfuric acid, ammonia and amines are the dominant NPF precursors there. A high NPF rate and a lower condensation sink lead to a greater survival probability for newly formed particles, highlighting the importance of gas-to-particle conversion for aerosol concentrations.
Arto Heitto, Cheng Wu, Diego Aliaga, Luis Blacutt, Xuemeng Chen, Yvette Gramlich, Liine Heikkinen, Wei Huang, Radovan Krejci, Paolo Laj, Isabel Moreno, Karine Sellegri, Fernando Velarde, Kay Weinhold, Alfred Wiedensohler, Qiaozhi Zha, Federico Bianchi, Marcos Andrade, Kari E. J. Lehtinen, Claudia Mohr, and Taina Yli-Juuti
Atmos. Chem. Phys., 24, 1315–1328, https://doi.org/10.5194/acp-24-1315-2024, https://doi.org/10.5194/acp-24-1315-2024, 2024
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Particle growth at the Chacaltaya station in Bolivia was simulated based on measured vapor concentrations and ambient conditions. Major contributors to the simulated growth were low-volatility organic compounds (LVOCs). Also, sulfuric acid had major role when volcanic activity was occurring in the area. This study provides insight on nanoparticle growth at this high-altitude Southern Hemispheric site and hence contributes to building knowledge of early growth of atmospheric particles.
Magdalena Okuljar, Olga Garmash, Miska Olin, Joni Kalliokoski, Hilkka Timonen, Jarkko V. Niemi, Pauli Paasonen, Jenni Kontkanen, Yanjun Zhang, Heidi Hellén, Heino Kuuluvainen, Minna Aurela, Hanna E. Manninen, Mikko Sipilä, Topi Rönkkö, Tuukka Petäjä, Markku Kulmala, Miikka Dal Maso, and Mikael Ehn
Atmos. Chem. Phys., 23, 12965–12983, https://doi.org/10.5194/acp-23-12965-2023, https://doi.org/10.5194/acp-23-12965-2023, 2023
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Highly oxygenated organic molecules (HOMs) form secondary organic aerosol that affects air quality and health. In this study, we demonstrate that in a moderately polluted city with abundant vegetation, the composition of HOMs is largely controlled by the effect of NOx on the biogenic volatile organic compound oxidation. Comparing the results from two nearby stations, we show that HOM composition and formation pathways can change considerably within small distances in urban environments.
Sophie L. Haslett, David M. Bell, Varun Kumar, Jay G. Slowik, Dongyu S. Wang, Suneeti Mishra, Neeraj Rastogi, Atinderpal Singh, Dilip Ganguly, Joel Thornton, Feixue Zheng, Yuanyuan Li, Wei Nie, Yongchun Liu, Wei Ma, Chao Yan, Markku Kulmala, Kaspar R. Daellenbach, David Hadden, Urs Baltensperger, Andre S. H. Prevot, Sachchida N. Tripathi, and Claudia Mohr
Atmos. Chem. Phys., 23, 9023–9036, https://doi.org/10.5194/acp-23-9023-2023, https://doi.org/10.5194/acp-23-9023-2023, 2023
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In Delhi, some aspects of daytime and nighttime atmospheric chemistry are inverted, and parodoxically, vehicle emissions may be limiting other forms of particle production. This is because the nighttime emissions of nitrogen oxide (NO) by traffic and biomass burning prevent some chemical processes that would otherwise create even more particles and worsen the urban haze.
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.
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.
Karolina Siegel, Yvette Gramlich, Sophie L. Haslett, Gabriel Freitas, Radovan Krejci, Paul Zieger, and Claudia Mohr
Atmos. Chem. Phys., 23, 7569–7587, https://doi.org/10.5194/acp-23-7569-2023, https://doi.org/10.5194/acp-23-7569-2023, 2023
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Hydroperoxymethyl thioformate (HPMTF) is a recently discovered oxidation product of dimethyl sulfide (DMS). We present a full year of concurrent gas- and particle-phase observations of HPMTF and other DMS oxidation products from the Arctic. We did not observe significant amounts of HPMTF in the particle phase but a good agreement between gas-phase HMPTF and methanesulfonic acid in the summer. Our study provides information about the relationship between HPMTF and other DMS oxidation products.
Emelie L. Graham, Cheng Wu, David M. Bell, Amelie Bertrand, Sophie L. Haslett, Urs Baltensperger, Imad El Haddad, Radovan Krejci, Ilona Riipinen, and Claudia Mohr
Atmos. Chem. Phys., 23, 7347–7362, https://doi.org/10.5194/acp-23-7347-2023, https://doi.org/10.5194/acp-23-7347-2023, 2023
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The volatility of an aerosol particle is an important parameter for describing its atmospheric lifetime. We studied the volatility of secondary organic aerosols from nitrate-initiated oxidation of three biogenic precursors with experimental methods and model simulations. We saw higher volatility than for the corresponding ozone system, and our simulations produced variable results with different parameterizations which warrant a re-evaluation of the treatment of the nitrate functional group.
Yvette Gramlich, Karolina Siegel, Sophie L. Haslett, Gabriel Freitas, Radovan Krejci, Paul Zieger, and Claudia Mohr
Atmos. Chem. Phys., 23, 6813–6834, https://doi.org/10.5194/acp-23-6813-2023, https://doi.org/10.5194/acp-23-6813-2023, 2023
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In this study, we investigate the chemical composition of aerosol particles forming clouds in the Arctic. During year-long observations at a mountain site on Svalbard, we find a large contribution of naturally derived aerosol particles in the fraction forming clouds in the summer. Our observations indicate that most aerosol particles can serve as cloud seeds in this remote environment.
Huan Yang, Ivo Neefjes, Valtteri Tikkanen, Jakub Kubečka, Theo Kurtén, Hanna Vehkamäki, and Bernhard Reischl
Atmos. Chem. Phys., 23, 5993–6009, https://doi.org/10.5194/acp-23-5993-2023, https://doi.org/10.5194/acp-23-5993-2023, 2023
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We present a new analytical model for collision rates between molecules and clusters of arbitrary sizes, accounting for long-range interactions. The model is verified against atomistic simulations of typical acid–base clusters participating in atmospheric new particle formation (NPF). Compared to non-interacting models, accounting for long-range interactions leads to 2–3 times higher collision rates for small clusters, indicating the necessity of including such interactions in NPF modeling.
Qiaozhi Zha, Wei Huang, Diego Aliaga, Otso Peräkylä, Liine Heikkinen, Alkuin Maximilian Koenig, Cheng Wu, Joonas Enroth, Yvette Gramlich, Jing Cai, Samara Carbone, Armin Hansel, Tuukka Petäjä, Markku Kulmala, Douglas Worsnop, Victoria Sinclair, Radovan Krejci, Marcos Andrade, Claudia Mohr, and Federico Bianchi
Atmos. Chem. Phys., 23, 4559–4576, https://doi.org/10.5194/acp-23-4559-2023, https://doi.org/10.5194/acp-23-4559-2023, 2023
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We investigate the chemical composition of atmospheric cluster ions from January to May 2018 at the high-altitude research station Chacaltaya (5240 m a.s.l.) in the Bolivian Andes. With state-of-the-art mass spectrometers and air mass history analysis, the measured cluster ions exhibited distinct diurnal and seasonal patterns, some of which contributed to new particle formation. Our study will improve the understanding of atmospheric ions and their role in high-altitude new particle 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.
Ella Häkkinen, Jian Zhao, Frans Graeffe, Nicolas Fauré, Jordan E. Krechmer, Douglas Worsnop, Hilkka Timonen, Mikael Ehn, and Juha Kangasluoma
Atmos. Meas. Tech., 16, 1705–1721, https://doi.org/10.5194/amt-16-1705-2023, https://doi.org/10.5194/amt-16-1705-2023, 2023
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Highly oxygenated compounds contribute to the formation and growth of atmospheric organic aerosol and thus impact the global climate. Knowledge of their transformations and fate after condensing into the particle phase has been limited by the lack of suitable detection techniques. Here, we present an online method for measuring highly oxygenated compounds from organic aerosol. We evaluate the performance of the method and demonstrate that the method is applicable to different organic species.
Jian Zhao, Ella Häkkinen, Frans Graeffe, Jordan E. Krechmer, Manjula R. Canagaratna, Douglas R. Worsnop, Juha Kangasluoma, and Mikael Ehn
Atmos. Chem. Phys., 23, 3707–3730, https://doi.org/10.5194/acp-23-3707-2023, https://doi.org/10.5194/acp-23-3707-2023, 2023
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Based on the combined measurements of gas- and particle-phase highly oxygenated organic molecules (HOMs) from α-pinene ozonolysis, enhancement of dimers in particles was observed. We conducted experiments wherein the dimer to monomer (D / M) ratios of HOMs in the gas phase were modified (adding CO / NO) to investigate the effects of the corresponding D / M ratios in the particles. These results are important for a better understanding of secondary organic aerosol formation in the atmosphere.
