Articles | Volume 22, issue 2
https://doi.org/10.5194/acp-22-1195-2022
© 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/acp-22-1195-2022
© Author(s) 2022. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
24 Jan 2022
Research article |
| 24 Jan 2022
| 24 Jan 2022
Comparison of saturation vapor pressures of α-pinene + O3 oxidation products derived from COSMO-RS computations and thermal desorption experiments
Department of Applied Physics, University of Eastern Finland, P.O. Box 1627, 70211 Kuopio, Finland
now at: Department of Chemistry, Nanoscience Center, University of Jyväskylä, 40014 Jyväskylä, Finland
Iida Pullinen
Department of Applied Physics, University of Eastern Finland, P.O. Box 1627, 70211 Kuopio, Finland
Aki Nissinen
Department of Applied Physics, University of Eastern Finland, P.O. Box 1627, 70211 Kuopio, Finland
Siegfried Schobesberger
Department of Applied Physics, University of Eastern Finland, P.O. Box 1627, 70211 Kuopio, Finland
Annele Virtanen
Department of Applied Physics, University of Eastern Finland, P.O. Box 1627, 70211 Kuopio, Finland
Taina Yli-Juuti
Department of Applied Physics, University of Eastern Finland, P.O. Box 1627, 70211 Kuopio, Finland
Related authors
Silvia M. Calderón, Noora Hyttinen, Harri Kokkola, Tomi Raatikainen, R. Paul Lawson, and Sami Romakkaniemi
EGUsphere, https://doi.org/10.5194/egusphere-2025-2730, https://doi.org/10.5194/egusphere-2025-2730, 2025
Short summary
Short summary
Field campaigns suggest that secondary ice production (SIP) via millimeter-sized supercooled droplets is responsible for the rapid glaciation and precipitation development in summer cumulus congestus clouds that lack of ice nucleating particles. We used large-eddy-simulations with sectional representation of aerosol and hydrometeor microphysics that reproduced observed hydrometeor size distributions and explained how SIP boosted rates of aggregation processes that increase surface precipitation.
Arttu Ylisirniö, Noora Hyttinen, Zijun Li, Mitchell Alton, Aki Nissinen, Iida Pullinen, Pasi Miettinen, Taina Yli-Juuti, and Siegfried Schobesberger
EGUsphere, https://doi.org/10.5194/egusphere-2025-2219, https://doi.org/10.5194/egusphere-2025-2219, 2025
Short summary
Short summary
This study aims to increase knowledge of the low volatility organic compouds observed in ambient aerosol particles by providing new volatility information about compounds used for calibrating volatility measurement instruments. Previously, such information has was not available and calibration of the instrument had to be extrapolated to cover the whole measurement range. Results of this study will provide the scientific community better tools for investigating the complexity of ambient aerosols.
Zijun Li, Angela Buchholz, and Noora Hyttinen
Atmos. Chem. Phys., 24, 11717–11725, https://doi.org/10.5194/acp-24-11717-2024, https://doi.org/10.5194/acp-24-11717-2024, 2024
Short summary
Short summary
Evaluating organosulfur (OS) hygroscopicity is important for assessing aerosol–cloud climate interactions in the post-fossil-fuel future, when SO2 emissions decrease and OS compounds become increasingly important. Here a state-of-the-art quantum-chemistry-based method was used to predict the hygroscopic growth factors (HGFs) of a group of atmospherically relevant OS compounds and their mixtures with (NH4)2SO4. A good agreement was observed between their model-estimated and experimental HGFs.
Noora Hyttinen
Atmos. Chem. Phys., 23, 13809–13817, https://doi.org/10.5194/acp-23-13809-2023, https://doi.org/10.5194/acp-23-13809-2023, 2023
Short summary
Short summary
Water activity in aerosol particles describes how particles respond to variations in relative humidity. Here, water activities were calculated for a set of 80 salts that may be present in aerosol particles using a state-of-the-art quantum-chemistry-based method. The effect of the dissociated salt on water activity varies with both the cation and anion. Most of the studied salts increase water uptake compared to pure water-soluble organic particles.
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
Short summary
Short summary
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.
Zijun Li, Noora Hyttinen, Miika Vainikka, Olli-Pekka Tikkasalo, Siegfried Schobesberger, and Taina Yli-Juuti
Atmos. Chem. Phys., 23, 6863–6877, https://doi.org/10.5194/acp-23-6863-2023, https://doi.org/10.5194/acp-23-6863-2023, 2023
Short summary
Short summary
The saturation vapor pressure (psat) of low-volatility organic compounds (LVOCs) governs their partitioning between the gas and particle phases. To estimate the psat of selected LVOCs, we performed particle evaporation measurements in a residence time chamber at a temperature setting relevant to atmospheric aerosol formation and conducted state-of-the-art computational calculations. We found good agreement between the experimentally measured and model-estimated psat values for most LVOCs.
Robin Wollesen de Jonge, Jonas Elm, Bernadette Rosati, Sigurd Christiansen, Noora Hyttinen, Dana Lüdemann, Merete Bilde, and Pontus Roldin
Atmos. Chem. Phys., 21, 9955–9976, https://doi.org/10.5194/acp-21-9955-2021, https://doi.org/10.5194/acp-21-9955-2021, 2021
Short summary
Short summary
This study presents a detailed analysis of the OH-initiated oxidation of dimethyl sulfide (DMS) based on experiments performed in the Aarhus University Research on Aerosol (AURA) smog chamber and the gas- and particle-phase chemistry kinetic multilayer model (ADCHAM). We capture the formation, growth and chemical composition of aerosols in the chamber setup by an improved multiphase oxidation mechanism and utilize our results to reproduce the important role of DMS in the marine boundary layer.
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
Short summary
Short summary
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.
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).
Short summary
Short summary
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.
Sungah Kang, Jürgen Wildt, Iida Pullinen, Luc Vereecken, Cheng Wu, Andreas Wahner, Sören R. Zorn, and Thomas F. Mentel
EGUsphere, https://doi.org/10.5194/egusphere-2025-2772, https://doi.org/10.5194/egusphere-2025-2772, 2025
Short summary
Short summary
Highly oxygenated organic molecules by atmospheric oxidation of plant emitted monoterpenes are important components in secondary organic aerosol formation. Autoxidation of organic peroxy radicals is one important pathway of their formation. We show that isomerization of highly oxygenated alkoxy radicals leads to highly oxygenated peroxy radicals that continue the autoxidation chain. Alkoxy-peroxy steps may dominate the formation of highly oxygenated molecules at high nitrogen oxide levels.
Silvia M. Calderón, Noora Hyttinen, Harri Kokkola, Tomi Raatikainen, R. Paul Lawson, and Sami Romakkaniemi
EGUsphere, https://doi.org/10.5194/egusphere-2025-2730, https://doi.org/10.5194/egusphere-2025-2730, 2025
Short summary
Short summary
Field campaigns suggest that secondary ice production (SIP) via millimeter-sized supercooled droplets is responsible for the rapid glaciation and precipitation development in summer cumulus congestus clouds that lack of ice nucleating particles. We used large-eddy-simulations with sectional representation of aerosol and hydrometeor microphysics that reproduced observed hydrometeor size distributions and explained how SIP boosted rates of aggregation processes that increase surface precipitation.
Arya Mukherjee, Anni Hartikainen, Markus Somero, Viljami Luostari, Mika Ihalainen, Christopher P. Rüger, Timo Kekäläinen, Ville H. Nissinen, Luis M. F. Barreira, Hanna Koponen, Tuukka Kokkola, Delun Li, Lejish Vettikkat, Pasi Yli-Pirilä, Muhammad Shahzaib, Meri M. Ruppel, Ville Vakkari, Kerneels Jaars, Stefan J. Siebert, Angela Buchholz, Kajar Köster, Pieter G. van Zyl, Hilkka Timonen, Niko Kinnunen, Janne Jänis, Annele Virtanen, Aki Virkkula, and Olli Sippula
EGUsphere, https://doi.org/10.5194/egusphere-2025-2759, https://doi.org/10.5194/egusphere-2025-2759, 2025
Short summary
Short summary
Warming climate is predicted to increase boreal and peatland fires in Northern Eurasia. Limited studies have characterized light absorbing aerosol emissions from these biomasses, thus necessitating this work. Brown carbon (BrC) emitted from laboratory-scale biomass burning had weak light absorptivities based on their complex refractive index values. A combustion temperature dependent light absorptivity continuum existed for emitted BrC. Photochemical aging decreased BrC light absorptivity.