Jing Cai, Kaspar R. Daellenbach, Cheng Wu, Yan Zheng, Feixue Zheng, Wei Du, Sophie L. Haslett, Qi Chen, Markku Kulmala, and Claudia Mohr
Atmos. Meas. Tech., 16, 1147–1165, https://doi.org/10.5194/amt-16-1147-2023, https://doi.org/10.5194/amt-16-1147-2023, 2023
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We introduce the offline application of FIGAERO-CIMS by analyzing Teflon and quartz filter samples that were collected at a typical urban site in Beijing with the deposition time varying from 30 min to 24 h. This method provides a feasible, simple, and quantitative way to investigate the molecular composition and volatility of OA compounds by using FIGAERO-CIMS to analyze offline samples.
Wiebke Scholz, Jiali Shen, Diego Aliaga, Cheng Wu, Samara Carbone, Isabel Moreno, Qiaozhi Zha, Wei Huang, Liine Heikkinen, Jean Luc Jaffrezo, Gaelle Uzu, Eva Partoll, Markus Leiminger, Fernando Velarde, Paolo Laj, Patrick Ginot, Paolo Artaxo, Alfred Wiedensohler, Markku Kulmala, Claudia Mohr, Marcos Andrade, Victoria Sinclair, Federico Bianchi, and Armin Hansel
Atmos. Chem. Phys., 23, 895–920, https://doi.org/10.5194/acp-23-895-2023, https://doi.org/10.5194/acp-23-895-2023, 2023
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Dimethyl sulfide (DMS), emitted from the ocean, is the most abundant biogenic sulfur emission into the atmosphere. OH radicals, among others, can oxidize DMS to sulfuric and methanesulfonic acid, which are relevant for aerosol formation. We quantified DMS and nearly all DMS oxidation products with novel mass spectrometric instruments for gas and particle phase at the high mountain station Chacaltaya (5240 m a.s.l.) in the Bolivian Andes in free tropospheric air after long-range transport.
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.
Peeyush Khare, Jordan E. Krechmer, Jo E. Machesky, Tori Hass-Mitchell, Cong Cao, Junqi Wang, Francesca Majluf, Felipe Lopez-Hilfiker, Sonja Malek, Will Wang, Karl Seltzer, Havala O. T. Pye, Roisin Commane, Brian C. McDonald, Ricardo Toledo-Crow, John E. Mak, and Drew R. Gentner
Atmos. Chem. Phys., 22, 14377–14399, https://doi.org/10.5194/acp-22-14377-2022, https://doi.org/10.5194/acp-22-14377-2022, 2022
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Ammonium adduct chemical ionization is used to examine the atmospheric abundances of oxygenated volatile organic compounds associated with emissions from volatile chemical products, which are now key contributors of reactive precursors to ozone and secondary organic aerosols in urban areas. The application of this valuable measurement approach in densely populated New York City enables the evaluation of emissions inventories and thus the role these oxygenated compounds play in urban air quality.
David M. Bell, Cheng Wu, Amelie Bertrand, Emelie Graham, Janne Schoonbaert, Stamatios Giannoukos, Urs Baltensperger, Andre S. H. Prevot, Ilona Riipinen, Imad El Haddad, and Claudia Mohr
Atmos. Chem. Phys., 22, 13167–13182, https://doi.org/10.5194/acp-22-13167-2022, https://doi.org/10.5194/acp-22-13167-2022, 2022
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A series of studies designed to investigate the evolution of organic aerosol were performed in an atmospheric simulation chamber, using a common oxidant found at night (NO3). The chemical composition steadily changed from its initial composition via different chemical reactions that were taking place inside of the aerosol particle. These results show that the composition of organic aerosol steadily changes during its lifetime in the atmosphere.
Lisa J. Beck, Siegfried Schobesberger, Heikki Junninen, Janne Lampilahti, Antti Manninen, Lubna Dada, Katri Leino, Xu-Cheng He, Iida Pullinen, Lauriane L. J. Quéléver, Anna Franck, Pyry Poutanen, Daniela Wimmer, Frans Korhonen, Mikko Sipilä, Mikael Ehn, Douglas R. Worsnop, Veli-Matti Kerminen, Tuukka Petäjä, Markku Kulmala, and Jonathan Duplissy
Atmos. Chem. Phys., 22, 8547–8577, https://doi.org/10.5194/acp-22-8547-2022, https://doi.org/10.5194/acp-22-8547-2022, 2022
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The presented article introduces an overview of atmospheric ions and their composition above the boreal forest. We provide the results of an extensive airborne measurement campaign with an air ion mass spectrometer and particle measurements, showing their diurnal evolution within the boundary layer and free troposphere. In addition, we compare the airborne dataset with the co-located data from the ground at SMEAR II station, Finland.
Varun Kumar, Stamatios Giannoukos, Sophie L. Haslett, Yandong Tong, Atinderpal Singh, Amelie Bertrand, Chuan Ping Lee, Dongyu S. Wang, Deepika Bhattu, Giulia Stefenelli, Jay S. Dave, Joseph V. Puthussery, Lu Qi, Pawan Vats, Pragati Rai, Roberto Casotto, Rangu Satish, Suneeti Mishra, Veronika Pospisilova, Claudia Mohr, David M. Bell, Dilip Ganguly, Vishal Verma, Neeraj Rastogi, Urs Baltensperger, Sachchida N. Tripathi, André S. H. Prévôt, and Jay G. Slowik
Atmos. Chem. Phys., 22, 7739–7761, https://doi.org/10.5194/acp-22-7739-2022, https://doi.org/10.5194/acp-22-7739-2022, 2022
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Here we present source apportionment results from the first field deployment in Delhi of an extractive electrospray ionization time-of-flight mass spectrometer (EESI-TOF). The EESI-TOF is a recently developed instrument capable of providing uniquely detailed online chemical characterization of organic aerosol (OA), in particular the secondary OA (SOA) fraction. Here, we are able to apportion not only primary OA but also SOA to specific sources, which is performed for the first time in Delhi.
Linyu Gao, Junwei Song, Claudia Mohr, Wei Huang, Magdalena Vallon, Feng Jiang, Thomas Leisner, and Harald Saathoff
Atmos. Chem. Phys., 22, 6001–6020, https://doi.org/10.5194/acp-22-6001-2022, https://doi.org/10.5194/acp-22-6001-2022, 2022
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We study secondary organic aerosol (SOA) from β-caryophyllene (BCP) ozonolysis with and without nitrogen oxides over 213–313 K in the simulation chamber. The yields and the rate constants were determined at 243–313 K. Chemical compositions varied at different temperatures, indicating a strong impact on the BCP ozonolysis pathways. This work helps to better understand the SOA from BCP ozonolysis for conditions representative of the real atmosphere from the boundary layer to the upper troposphere.
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.
Andrew J. Lindsay, Daniel C. Anderson, Rebecca A. Wernis, Yutong Liang, Allen H. Goldstein, Scott C. Herndon, Joseph R. Roscioli, Christoph Dyroff, Ed C. Fortner, Philip L. Croteau, Francesca Majluf, Jordan E. Krechmer, Tara I. Yacovitch, Walter B. Knighton, and Ezra C. Wood
Atmos. Chem. Phys., 22, 4909–4928, https://doi.org/10.5194/acp-22-4909-2022, https://doi.org/10.5194/acp-22-4909-2022, 2022
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Wildfire smoke dramatically impacts air quality and often has elevated concentrations of ozone. We present measurements of ozone and its precursors at a rural site periodically impacted by wildfire smoke. Measurements of total peroxy radicals, key ozone precursors that have been studied little within wildfires, compare well with chemical box model predictions. Our results indicate no serious issues with using current chemistry mechanisms to model chemistry in aged wildfire plumes.
Douglas A. Day, Pedro Campuzano-Jost, Benjamin A. Nault, Brett B. Palm, Weiwei Hu, Hongyu Guo, Paul J. Wooldridge, Ronald C. Cohen, Kenneth S. Docherty, J. Alex Huffman, Suzane S. de Sá, Scot T. Martin, and Jose L. Jimenez
Atmos. Meas. Tech., 15, 459–483, https://doi.org/10.5194/amt-15-459-2022, https://doi.org/10.5194/amt-15-459-2022, 2022
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Particle-phase nitrates are an important component of atmospheric aerosols and chemistry. In this paper, we systematically explore the application of aerosol mass spectrometry (AMS) to quantify the organic and inorganic nitrate fractions of aerosols in the atmosphere. While AMS has been used for a decade to quantify nitrates, methods are not standardized. We make recommendations for a more universal approach based on this analysis of a large range of field and laboratory observations.
Jing Cai, Cheng Wu, Jiandong Wang, Wei Du, Feixue Zheng, Simo Hakala, Xiaolong Fan, Biwu Chu, Lei Yao, Zemin Feng, Yongchun Liu, Yele Sun, Jun Zheng, Chao Yan, Federico Bianchi, Markku Kulmala, Claudia Mohr, and Kaspar R. Daellenbach
Atmos. Chem. Phys., 22, 1251–1269, https://doi.org/10.5194/acp-22-1251-2022, https://doi.org/10.5194/acp-22-1251-2022, 2022
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This study investigates the connection between organic aerosol (OA) molecular composition and particle absorptive properties in autumn in Beijing. We find that the molecular properties of OA compounds in different episodes influence particle light absorption properties differently: the light absorption enhancement of black carbon and light absorption coefficient of brown carbon were mostly related to more oxygenated OA (low C number and four O atoms) and aromatics/nitro-aromatics, respectively.