Arttu Ylisirniö, Noora Hyttinen, Zijun Li, Mitchell Alton, Aki Nissinen, Iida Pullinen, Pasi Miettinen, Taina Yli-Juuti, and Siegfried Schobesberger
EGUsphere, https://doi.org/10.5194/egusphere-2025-2219, https://doi.org/10.5194/egusphere-2025-2219, 2025
Short summary
Short summary
This study aims to increase knowledge of the low volatility organic compouds observed in ambient aerosol particles by providing new volatility information about compounds used for calibrating volatility measurement instruments. Previously, such information has was not available and calibration of the instrument had to be extrapolated to cover the whole measurement range. Results of this study will provide the scientific community better tools for investigating the complexity of ambient aerosols.
Sini Talvinen, Paul Kim, Emanuele Tovazzi, Eemeli Holopainen, Roxana Cremer, Thomas Kühn, Harri Kokkola, Zak Kipling, David Neubauer, João C. Teixeira, Alistair Sellar, Duncan Watson-Parris, Yang Yang, Jialei Zhu, Srinath Krishnan, Annele Virtanen, and Daniel G. Partridge
EGUsphere, https://doi.org/10.5194/egusphere-2025-721, https://doi.org/10.5194/egusphere-2025-721, 2025
Short summary
Short summary
Climate models struggle to predict how clouds and aerosols interact, affecting Earth’s energy balance. This study compares models to observations to see how they describe effects of clouds and rain on aerosols. While both models show similar overall trends, seasonal differences emerged. These, however, align with differences in key variables participating in cloud formation. The study provides tools to improve the representation of aerosol-cloud interactions in climate models.
Zijun Li, Angela Buchholz, and Noora Hyttinen
Atmos. Chem. Phys., 24, 11717–11725, https://doi.org/10.5194/acp-24-11717-2024, https://doi.org/10.5194/acp-24-11717-2024, 2024
Short summary
Short summary
Evaluating organosulfur (OS) hygroscopicity is important for assessing aerosol–cloud climate interactions in the post-fossil-fuel future, when SO2 emissions decrease and OS compounds become increasingly important. Here a state-of-the-art quantum-chemistry-based method was used to predict the hygroscopic growth factors (HGFs) of a group of atmospherically relevant OS compounds and their mixtures with (NH4)2SO4. A good agreement was observed between their model-estimated and experimental HGFs.
Muhammed Irfan, Thomas Kühn, Taina Yli-Juuti, Anton Laakso, Eemeli Holopainen, Douglas R. Worsnop, Annele Virtanen, and Harri Kokkola
Atmos. Chem. Phys., 24, 8489–8506, https://doi.org/10.5194/acp-24-8489-2024, https://doi.org/10.5194/acp-24-8489-2024, 2024
Short summary
Short summary
The study examines how the volatility of semi-volatile organic compounds affects secondary organic aerosol (SOA) formation and climate. Our simulations show that uncertainties in these volatilities influence aerosol mass and climate impacts. Accurate representation of these compounds in climate models is crucial for predicting global climate patterns.
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
Atmos. Chem. Phys., 24, 2607–2624, https://doi.org/10.5194/acp-24-2607-2024, https://doi.org/10.5194/acp-24-2607-2024, 2024
Short summary
Short summary
We present distinct molecular composition and volatility of oxygenated organic aerosol particles in different rural, urban, and mountain environments. We do a comprehensive investigation of the relationship between the chemical composition and volatility of oxygenated organic aerosol particles across different systems and environments. This study provides implications for volatility descriptions of oxygenated organic aerosol particles in different model frameworks.
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
Short summary
Short summary
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.
Markku Kulmala, Anna Lintunen, Hanna Lappalainen, Annele Virtanen, Chao Yan, Ekaterina Ezhova, Tuomo Nieminen, Ilona Riipinen, Risto Makkonen, Johanna Tamminen, Anu-Maija Sundström, Antti Arola, Armin Hansel, Kari Lehtinen, Timo Vesala, Tuukka Petäjä, Jaana Bäck, Tom Kokkonen, and Veli-Matti Kerminen
Atmos. Chem. Phys., 23, 14949–14971, https://doi.org/10.5194/acp-23-14949-2023, https://doi.org/10.5194/acp-23-14949-2023, 2023
Short summary
Short summary
To be able to meet global grand challenges, we need comprehensive open data with proper metadata. In this opinion paper, we describe the SMEAR (Station for Measuring Earth surface – Atmosphere Relations) concept and include several examples (cases), such as new particle formation and growth, feedback loops and the effect of COVID-19, and what has been learned from these investigations. The future needs and the potential of comprehensive observations of the environment are summarized.