Juliana Gil-Loaiza, Joseph R. Roscioli, Joanne H. Shorter, Till H. M. Volkmann, Wei-Ren Ng, Jordan E. Krechmer, and Laura K. Meredith
Biogeosciences, 19, 165–185, https://doi.org/10.5194/bg-19-165-2022, https://doi.org/10.5194/bg-19-165-2022, 2022
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We evaluated a new diffusive soil probe integrated with high-resolution gas analyzers to measure soil gases in real time at a centimeter scale. Using columns with simple silica and soil, we captured changes in carbon dioxide (CO2), volatile organic compounds (VOCs), and nitrous oxide (N2O) with its isotopes to distinguish potential nutrient sources and microbial metabolism. This approach will advance the use of soil gases as important signals to understand and monitor soil fertility and health.
Ditte Taipale, Veli-Matti Kerminen, Mikael Ehn, Markku Kulmala, and Ülo Niinemets
Atmos. Chem. Phys., 21, 17389–17431, https://doi.org/10.5194/acp-21-17389-2021, https://doi.org/10.5194/acp-21-17389-2021, 2021
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Larval feeding and fungal infections of leaves can greatly change the emission of volatile compounds from plants and thereby influence aerosol processes in the air. We developed a model that considers the dynamics of larvae and fungi and the dependency of the emission on the severity of stress. We show that the infections can be highly atmospherically relevant during long periods of time and at times more important to consider than the parameters that are currently used in emission models.
Zachary C. J. Decker, Michael A. Robinson, Kelley C. Barsanti, Ilann Bourgeois, Matthew M. Coggon, Joshua P. DiGangi, Glenn S. Diskin, Frank M. Flocke, Alessandro Franchin, Carley D. Fredrickson, Georgios I. Gkatzelis, Samuel R. Hall, Hannah Halliday, Christopher D. Holmes, L. Gregory Huey, Young Ro Lee, Jakob Lindaas, Ann M. Middlebrook, Denise D. Montzka, Richard Moore, J. Andrew Neuman, John B. Nowak, Brett B. Palm, Jeff Peischl, Felix Piel, Pamela S. Rickly, Andrew W. Rollins, Thomas B. Ryerson, Rebecca H. Schwantes, Kanako Sekimoto, Lee Thornhill, Joel A. Thornton, Geoffrey S. Tyndall, Kirk Ullmann, Paul Van Rooy, Patrick R. Veres, Carsten Warneke, Rebecca A. Washenfelder, Andrew J. Weinheimer, Elizabeth Wiggins, Edward Winstead, Armin Wisthaler, Caroline Womack, and Steven S. Brown
Atmos. Chem. Phys., 21, 16293–16317, https://doi.org/10.5194/acp-21-16293-2021, https://doi.org/10.5194/acp-21-16293-2021, 2021
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To understand air quality impacts from wildfires, we need an accurate picture of how wildfire smoke changes chemically both day and night as sunlight changes the chemistry of smoke. We present a chemical analysis of wildfire smoke as it changes from midday through the night. We use aircraft observations from the FIREX-AQ field campaign with a chemical box model. We find that even under sunlight typical
nighttimechemistry thrives and controls the fate of key smoke plume chemical processes.
Dongyu S. Wang, Chuan Ping Lee, Jordan E. Krechmer, Francesca Majluf, Yandong Tong, Manjula R. Canagaratna, Julia Schmale, André S. H. Prévôt, Urs Baltensperger, Josef Dommen, Imad El Haddad, Jay G. Slowik, and David M. Bell
Atmos. Meas. Tech., 14, 6955–6972, https://doi.org/10.5194/amt-14-6955-2021, https://doi.org/10.5194/amt-14-6955-2021, 2021
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To understand the sources and fate of particulate matter in the atmosphere, the ability to quantitatively describe its chemical composition is essential. In this work, we developed a calibration method for a state-of-the-art measurement technique without the need for chemical standards. Statistical analyses identified the driving factors behind instrument sensitivity variability towards individual components of particulate matter.
Chenyang Bi, Jordan E. Krechmer, Graham O. Frazier, Wen Xu, Andrew T. Lambe, Megan S. Claflin, Brian M. Lerner, John T. Jayne, Douglas R. Worsnop, Manjula R. Canagaratna, and Gabriel Isaacman-VanWertz
Atmos. Meas. Tech., 14, 6835–6850, https://doi.org/10.5194/amt-14-6835-2021, https://doi.org/10.5194/amt-14-6835-2021, 2021
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Iodide-adduct chemical ionization mass spectrometry (I-CIMS) has been widely used to analyze airborne organics. In this study, I-CIMS sensitivities of isomers within a formula are found to generally vary by 1 and up to 2 orders of magnitude. Comparisons between measured and predicted moles, obtained using a voltage-scanning calibration approach, show that predictions for individual compounds or formulas might carry high uncertainty, yet the summed moles of analytes agree reasonably well.
Chenyang Bi, Jordan E. Krechmer, Manjula R. Canagaratna, and Gabriel Isaacman-VanWertz
Atmos. Meas. Tech., 14, 6551–6560, https://doi.org/10.5194/amt-14-6551-2021, https://doi.org/10.5194/amt-14-6551-2021, 2021
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Calibration techniques have been recently developed to log-linearly correlate analyte sensitivity with CIMS operating conditions particularly for compounds without authentic standards. In this work, we examine the previously ignored bias in the log-linear-based calibration method and estimate an average bias of 30 %, with 1 order of magnitude for less sensitive compounds in some circumstances. A step-by-step guide was provided to reduce and even remove the bias.
Cheng Wu, David M. Bell, Emelie L. Graham, Sophie Haslett, Ilona Riipinen, Urs Baltensperger, Amelie Bertrand, Stamatios Giannoukos, Janne Schoonbaert, Imad El Haddad, Andre S. H. Prevot, Wei Huang, and Claudia Mohr
Atmos. Chem. Phys., 21, 14907–14925, https://doi.org/10.5194/acp-21-14907-2021, https://doi.org/10.5194/acp-21-14907-2021, 2021
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Night-time reactions of biogenic volatile organic compounds and nitrate radicals can lead to the formation of secondary organic aerosol (BSOANO3). Here, we study the impacts of light exposure on the BSOANO3 from three biogenic precursors. Our results suggest that photolysis causes photodegradation of a substantial fraction of BSOANO3, changes the chemical composition and bulk volatility, and might be a potentially important loss pathway of BSOANO3 during the night-to-day transition.
Yuliang Liu, Wei Nie, Yuanyuan Li, Dafeng Ge, Chong Liu, Zhengning Xu, Liangduo Chen, Tianyi Wang, Lei Wang, Peng Sun, Ximeng Qi, Jiaping Wang, Zheng Xu, Jian Yuan, Chao Yan, Yanjun Zhang, Dandan Huang, Zhe Wang, Neil M. Donahue, Douglas Worsnop, Xuguang Chi, Mikael Ehn, and Aijun Ding
Atmos. Chem. Phys., 21, 14789–14814, https://doi.org/10.5194/acp-21-14789-2021, https://doi.org/10.5194/acp-21-14789-2021, 2021
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Oxygenated organic molecules (OOMs) are crucial intermediates linking volatile organic compounds to secondary organic aerosols. Using nitrate time-of-flight chemical ionization mass spectrometry in eastern China, we performed positive matrix factorization (PMF) on binned OOM mass spectra. We reconstructed over 1000 molecules from 14 derived PMF factors and identified about 72 % of the observed OOMs as organic nitrates, highlighting the decisive role of NOx in OOM formation in populated areas.
Emma Lumiaro, Milica Todorović, Theo Kurten, Hanna Vehkamäki, and Patrick Rinke
Atmos. Chem. Phys., 21, 13227–13246, https://doi.org/10.5194/acp-21-13227-2021, https://doi.org/10.5194/acp-21-13227-2021, 2021
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The study of climate change relies on climate models, which require an understanding of aerosol formation. We train a machine-learning model to predict the partitioning coefficients of atmospheric molecules, which govern condensation into aerosols. The model can make instant predictions based on molecular structures with accuracy surpassing that of standard computational methods. This will allow the screening of low-volatility molecules that contribute most to aerosol formation.
Hong Ren, Wei Hu, Lianfang Wei, Siyao Yue, Jian Zhao, Linjie Li, Libin Wu, Wanyu Zhao, Lujie Ren, Mingjie Kang, Qiaorong Xie, Sihui Su, Xiaole Pan, Zifa Wang, Yele Sun, Kimitaka Kawamura, and Pingqing Fu
Atmos. Chem. Phys., 21, 12949–12963, https://doi.org/10.5194/acp-21-12949-2021, https://doi.org/10.5194/acp-21-12949-2021, 2021
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This study presents vertical profiles of biogenic and anthropogenic secondary organic aerosols (SOAs) in the urban boundary layer based on a 325 m tower in Beijing in late summer. The increases in the isoprene and toluene SOAs with height were found to be more related to regional transport, whereas the decrease in those from monoterpenes and sesquiterpene were more subject to local emissions. Such complicated vertical distributions of SOA should be considered in future modeling work.