Noora Hyttinen
Atmos. Chem. Phys., 23, 13809–13817, https://doi.org/10.5194/acp-23-13809-2023, https://doi.org/10.5194/acp-23-13809-2023, 2023
Short summary
Short summary
Water activity in aerosol particles describes how particles respond to variations in relative humidity. Here, water activities were calculated for a set of 80 salts that may be present in aerosol particles using a state-of-the-art quantum-chemistry-based method. The effect of the dissociated salt on water activity varies with both the cation and anion. Most of the studied salts increase water uptake compared to pure water-soluble organic particles.
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
Short summary
Short summary
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.
Jonas Elm, Aladár Czitrovszky, Andreas Held, Annele Virtanen, Astrid Kiendler-Scharr, Benjamin J. Murray, Daniel McCluskey, Daniele Contini, David Broday, Eirini Goudeli, Hilkka Timonen, Joan Rosell-Llompart, Jose L. Castillo, Evangelia Diapouli, Mar Viana, Maria E. Messing, Markku Kulmala, Naděžda Zíková, and Sebastian H. Schmitt
Aerosol Research, 1, 13–16, https://doi.org/10.5194/ar-1-13-2023, https://doi.org/10.5194/ar-1-13-2023, 2023
Hao Luo, Luc Vereecken, Hongru Shen, Sungah Kang, Iida Pullinen, Mattias Hallquist, Hendrik Fuchs, Andreas Wahner, Astrid Kiendler-Scharr, Thomas F. Mentel, and Defeng Zhao
Atmos. Chem. Phys., 23, 7297–7319, https://doi.org/10.5194/acp-23-7297-2023, https://doi.org/10.5194/acp-23-7297-2023, 2023
Short summary
Short summary
Oxidation of limonene, an element emitted by trees and chemical products, by OH, a daytime oxidant, forms many highly oxygenated organic molecules (HOMs), including C10-20 compounds. HOMs play an important role in new particle formation and growth. HOM formation can be explained by the chemistry of peroxy radicals. We found that a minor branching ratio initial pathway plays an unexpected, significant role. Considering this pathway enables accurate simulations of HOMs and other concentrations.
Zijun Li, Noora Hyttinen, Miika Vainikka, Olli-Pekka Tikkasalo, Siegfried Schobesberger, and Taina Yli-Juuti
Atmos. Chem. Phys., 23, 6863–6877, https://doi.org/10.5194/acp-23-6863-2023, https://doi.org/10.5194/acp-23-6863-2023, 2023
Short summary
Short summary
The saturation vapor pressure (psat) of low-volatility organic compounds (LVOCs) governs their partitioning between the gas and particle phases. To estimate the psat of selected LVOCs, we performed particle evaporation measurements in a residence time chamber at a temperature setting relevant to atmospheric aerosol formation and conducted state-of-the-art computational calculations. We found good agreement between the experimentally measured and model-estimated psat values for most LVOCs.
Lejish Vettikkat, Pasi Miettinen, Angela Buchholz, Pekka Rantala, Hao Yu, Simon Schallhart, Tuukka Petäjä, Roger Seco, Elisa Männistö, Markku Kulmala, Eeva-Stiina Tuittila, Alex B. Guenther, and Siegfried Schobesberger
Atmos. Chem. Phys., 23, 2683–2698, https://doi.org/10.5194/acp-23-2683-2023, https://doi.org/10.5194/acp-23-2683-2023, 2023
Short summary
Short summary
Wetlands cover a substantial fraction of the land mass in the northern latitudes, from northern Europe to Siberia and Canada. Yet, their isoprene and terpene emissions remain understudied. Here, we used a state-of-the-art measurement technique to quantify ecosystem-scale emissions from a boreal wetland during an unusually warm spring/summer. We found that the emissions from this wetland were (a) higher and (b) even more strongly dependent on temperature than commonly thought.