Janne Lampilahti, Hanna E. Manninen, Tuomo Nieminen, Sander Mirme, Mikael Ehn, Iida Pullinen, Katri Leino, Siegfried Schobesberger, Juha Kangasluoma, Jenni Kontkanen, Emma Järvinen, Riikka Väänänen, Taina Yli-Juuti, Radovan Krejci, Katrianne Lehtipalo, Janne Levula, Aadu Mirme, Stefano Decesari, Ralf Tillmann, Douglas R. Worsnop, Franz Rohrer, Astrid Kiendler-Scharr, Tuukka Petäjä, Veli-Matti Kerminen, Thomas F. Mentel, and Markku Kulmala
Atmos. Chem. Phys., 21, 12649–12663, https://doi.org/10.5194/acp-21-12649-2021, https://doi.org/10.5194/acp-21-12649-2021, 2021
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We studied aerosol particle formation and growth in different parts of the planetary boundary layer at two different locations (Po Valley, Italy, and Hyytiälä, Finland). The observations consist of airborne measurements on board an instrumented Zeppelin and a small airplane combined with comprehensive ground-based measurements.
Louise N. Jensen, Manjula R. Canagaratna, Kasper Kristensen, Lauriane L. J. Quéléver, Bernadette Rosati, Ricky Teiwes, Marianne Glasius, Henrik B. Pedersen, Mikael Ehn, and Merete Bilde
Atmos. Chem. Phys., 21, 11545–11562, https://doi.org/10.5194/acp-21-11545-2021, https://doi.org/10.5194/acp-21-11545-2021, 2021
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This work targets the chemical composition of α-pinene-derived secondary organic aerosol (SOA) formed in the temperature range from -15 to 20°C. Experiments were conducted in an atmospheric simulation chamber. Positive matrix factorization analysis of data obtained by a high-resolution time-of-flight aerosol mass spectrometer shows that the elemental aerosol composition is controlled by the initial α-pinene concentration and temperature during SOA formation.
Xiaolong Fan, Jing Cai, Chao Yan, Jian Zhao, Yishuo Guo, Chang Li, Kaspar R. Dällenbach, Feixue Zheng, Zhuohui Lin, Biwu Chu, Yonghong Wang, Lubna Dada, Qiaozhi Zha, Wei Du, Jenni Kontkanen, Theo Kurtén, Siddhart Iyer, Joni T. Kujansuu, Tuukka Petäjä, Douglas R. Worsnop, Veli-Matti Kerminen, Yongchun Liu, Federico Bianchi, Yee Jun Tham, Lei Yao, and Markku Kulmala
Atmos. Chem. Phys., 21, 11437–11452, https://doi.org/10.5194/acp-21-11437-2021, https://doi.org/10.5194/acp-21-11437-2021, 2021
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We observed significant concentrations of gaseous HBr and HCl throughout the winter and springtime in urban Beijing, China. Our results indicate that gaseous HCl and HBr are most likely originated from anthropogenic emissions such as burning activities, and the gas–aerosol partitioning may play a crucial role in contributing to the gaseous HCl and HBr. These observations suggest that there is an important recycling pathway of halogen species in inland megacities.
Liine Heikkinen, Mikko Äijälä, Kaspar R. Daellenbach, Gang Chen, Olga Garmash, Diego Aliaga, Frans Graeffe, Meri Räty, Krista Luoma, Pasi Aalto, Markku Kulmala, Tuukka Petäjä, Douglas Worsnop, and Mikael Ehn
Atmos. Chem. Phys., 21, 10081–10109, https://doi.org/10.5194/acp-21-10081-2021, https://doi.org/10.5194/acp-21-10081-2021, 2021
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In many locations worldwide aerosol particles have been shown to be made up of organic aerosol (OA). The boreal forest is a region where aerosol particles possess a high OA mass fraction. Here, we studied OA composition using the longest time series of OA composition ever obtained from a boreal environment. For this purpose, we tested a new analysis framework and discovered that most of the OA was highly oxidized, with strong seasonal behaviour reflecting different sources in summer and winter.
Xueshun Chen, Fangqun Yu, Wenyi Yang, Yele Sun, Huansheng Chen, Wei Du, Jian Zhao, Ying Wei, Lianfang Wei, Huiyun Du, Zhe Wang, Qizhong Wu, Jie Li, Junling An, and Zifa Wang
Atmos. Chem. Phys., 21, 9343–9366, https://doi.org/10.5194/acp-21-9343-2021, https://doi.org/10.5194/acp-21-9343-2021, 2021
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Atmospheric aerosol particles have significant climate and health effects that depend on aerosol size, composition, and mixing state. A new global-regional nested aerosol model with an advanced particle microphysics module and a volatility basis set organic aerosol module was developed to simulate aerosol microphysical processes. Simulations strongly suggest the important role of anthropogenic organic species in particle formation over the areas influenced by anthropogenic sources.
Wei Huang, Haiyan Li, Nina Sarnela, Liine Heikkinen, Yee Jun Tham, Jyri Mikkilä, Steven J. Thomas, Neil M. Donahue, Markku Kulmala, and Federico Bianchi
Atmos. Chem. Phys., 21, 8961–8977, https://doi.org/10.5194/acp-21-8961-2021, https://doi.org/10.5194/acp-21-8961-2021, 2021
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We show full characterization of gaseous organic compounds in a boreal forest. Molecular composition and volatility of gaseous organic compounds with different oxidation extents (from volatile organic compounds to highly oxygenated organic molecules) were investigated and discussed. We provide a more comprehensive understanding of atmospheric organic compounds in this boreal forest and new insights into interpreting ambient measurements or testing and improving parameterizations in models.
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.
Chenshuo Ye, Bin Yuan, Yi Lin, Zelong Wang, Weiwei Hu, Tiange Li, Wei Chen, Caihong Wu, Chaomin Wang, Shan Huang, Jipeng Qi, Baolin Wang, Chen Wang, Wei Song, Xinming Wang, E Zheng, Jordan E. Krechmer, Penglin Ye, Zhanyi Zhang, Xuemei Wang, Douglas R. Worsnop, and Min Shao
Atmos. Chem. Phys., 21, 8455–8478, https://doi.org/10.5194/acp-21-8455-2021, https://doi.org/10.5194/acp-21-8455-2021, 2021
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We performed measurements of gaseous and particulate organic compounds using a state-of-the-art online mass spectrometer in urban air. Using the dataset, we provide a holistic chemical characterization of oxygenated organic compounds in the polluted urban atmosphere, which can serve as a reference for the future field measurements of organic compounds in cities.
Chenyang Bi, Jordan E. Krechmer, Graham O. Frazier, Wen Xu, Andrew T. Lambe, Megan S. Claflin, Brian M. Lerner, John T. Jayne, Douglas R. Worsnop, Manjula R. Canagaratna, and Gabriel Isaacman-VanWertz
Atmos. Meas. Tech., 14, 3895–3907, https://doi.org/10.5194/amt-14-3895-2021, https://doi.org/10.5194/amt-14-3895-2021, 2021
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Measurement techniques that can achieve molecular characterizations are necessary to understand the differences of fate and transport within isomers produced in the atmospheric oxidation process. In this work, we develop an instrument to conduct isomer-resolved measurements of particle-phase organics. We assess the number of isomers per chemical formula in atmospherically relevant samples and examine the feasibility of extending the use of an existing instrument to a broader range of analytes.
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.
Runlong Cai, Yihao Li, Yohann Clément, Dandan Li, Clément Dubois, Marlène Fabre, Laurence Besson, Sebastien Perrier, Christian George, Mikael Ehn, Cheng Huang, Ping Yi, Yingge Ma, and Matthieu Riva
Atmos. Meas. Tech., 14, 2377–2387, https://doi.org/10.5194/amt-14-2377-2021, https://doi.org/10.5194/amt-14-2377-2021, 2021
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Orbitool is an open-source software tool, mainly coded in Python, with a graphical user interface (GUI), specifically developed to facilitate the analysis of online Orbitrap mass spectrometric data. It is notably optimized for long-term atmospheric measurements and laboratory studies.
Melinda K. Schueneman, Benjamin A. Nault, Pedro Campuzano-Jost, Duseong S. Jo, Douglas A. Day, Jason C. Schroder, Brett B. Palm, Alma Hodzic, Jack E. Dibb, and Jose L. Jimenez
Atmos. Meas. Tech., 14, 2237–2260, https://doi.org/10.5194/amt-14-2237-2021, https://doi.org/10.5194/amt-14-2237-2021, 2021
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This work focuses on two important properties of the aerosol, acidity, and sulfate composition, which is important for our understanding of aerosol health and environmental impacts. We explore different methods to understand the composition of the aerosol with measurements from a specific instrument and apply those methods to a large dataset. These measurements are confounded by other factors, making it challenging to predict aerosol sulfate composition; pH estimations, however, show promise.
Haiyan Li, Manjula R. Canagaratna, Matthieu Riva, Pekka Rantala, Yanjun Zhang, Steven Thomas, Liine Heikkinen, Pierre-Marie Flaud, Eric Villenave, Emilie Perraudin, Douglas Worsnop, Markku Kulmala, Mikael Ehn, and Federico Bianchi
Atmos. Chem. Phys., 21, 4123–4147, https://doi.org/10.5194/acp-21-4123-2021, https://doi.org/10.5194/acp-21-4123-2021, 2021
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For the first time, we performed binPMF analysis on the complex mass spectra acquired with the Vocus PTR-TOF in two European pine forests and identified various primary emission sources and secondary oxidation processes of atmospheric organic vapors, i.e., terpenes and their oxidation products, with varying oxidation degrees. Further insights were gained regarding monoterpene and sesquiterpene reactions based on the interpretation results.
Michael Priestley, Thomas J. Bannan, Michael Le Breton, Stephen D. Worrall, Sungah Kang, Iida Pullinen, Sebastian Schmitt, Ralf Tillmann, Einhard Kleist, Defeng Zhao, Jürgen Wildt, Olga Garmash, Archit Mehra, Asan Bacak, Dudley E. Shallcross, Astrid Kiendler-Scharr, Åsa M. Hallquist, Mikael Ehn, Hugh Coe, Carl J. Percival, Mattias Hallquist, Thomas F. Mentel, and Gordon McFiggans
Atmos. Chem. Phys., 21, 3473–3490, https://doi.org/10.5194/acp-21-3473-2021, https://doi.org/10.5194/acp-21-3473-2021, 2021
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A significant fraction of emissions from human activity consists of aromatic hydrocarbons, e.g. benzene, which oxidise to form new compounds important for particle growth. Characterisation of benzene oxidation products highlights the range of species produced as well as their chemical properties and contextualises them within relevant frameworks, e.g. MCM. Cluster analysis of the oxidation product time series distinguishes behaviours of CHON compounds that could aid in identifying functionality.
Demetrios Pagonis, Pedro Campuzano-Jost, Hongyu Guo, Douglas A. Day, Melinda K. Schueneman, Wyatt L. Brown, Benjamin A. Nault, Harald Stark, Kyla Siemens, Alex Laskin, Felix Piel, Laura Tomsche, Armin Wisthaler, Matthew M. Coggon, Georgios I. Gkatzelis, Hannah S. Halliday, Jordan E. Krechmer, Richard H. Moore, David S. Thomson, Carsten Warneke, Elizabeth B. Wiggins, and Jose L. Jimenez
Atmos. Meas. Tech., 14, 1545–1559, https://doi.org/10.5194/amt-14-1545-2021, https://doi.org/10.5194/amt-14-1545-2021, 2021
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We describe the airborne deployment of an extractive electrospray time-of-flight mass spectrometer (EESI-MS). The instrument provides a quantitative 1 Hz measurement of the chemical composition of organic aerosol up to altitudes of
7 km, with single-compound detection limits as low as 50 ng per standard cubic meter.
Georgia Michailoudi, Jack J. Lin, Hayato Yuzawa, Masanari Nagasaka, Marko Huttula, Nobuhiro Kosugi, Theo Kurtén, Minna Patanen, and Nønne L. Prisle
Atmos. Chem. Phys., 21, 2881–2894, https://doi.org/10.5194/acp-21-2881-2021, https://doi.org/10.5194/acp-21-2881-2021, 2021
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This study provides insight into hydration of two significant atmospheric compounds, glyoxal and methylglyoxal. Using synchrotron radiation excited X-ray absorption spectroscopy, we confirm that glyoxal is fully hydrated in water, and for the first time, we experimentally detect enol structures in aqueous methylglyoxal. Our results support the contribution of these compounds to secondary organic aerosol formation, known to have a large uncertainty in atmospheric models and climate predictions.
Arttu Ylisirniö, Luis M. F. Barreira, Iida Pullinen, Angela Buchholz, John Jayne, Jordan E. Krechmer, Douglas R. Worsnop, Annele Virtanen, and Siegfried Schobesberger
Atmos. Meas. Tech., 14, 355–367, https://doi.org/10.5194/amt-14-355-2021, https://doi.org/10.5194/amt-14-355-2021, 2021
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FIGAERO-ToF-CIMS enables online volatility measurements of chemical compounds in ambient aerosols. Previously published volatility calibration results however differ from each other significantly. In this study we investigate the reason for this discrepancy. We found a major source of error in the widely used syringe deposition method and propose a new method for volatility calibration by using atomized calibration compounds.
Anna Shcherbacheva, Tracey Balehowsky, Jakub Kubečka, Tinja Olenius, Tapio Helin, Heikki Haario, Marko Laine, Theo Kurtén, and Hanna Vehkamäki
Atmos. Chem. Phys., 20, 15867–15906, https://doi.org/10.5194/acp-20-15867-2020, https://doi.org/10.5194/acp-20-15867-2020, 2020
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Atmospheric new particle formation and cluster growth to aerosol particles is an important field of research, in particular due to the climate change phenomenon. Evaporation rates are very difficult to account for but they are important to explain the formation and growth of particles. Different quantum chemistry (QC) methods produce substantially different values for the evaporation rates. We propose a novel approach for inferring evaporation rates of clusters from available measurements.
Junfeng Wang, Jianhuai Ye, Dantong Liu, Yangzhou Wu, Jian Zhao, Weiqi Xu, Conghui Xie, Fuzhen Shen, Jie Zhang, Paul E. Ohno, Yiming Qin, Xiuyong Zhao, Scot T. Martin, Alex K. Y. Lee, Pingqing Fu, Daniel J. Jacob, Qi Zhang, Yele Sun, Mindong Chen, and Xinlei Ge
Atmos. Chem. Phys., 20, 14091–14102, https://doi.org/10.5194/acp-20-14091-2020, https://doi.org/10.5194/acp-20-14091-2020, 2020
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We compared the organics in total submicron matter and those coated on BC cores during summertime in Beijing and found large differences between them. Traffic-related OA was associated significantly with BC, while cooking-related OA did not coat BC. In addition, a factor likely originated from primary biomass burning OA was only identified in BC-containing particles. Such a unique BBOA requires further field and laboratory studies to verify its presence and elucidate its properties and impacts.
Benjamin A. Nault, Pedro Campuzano-Jost, Douglas A. Day, Hongyu Guo, Duseong S. Jo, Anne V. Handschy, Demetrios Pagonis, Jason C. Schroder, Melinda K. Schueneman, Michael J. Cubison, Jack E. Dibb, Alma Hodzic, Weiwei Hu, Brett B. Palm, and Jose L. Jimenez
Atmos. Meas. Tech., 13, 6193–6213, https://doi.org/10.5194/amt-13-6193-2020, https://doi.org/10.5194/amt-13-6193-2020, 2020
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Collecting particulate matter, or aerosols, onto filters to be analyzed offline is a widely used method to investigate the mass concentration and chemical composition of the aerosol, especially the inorganic portion. Here, we show that acidic aerosol (sulfuric acid) collected onto filters and then exposed to high ammonia mixing ratios (from human emissions) will lead to biases in the ammonium collected onto filters, and the uptake of ammonia is rapid (< 10 s), which impacts the filter data.
Noora Hyttinen, Reyhaneh Heshmatnezhad, Jonas Elm, Theo Kurtén, and Nønne L. Prisle
Atmos. Chem. Phys., 20, 13131–13143, https://doi.org/10.5194/acp-20-13131-2020, https://doi.org/10.5194/acp-20-13131-2020, 2020
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We present aqueous solubilities and activity coefficients of mono- and dicarboxylic acids (C1–C6 and C2–C8, respectively) estimated using the COSMOtherm program. In addition, we have calculated effective equilibrium constants of dimerization and hydration of the same acids in the condensed phase. We were also able to improve the agreement between experimental and estimated properties of monocarboxylic acids in aqueous solutions by including clustering reactions in COSMOtherm calculations.
Jing Cai, Biwu Chu, Lei Yao, Chao Yan, Liine M. Heikkinen, Feixue Zheng, Chang Li, Xiaolong Fan, Shaojun Zhang, Daoyuan Yang, Yonghong Wang, Tom V. Kokkonen, Tommy Chan, Ying Zhou, Lubna Dada, Yongchun Liu, Hong He, Pauli Paasonen, Joni T. Kujansuu, Tuukka Petäjä, Claudia Mohr, Juha Kangasluoma, Federico Bianchi, Yele Sun, Philip L. Croteau, Douglas R. Worsnop, Veli-Matti Kerminen, Wei Du, Markku Kulmala, and Kaspar R. Daellenbach
Atmos. Chem. Phys., 20, 12721–12740, https://doi.org/10.5194/acp-20-12721-2020, https://doi.org/10.5194/acp-20-12721-2020, 2020
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By applying both OA PMF and size PMF at the same urban measurement site in Beijing, similar particle source types, including vehicular emissions, cooking emissions and secondary formation-related sources, were resolved by both frameworks and agreed well. It is also found that in the absence of new particle formation, vehicular and cooking emissions dominate the particle number concentration, while secondary particulate matter governed PM2.5 mass during spring and summer in Beijing.