Siegfried Schobesberger, Emma L. D'Ambro, Lejish Vettikkat, Ben H. Lee, Qiaoyun Peng, David M. Bell, John E. Shilling, Manish Shrivastava, Mikhail Pekour, Jerome Fast, and Joel A. Thornton
Atmos. Meas. Tech., 16, 247–271, https://doi.org/10.5194/amt-16-247-2023, https://doi.org/10.5194/amt-16-247-2023, 2023
Short summary
Short summary
We present a new, highly sensitive technique for measuring atmospheric ammonia, an important trace gas that is emitted mainly by agriculture. We deployed the instrument on an aircraft during research flights over rural Oklahoma. Due to its fast response, we could analyze correlations with turbulent winds and calculate ammonia emissions from nearby areas at 1 to 2 km resolution. We observed high spatial variability and point sources that are not resolved in the US National Emissions Inventory.
Zijun Li, Angela Buchholz, Luis M. F. Barreira, Arttu Ylisirniö, Liqing Hao, Iida Pullinen, Siegfried Schobesberger, and Annele Virtanen
Atmos. Chem. Phys., 23, 203–220, https://doi.org/10.5194/acp-23-203-2023, https://doi.org/10.5194/acp-23-203-2023, 2023
Short summary
Short summary
Interaction between NOx and biogenic emissions can be important in suburban areas. Our study showed that the addition of NOx during α-pinene SOA formation produced considerable amounts of organic nitrates and affected the composition of non-nitrated organic compounds. The compositional difference consequently altered the primary type of aqueous-phase processes during the isothermal particle evaporation.
Bernadette Rosati, Sini Isokääntä, Sigurd Christiansen, Mads Mørk Jensen, Shamjad P. Moosakutty, Robin Wollesen de Jonge, Andreas Massling, Marianne Glasius, Jonas Elm, Annele Virtanen, and Merete Bilde
Atmos. Chem. Phys., 22, 13449–13466, https://doi.org/10.5194/acp-22-13449-2022, https://doi.org/10.5194/acp-22-13449-2022, 2022
Short summary
Short summary
Sulfate aerosols have a strong influence on climate. Due to the reduction in sulfur-based fossil fuels, natural sulfur emissions play an increasingly important role. Studies investigating the climate relevance of natural sulfur aerosols are scarce. We study the water uptake of such particles in the laboratory, demonstrating a high potential to take up water and form cloud droplets. During atmospheric transit, chemical processing affects the particles’ composition and thus their water uptake.
Ville Leinonen, Harri Kokkola, Taina Yli-Juuti, Tero Mielonen, Thomas Kühn, Tuomo Nieminen, Simo Heikkinen, Tuuli Miinalainen, Tommi Bergman, Ken Carslaw, Stefano Decesari, Markus Fiebig, Tareq Hussein, Niku Kivekäs, Radovan Krejci, Markku Kulmala, Ari Leskinen, Andreas Massling, Nikos Mihalopoulos, Jane P. Mulcahy, Steffen M. Noe, Twan van Noije, Fiona M. O'Connor, Colin O'Dowd, Dirk Olivie, Jakob B. Pernov, Tuukka Petäjä, Øyvind Seland, Michael Schulz, Catherine E. Scott, Henrik Skov, Erik Swietlicki, Thomas Tuch, Alfred Wiedensohler, Annele Virtanen, and Santtu Mikkonen
Atmos. Chem. Phys., 22, 12873–12905, https://doi.org/10.5194/acp-22-12873-2022, https://doi.org/10.5194/acp-22-12873-2022, 2022
Short summary
Short summary
We provide the first extensive comparison of detailed aerosol size distribution trends between in situ observations from Europe and five different earth system models. We investigated aerosol modes (nucleation, Aitken, and accumulation) separately and were able to show the differences between measured and modeled trends and especially their seasonal patterns. The differences in model results are likely due to complex effects of several processes instead of certain specific model features.
Silvia M. Calderón, Juha Tonttila, Angela Buchholz, Jorma Joutsensaari, Mika Komppula, Ari Leskinen, Liqing Hao, Dmitri Moisseev, Iida Pullinen, Petri Tiitta, Jian Xu, Annele Virtanen, Harri Kokkola, and Sami Romakkaniemi
Atmos. Chem. Phys., 22, 12417–12441, https://doi.org/10.5194/acp-22-12417-2022, https://doi.org/10.5194/acp-22-12417-2022, 2022
Short summary
Short summary
The spatial and temporal restrictions of observations and oversimplified aerosol representation in large eddy simulations (LES) limit our understanding of aerosol–stratocumulus interactions. In this closure study of in situ and remote sensing observations and outputs from UCLALES–SALSA, we have assessed the role of convective overturning and aerosol effects in two cloud events observed at the Puijo SMEAR IV station, Finland, a diurnal-high aerosol case and a nocturnal-low aerosol case.