Kasper Kristensen, Louise N. Jensen, Lauriane L. J. Quéléver, Sigurd Christiansen, Bernadette Rosati, Jonas Elm, Ricky Teiwes, Henrik B. Pedersen, Marianne Glasius, Mikael Ehn, and Merete Bilde
Atmos. Chem. Phys., 20, 12549–12567, https://doi.org/10.5194/acp-20-12549-2020, https://doi.org/10.5194/acp-20-12549-2020, 2020
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Atmospheric particles are important in relation to human health and the global climate. As the global temperature changes, so may the atmospheric chemistry controlling the formation of particles from reactions of naturally emitted volatile organic compounds (VOCs). In the current work, we show how temperatures influence the formation and chemical composition of atmospheric particles from α-pinene: a biogenic VOC largely emitted in high-latitude environments such as the boreal forests.
Archit Mehra, Jordan E. Krechmer, Andrew Lambe, Chinmoy Sarkar, Leah Williams, Farzaneh Khalaj, Alex Guenther, John Jayne, Hugh Coe, Douglas Worsnop, Celia Faiola, and Manjula Canagaratna
Atmos. Chem. Phys., 20, 10953–10965, https://doi.org/10.5194/acp-20-10953-2020, https://doi.org/10.5194/acp-20-10953-2020, 2020
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Emissions of volatile organic compounds (VOCs) from plants are important for tropospheric ozone and secondary organic aerosol (SOA) formation. Real plant emissions are much more diverse than the few proxies widely used for studies of plant SOA. Here we present the first study of SOA from Californian sage plants and the oxygenated monoterpenes representing their major emissions. We identify SOA products and show the importance of the formation of highly oxygenated organic molecules and oligomers.
Cited articles
Aprea, E., Biasioli, F., Märk, T. D., and Gasperi, F.: PTR-MS study of
esters in water and water/ethanol solutions: Fragmentation patterns and
partition coefficients, Int. J. Mass Spectrom., 262,
114–121, https://doi.org/10.1016/j.ijms.2006.10.016, 2007.
Aschmann, S. M., Arey, J., and Atkinson, R.: Kinetics and Products of the
Reactions of OH Radicals with Cyclohexene, 1-Methyl-1-cyclohexene,
cis-Cyclooctene, and cis-Cyclodecene, J. Phys. Chem. A,
116, 9507–9515, https://doi.org/10.1021/jp307217m, 2012.
Barker, J. R.: Energy transfer in master equation simulations: A new
approach, International Journal of Chemical Kinetics, 41, 748–763,
https://doi.org/10.1002/kin.20447, 2009.
Barker, J. R. and Weston, R. E.: Collisional Energy Transfer Probability
Densities P(E, J; E', J') for Monatomics Colliding with Large Molecules, J. Phys. Chem. A, 114, 10619–10633, https://doi.org/10.1021/jp106443d, 2010.
Becke, A. D.: A new mixing of Hartree-Fock and Local Density-Functional
Theories, J. Chem. Phys., 98, 1372–1377, https://doi.org/10.1063/1.464304, 1993.
Berndt, T., Mentler, B., Scholz, W., Fischer, L., Herrmann, H., Kulmala, M.,
and Hansel, A.: Accretion Product Formation from Ozonolysis and OH Radical
Reaction of α-Pinene: Mechanistic Insight and the Influence of
Isoprene and Ethylene, Environ. Sci. Technol., 52,
11069–11077, https://doi.org/10.1021/acs.est.8b02210, 2018a.
Berndt, T., Scholz, W., Mentler, B., Fischer, L., Herrmann, H., Kulmala, M.,
and Hansel, A.: Accretion Product Formation from Self- and Cross-Reactions
of RO2 Radicals in the Atmosphere, Angew. Chem. Int. Edit.,
57, 3820–3824, https://doi.org/10.1002/anie.201710989, 2018b.
Bernhammer, A.-K., Fischer, L., Mentler, B., Heinritzi, M., Simon, M., and Hansel, A.: Production of highly oxygenated organic molecules (HOMs) from trace contaminants during isoprene oxidation, Atmos. Meas. Tech., 11, 4763–4773, https://doi.org/10.5194/amt-11-4763-2018, 2018.
Bertram, T. H., Kimmel, J. R., Crisp, T. A., Ryder, O. S., Yatavelli, R. L. N., Thornton, J. A., Cubison, M. J., Gonin, M., and Worsnop, D. R.: A field-deployable, chemical ionization time-of-flight mass spectrometer, Atmos. Meas. Tech., 4, 1471–1479, https://doi.org/10.5194/amt-4-1471-2011, 2011.
Bianchi, F., Kurtén, T., Riva, M., Mohr, C., Rissanen, M. P., Roldin,
P., Berndt, T., Crounse, J. D., Wennberg, P. O., Mentel, T. F., Wildt, J.,
Junninen, H., Jokinen, T., Kulmala, M., Worsnop, D. R., Thornton, J. A.,
Donahue, N., Kjaergaard, H. G., and Ehn, M.: Highly Oxygenated Organic
Molecules (HOM) from Gas-Phase Autoxidation Involving Peroxy Radicals: A Key
Contributor to Atmospheric Aerosol, Chem. Rev., 119, 3472–3509, https://doi.org/10.1021/acs.chemrev.8b00395, 2019.
Breitenlechner, M., Fischer, L., Hainer, M., Heinritzi, M., Curtius, J., and
Hansel, A.: PTR3: An Instrument for Studying the Lifecycle of Reactive
Organic Carbon in the Atmosphere, Anal. Chem., 89, 5824–5831, https://doi.org/10.1021/acs.analchem.6b05110, 2017.
Carter, W. P. L.: Development of Ozone Reactivity Scales for Volatile
Organic Compounds, Air & Waste, 44, 881–899, https://doi.org/10.1080/1073161X.1994.10467290, 1994.
Chai, J. D. and Head-Gordon, M.: Long-range corrected hybrid density
functionals with damped atom-atom dispersion corrections, Phys. Chem. Chem.
Phys., 10, 6615–6620, https://doi.org/10.1039/b810189b, 2008.
Charlson, R. J., Schwartz, S. E., Hales, J. M., Cess, R. D., Coakley, J. A.,
Hansen, J. E., and Hofmann, D. J.: Climate Forcing by Anthropogenic
Aerosols, Science, 255, 423–430, https://doi.org/10.1126/science.255.5043.423, 1992.
Chen, X., Hopke, P. K., and Carter, W. P. L.: Secondary Organic Aerosol from
Ozonolysis of Biogenic Volatile Organic Compounds: Chamber Studies of
Particle and Reactive Oxygen Species Formation, Environ. Sci. Technol., 45, 276–282, https://doi.org/10.1021/es102166c, 2011.
Crounse, J. D., Nielsen, L. B., Jørgensen, S., Kjaergaard, H. G., and
Wennberg, P. O.: Autoxidation of Organic Compounds in the Atmosphere,
J. Phys. Chem. Lett., 4, 3513–3520, https://doi.org/10.1021/jz4019207,
2013.
Donahue, N. M., Kroll, J. H., Pandis, S. N., and Robinson, A. L.: A two-dimensional volatility basis set – Part 2: Diagnostics of organic-aerosol evolution, Atmos. Chem. Phys., 12, 615–634, https://doi.org/10.5194/acp-12-615-2012, 2012.
Ehn, M., Thornton, J. A., Kleist, E., Sipilä, M., Junninen, H.,
Pullinen, I., Springer, M., Rubach, F., Tillmann, R., Lee, B.,
Lopez-Hilfiker, F., Andres, S., Acir, I.-H., Rissanen, M., Jokinen, T.,
Schobesberger, S., Kangasluoma, J., Kontkanen, J., Nieminen, T., Kurtén,
T., Nielsen, L. B., Jørgensen, S., Kjaergaard, H. G., Canagaratna, M.,
Maso, M. D., Berndt, T., Petäjä, T., Wahner, A., Kerminen, V.-M.,
Kulmala, M., Worsnop, D. R., Wildt, J., and Mentel, T. F.: A large source of
low-volatility secondary organic aerosol, Nature, 506, 476–479, https://doi.org/10.1038/nature13032, 2014.
Friedrich, R. and Obermeier, A.: Chapter 1 – Anthropogenic Emissions of
Volatile Organic Compounds, in: Reactive Hydrocarbons in the Atmosphere,
edited by: Hewitt, C. N., Academic Press, San Diego, 1–39, https://doi.org/10.1016/B978-012346240-4/50002-3, 1999.
Glowacki, D. R., Liang, C. H., Morley, C., Pilling, M. J., and Robertson, S.
H.: MESMER: An Open-Source Master Equation Solver for Multi-Energy Well
Reactions, J. Phys. Chem. A, 116, 9545–9560, https://doi.org/10.1021/jp3051033, 2012.
Gueneron, M., Erickson, M. H., VanderSchelden, G. S., and Jobson, B. T.:
PTR-MS fragmentation patterns of gasoline hydrocarbons, Int. J. Mass Spectrom., 379, 97–109, https://doi.org/10.1016/j.ijms.2015.01.001, 2015.
Guenther, A. B., Jiang, X., Heald, C. L., Sakulyanontvittaya, T., Duhl, T., Emmons, L. K., and Wang, X.: The Model of Emissions of Gases and Aerosols from Nature version 2.1 (MEGAN2.1): an extended and updated framework for modeling biogenic emissions, Geosci. Model Dev., 5, 1471–1492, https://doi.org/10.5194/gmd-5-1471-2012, 2012.
Halgren, T. A.: MMFF VII. Characterization of MMFF94, MMFF94s, and other
widely available force fields for conformational energies and for
intermolecular-interaction energies and geometries, J. Comput. Chem., 20,
730–748, https://doi.org/10.1002/(sici)1096-987x(199905)20:7<730::Aid-jcc8>3.3.Co;2-k, 1999.
Hansel, A., Scholz, W., Mentler, B., Fischer, L., and Berndt, T.: Detection
of RO2 radicals and other products from cyclohexene ozonolysis with NH
Huang, C., Chen, C. H., Li, L., Cheng, Z., Wang, H. L., Huang, H. Y., Streets, D. G., Wang, Y. J., Zhang, G. F., and Chen, Y. R.: Emission inventory of anthropogenic air pollutants and VOC species in the Yangtze River Delta region, China, Atmos. Chem. Phys., 11, 4105–4120, https://doi.org/10.5194/acp-11-4105-2011, 2011.
Hyttinen, N., Kupiainen-Määttä, O., Rissanen, M. P., Muuronen,
M., Ehn, M., and Kurtén, T.: Modeling the Charging of Highly Oxidized
Cyclohexene Ozonolysis Products Using Nitrate-Based Chemical Ionization, J. Phys. Chem. A, 119, 6339–6345, https://doi.org/10.1021/acs.jpca.5b01818, 2015.
Hyttinen, N., Otkjær, R. V., Iyer, S., Kjaergaard, H. G., Rissanen, M.
P., Wennberg, P. O., and Kurtén, T.: Computational Comparison of
Different Reagent Ions in the Chemical Ionization of Oxidized
Multifunctional Compounds, J. Phys. Chem. A, 122,
269–279, https://doi.org/10.1021/acs.jpca.7b10015, 2018.
Isaacman-VanWertz, G., Massoli, P., O'Brien, R., Lim, C., Franklin, J. P.,
Moss, J. A., Hunter, J. F., Nowak, J. B., Canagaratna, M. R., Misztal, P.
K., Arata, C., Roscioli, J. R., Herndon, S. T., Onasch, T. B., Lambe, A. T.,
Jayne, J. T., Su, L., Knopf, D. A., Goldstein, A. H., Worsnop, D. R., and
Kroll, J. H.: Chemical evolution of atmospheric organic carbon over multiple
generations of oxidation, Nat. Chem., 10, 462–468, https://doi.org/10.1038/s41557-018-0002-2, 2018.
Iyer, S., He, X., Hyttinen, N., Kurtén, T., and Rissanen, M. P.:
Computational and Experimental Investigation of the Detection of HO2 Radical and the Products of Its Reaction with Cyclohexene Ozonolysis Derived RO2 Radicals by an Iodide-Based Chemical Ionization Mass Spectrometer, J. Phys. Chem. A, 121, 6778–6789, https://doi.org/10.1021/acs.jpca.7b01588,
2017.
Jasper, A. W., Pelzer, K. M., Miller, J. A., Kamarchik, E., Harding, L. B.,
and Klippenstein, S. J.: Predictive a priori pressure-dependent kinetics,
Science, 346, 1212–1215, https://doi.org/10.1126/science.1260856, 2014.
Jimenez, J. L., Canagaratna, M. R., Donahue, N. M., Prevot, A. S. H., Zhang,
Q., Kroll, J. H., DeCarlo, P. F., Allan, J. D., Coe, H., Ng, N. L., Aiken,
A. C., Docherty, K. S., Ulbrich, I. M., Grieshop, A. P., Robinson, A. L.,
Duplissy, J., Smith, J. D., Wilson, K. R., Lanz, V. A., Hueglin, C., Sun, Y.
L., Tian, J., Laaksonen, A., Raatikainen, T., Rautiainen, J., Vaattovaara,
P., Ehn, M., Kulmala, M., Tomlinson, J. M., Collins, D. R., Cubison, M. J.,
Dunlea, J., Huffman, J. A., Onasch, T. B., Alfarra, M. R., Williams, P. I.,
Bower, K., Kondo, Y., Schneider, J., Drewnick, F., Borrmann, S., Weimer, S.,
Demerjian, K., Salcedo, D., Cottrell, L., Griffin, R., Takami, A., Miyoshi,
T., Hatakeyama, S., Shimono, A., Sun, J. Y., Zhang, Y. M., Dzepina, K.,
Kimmel, J. R., Sueper, D., Jayne, J. T., Herndon, S. C., Trimborn, A. M.,
Williams, L. R., Wood, E. C., Middlebrook, A. M., Kolb, C. E.,
Baltensperger, U., and Worsnop, D. R.: Evolution of Organic Aerosols in the
Atmosphere, Science, 326, 1525, https://doi.org/10.1126/science.1180353, 2009.
Jokinen, T., Sipilä, M., Junninen, H., Ehn, M., Lönn, G., Hakala, J., Petäjä, T., Mauldin III, R. L., Kulmala, M., and Worsnop, D. R.: Atmospheric sulphuric acid and neutral cluster measurements using CI-APi-TOF, Atmos. Chem. Phys., 12, 4117–4125, https://doi.org/10.5194/acp-12-4117-2012, 2012.
Kendall, R. A., Dunning, T. H., and Harrison, R. J.: Electron affinities of
the first-row atoms revisited. Systematic basis sets and wave functions,
J. Chem. Phys., 96, 6796–6806, https://doi.org/10.1063/1.462569, 1992.
Kesselmeier, J. and Staudt, M.: Biogenic Volatile Organic Compounds (VOC):
An Overview on Emission, Physiology and Ecology, J. Atmos. Chem., 33, 23–88, https://doi.org/10.1023/A:1006127516791, 1999.
Knizia, G., Adler, T. B., and Werner, H. J.: Simplified CCSD(T)-F12 methods:
Theory and benchmarks, J. Chem. Phys., 130, 054104, https://doi.org/10.1063/1.3054300, 2009.
Koopman, J. and Grimme, S.: From QCEIMS to QCxMS: A Tool to Routinely
Calculate CID Mass Spectra Using Molecular Dynamics, J. Am. Soc. Mass Spectrom., 32, 1735–1751, https://doi.org/10.1021/jasms.1c00098, 2021.
Krechmer, J., Lopez-Hilfiker, F., Koss, A., Hutterli, M., Stoermer, C.,
Deming, B., Kimmel, J., Warneke, C., Holzinger, R., Jayne, J., Worsnop, D.,
Fuhrer, K., Gonin, M., and de Gouw, J.: Evaluation of a New Reagent-Ion
Source and Focusing Ion–Molecule Reactor for Use in
Proton-Transfer-Reaction Mass Spectrometry, Anal. Chem., 90,
12011–12018, https://doi.org/10.1021/acs.analchem.8b02641, 2018.
Kupiainen-Määttä, O., Olenius, T., Kurtén, T., and
Vehkamäki, H.: CIMS Sulfuric Acid Detection Efficiency Enhanced by
Amines Due to Higher Dipole Moments: A Computational Study, J. Phys. Chem. A, 117, 14109–14119, https://doi.org/10.1021/jp4049764, 2013.
Lee, B. H., Lopez-Hilfiker, F. D., Mohr, C., Kurten, T., Worsnop, D. R., and
Thornton, J. A.: An Iodide-Adduct High-Resolution Time-of-Flight
Chemical-Ionization Mass Spectrometer: Application to Atmospheric Inorganic
and Organic Compounds, Environ. Sci. Technol., 48, 6309–6317,
2014a.
Lee, B. H., Lopez-Hilfiker, F. D., Mohr, C., Kurtén, T., Worsnop, D. R.,
and Thornton, J. A.: An Iodide-Adduct High-Resolution Time-of-Flight
Chemical-Ionization Mass Spectrometer: Application to Atmospheric Inorganic
and Organic Compounds, Environ. Sci. Technol., 48, 6309–6317, https://doi.org/10.1021/es500362a, 2014b.
Lee, C. T., Yang, W. T., and Parr, R. G.: Development of the Colle-Salvetti
correlation-energy formula into a functional of the electron-density, Phys.
Rev. B, 37, 785–789, https://doi.org/10.1103/PhysRevB.37.785, 1988.
Li, H., Riva, M., Rantala, P., Heikkinen, L., Daellenbach, K., Krechmer, J. E., Flaud, P.-M., Worsnop, D., Kulmala, M., Villenave, E., Perraudin, E., Ehn, M., and Bianchi, F.: Terpenes and their oxidation products in the French Landes forest: insights from Vocus PTR-TOF measurements, Atmos. Chem. Phys., 20, 1941–1959, https://doi.org/10.5194/acp-20-1941-2020, 2020.
Li, H., Canagaratna, M. R., Riva, M., Rantala, P., Zhang, Y., Thomas, S., Heikkinen, L., Flaud, P.-M., Villenave, E., Perraudin, E., Worsnop, D., Kulmala, M., Ehn, M., and Bianchi, F.: Atmospheric organic vapors in two European pine forests measured by a Vocus PTR-TOF: insights into monoterpene and sesquiterpene oxidation processes, Atmos. Chem. Phys., 21, 4123–4147, https://doi.org/10.5194/acp-21-4123-2021, 2021.
Lopez-Hilfiker, F. D., Pospisilova, V., Huang, W., Kalberer, M., Mohr, C., Stefenelli, G., Thornton, J. A., Baltensperger, U., Prevot, A. S. H., and Slowik, J. G.: An extractive electrospray ionization time-of-flight mass spectrometer (EESI-TOF) for online measurement of atmospheric aerosol particles, Atmos. Meas. Tech., 12, 4867–4886, https://doi.org/10.5194/amt-12-4867-2019, 2019.
Mohr, C., Thornton, J. A., Heitto, A., Lopez-Hilfiker, F. D., Lutz, A.,
Riipinen, I., Hong, J., Donahue, N. M., Hallquist, M., Petäjä, T.,
Kulmala, M., and Yli-Juuti, T.: Molecular identification of organic vapors
driving atmospheric nanoparticle growth, Nat. Commun., 10, 4442, https://doi.org/10.1038/s41467-019-12473-2, 2019.
Møller, K. H., Otkjaer, R. V., Hyttinen, N., Kurten, T., and Kjaergaard,
H. G.: Cost-Effective Implementation of Multiconformer Transition State
Theory for Peroxy Radical Hydrogen Shift Reactions, J. Phys. Chem. A, 120,
10072–10087, https://doi.org/10.1021/acs.jpca.6b09370, 2016.
Pagonis, D., Sekimoto, K., and de Gouw, J.: A Library of Proton-Transfer
Reactions of H3O+ Ions Used for Trace Gas Detection, J. Am. Soc. Mass Spectrom., 30, 1330–1335, https://doi.org/10.1007/s13361-019-02209-3, 2019.
Peräkylä, O., Riva, M., Heikkinen, L., Quéléver, L., Roldin, P., and Ehn, M.: Experimental investigation into the volatilities of highly oxygenated organic molecules (HOMs) , Atmos. Chem. Phys., 20, 649–669, https://doi.org/10.5194/acp-20-649-2020, 2020.
Rap, A., Scott, C. E., Spracklen, D. V., Bellouin, N., Forster, P. M.,
Carslaw, K. S., Schmidt, A., and Mann, G.: Natural aerosol direct and
indirect radiative effects, Geophys. Res. Lett., 40, 3297–3301, https://doi.org/10.1002/grl.50441, 2013.
Rissanen, M. P., Kurtén, T., Sipilä, M., Thornton, J. A.,
Kangasluoma, J., Sarnela, N., Junninen, H., Jørgensen, S., Schallhart,
S., Kajos, M. K., Taipale, R., Springer, M., Mentel, T. F., Ruuskanen, T.,
Petäjä, T., Worsnop, D. R., Kjaergaard, H. G., and Ehn, M.: The
Formation of Highly Oxidized Multifunctional Products in the Ozonolysis of
Cyclohexene, J. Am. Chem. Soc., 136, 15596–15606, https://doi.org/10.1021/ja507146s, 2014.
Riva, M., Rantala, P., Krechmer, J. E., Peräkylä, O., Zhang, Y., Heikkinen, L., Garmash, O., Yan, C., Kulmala, M., Worsnop, D., and Ehn, M.: Evaluating the performance of five different chemical ionization techniques for detecting gaseous oxygenated organic species, Atmos. Meas. Tech., 12, 2403–2421, https://doi.org/10.5194/amt-12-2403-2019, 2019.
Schalley, C. A., Dieterle, M., Schröder, D., Schwarz, H., and Uggerud,
E.: On the cleavage of the peroxide O-O bond in methyl hydroperoxide and dimethyl peroxide upon protonation, Int. J. Mass Spectrom., 163, 101–119, https://doi.org/10.1016/S0168-1176(97)00001-3, 1997.
Schervish, M. and Donahue, N. M.: Peroxy radical chemistry and the volatility basis set, Atmos. Chem. Phys., 20, 1183–1199, https://doi.org/10.5194/acp-20-1183-2020, 2020.
Schreckenbach, S. A., Anderson, J. S. M., Koopman, J., Grimme, S., Simpson,
M. J., and Jobst, K. J.: Predicting the Mass Spectra of Environmental
Pollutants Using Computational Chemistry: A Case Study and Critical
Evaluation, J. Am. Soc. Mass Spectrom., 32, 1508–1518, https://doi.org/10.1021/jasms.1c00078, 2021.
Sindelarova, K., Granier, C., Bouarar, I., Guenther, A., Tilmes, S., Stavrakou, T., Müller, J.-F., Kuhn, U., Stefani, P., and Knorr, W.: Global data set of biogenic VOC emissions calculated by the MEGAN model over the last 30 years, Atmos. Chem. Phys., 14, 9317–9341, https://doi.org/10.5194/acp-14-9317-2014, 2014.
Swanton, D. J., Marsden, D. C. J., and Radom, L.: Theoretical study of the
structure and unimolecular decomposition pathways of ethyloxonium,
[CH3CH2OH2]+, Org. Mass Spectrom., 26, 227–234, https://doi.org/10.1002/oms.1210260409, 1991.
Tani, A., Hayward, S., and Hewitt, C. N.: Measurement of monoterpenes and
related compounds by proton transfer reaction-mass spectrometry (PTR-MS),
Int. J. Mass Spectrom., 223–224, 561–578, https://doi.org/10.1016/S1387-3806(02)00880-1, 2003.
Tani, A., Hayward, S., Hansel, A., and Hewitt, C. N.: Effect of water vapour
pressure on monoterpene measurements using proton transfer reaction-mass
spectrometry (PTR-MS), Int. J. Mass Spectrom., 239,
161–169, https://doi.org/10.1016/j.ijms.2004.07.020, 2004.
Theloke, J. and Friedrich, R.: Compilation of a database on the composition
of anthropogenic VOC emissions for atmospheric modeling in Europe, Atmos.
Environ., 41, 4148–4160, https://doi.org/10.1016/j.atmosenv.2006.12.026, 2007.
Tomaz, S., Wang, D., Zabalegui, N., Li, D., Lamkaddam, H., Bachmeier, F.,
Vogel, A., Monge, M. E., Perrier, S., Baltensperger, U., George, C.,
Rissanen, M., Ehn, M., El Haddad, I., and Riva, M.: Structures and
reactivity of peroxy radicals and dimeric products revealed by online tandem
mass spectrometry, Nat. Commun., 12, 300, https://doi.org/10.1038/s41467-020-20532-2, 2021.
Valiev, R. R., Hasan, G., Salo, V.-T., Kubečka, J., and Kurten, T.:
Intersystem Crossings Drive Atmospheric Gas-Phase Dimer Formation, J. Phys. Chem. A, 123, 6596–6604, https://doi.org/10.1021/acs.jpca.9b02559, 2019.
Werner, H. J., Knowles, P. J., Knizia, G., Manby, F. R., and Schutz, M.:
Molpro: a general-purpose quantum chemistry program package, Wiley
Interdiscip. Rev.-Comput. Mol. Sci., 2, 242–253, https://doi.org/10.1002/wcms.82, 2012.
Yan, C., Nie, W., Äijälä, M., Rissanen, M. P., Canagaratna, M. R., Massoli, P., Junninen, H., Jokinen, T., Sarnela, N., Häme, S. A. K., Schobesberger, S., Canonaco, F., Yao, L., Prévôt, A. S. H., Petäjä, T., Kulmala, M., Sipilä, M., Worsnop, D. R., and Ehn, M.: Source characterization of highly oxidized multifunctional compounds in a boreal forest environment using positive matrix factorization, Atmos. Chem. Phys., 16, 12715–12731, https://doi.org/10.5194/acp-16-12715-2016, 2016.
Ying, Q. and Krishnan, A.: Source contributions of volatile organic
compounds to ozone formation in southeast Texas, J. Geophys. Res.-Atmos., 115, D17306, https://doi.org/10.1029/2010JD013931, 2010.
Yuan, B., Koss, A. R., Warneke, C., Coggon, M., Sekimoto, K., and de Gouw,
J. A.: Proton-Transfer-Reaction Mass Spectrometry: Applications in
Atmospheric Sciences, Chem. Rev., 117, 13187–13229, 2017.
Zhao, Y., Thornton, J. A., and Pye, H. O. T.: Quantitative constraints on
autoxidation and dimer formation from direct probing of monoterpene-derived
peroxy radical chemistry, P. Natl. Acad. Sci. USA, 115, 12142, https://doi.org/10.1073/pnas.1812147115, 2018.
Short summary
This work evaluated the potential for PTR-based mass spectrometers to detect ROOR and ROOH peroxides both experimentally and through computations. Laboratory experiments using a Vocus PTR observed only noisy signals of potential dimers during α-pinene ozonolysis and a few small signals of dimeric compounds during cyclohexene ozonolysis. Quantum chemical calculations for model ROOR and ROOH systems showed that most of these peroxides should fragment partially following protonation.
This work evaluated the potential for PTR-based mass spectrometers to detect ROOR and ROOH...