Sini Isokääntä, Paul Kim, Santtu Mikkonen, Thomas Kühn, Harri Kokkola, Taina Yli-Juuti, Liine Heikkinen, Krista Luoma, Tuukka Petäjä, Zak Kipling, Daniel Partridge, and Annele Virtanen
Atmos. Chem. Phys., 22, 11823–11843, https://doi.org/10.5194/acp-22-11823-2022, https://doi.org/10.5194/acp-22-11823-2022, 2022
Short summary
Short summary
This research employs air mass history analysis and observations to study how clouds and precipitation affect atmospheric aerosols during transport to a boreal forest site. The mass concentrations of studied chemical species showed exponential decrease as a function of accumulated rain along the air mass route. Our analysis revealed in-cloud sulfate formation, while no major changes in organic mass were seen. Most of the in-cloud-formed sulfate could be assigned to particle sizes above 200 nm.
Yindong Guo, Hongru Shen, Iida Pullinen, Hao Luo, Sungah Kang, Luc Vereecken, Hendrik Fuchs, Mattias Hallquist, Ismail-Hakki Acir, Ralf Tillmann, Franz Rohrer, Jürgen Wildt, Astrid Kiendler-Scharr, Andreas Wahner, Defeng Zhao, and Thomas F. Mentel
Atmos. Chem. Phys., 22, 11323–11346, https://doi.org/10.5194/acp-22-11323-2022, https://doi.org/10.5194/acp-22-11323-2022, 2022
Short summary
Short summary
The oxidation of limonene, a common volatile emitted by trees and chemical products, by NO3, a nighttime oxidant, forms many highly oxygenated organic molecules (HOM), including C10-30 compounds. Most of the HOM are second-generation organic nitrates, in which carbonyl-substituted C10 nitrates accounted for a major fraction. Their formation can be explained by chemistry of peroxy radicals. HOM, especially low-volatile ones, play an important role in nighttime new particle formation and growth.
Lisa J. Beck, Siegfried Schobesberger, Heikki Junninen, Janne Lampilahti, Antti Manninen, Lubna Dada, Katri Leino, Xu-Cheng He, Iida Pullinen, Lauriane L. J. Quéléver, Anna Franck, Pyry Poutanen, Daniela Wimmer, Frans Korhonen, Mikko Sipilä, Mikael Ehn, Douglas R. Worsnop, Veli-Matti Kerminen, Tuukka Petäjä, Markku Kulmala, and Jonathan Duplissy
Atmos. Chem. Phys., 22, 8547–8577, https://doi.org/10.5194/acp-22-8547-2022, https://doi.org/10.5194/acp-22-8547-2022, 2022
Short summary
Short summary
The presented article introduces an overview of atmospheric ions and their composition above the boreal forest. We provide the results of an extensive airborne measurement campaign with an air ion mass spectrometer and particle measurements, showing their diurnal evolution within the boundary layer and free troposphere. In addition, we compare the airborne dataset with the co-located data from the ground at SMEAR II station, Finland.
Zoé Brasseur, Dimitri Castarède, Erik S. Thomson, Michael P. Adams, Saskia Drossaart van Dusseldorp, Paavo Heikkilä, Kimmo Korhonen, Janne Lampilahti, Mikhail Paramonov, Julia Schneider, Franziska Vogel, Yusheng Wu, Jonathan P. D. Abbatt, Nina S. Atanasova, Dennis H. Bamford, Barbara Bertozzi, Matthew Boyer, David Brus, Martin I. Daily, Romy Fösig, Ellen Gute, Alexander D. Harrison, Paula Hietala, Kristina Höhler, Zamin A. Kanji, Jorma Keskinen, Larissa Lacher, Markus Lampimäki, Janne Levula, Antti Manninen, Jens Nadolny, Maija Peltola, Grace C. E. Porter, Pyry Poutanen, Ulrike Proske, Tobias Schorr, Nsikanabasi Silas Umo, János Stenszky, Annele Virtanen, Dmitri Moisseev, Markku Kulmala, Benjamin J. Murray, Tuukka Petäjä, Ottmar Möhler, and Jonathan Duplissy
Atmos. Chem. Phys., 22, 5117–5145, https://doi.org/10.5194/acp-22-5117-2022, https://doi.org/10.5194/acp-22-5117-2022, 2022
Short summary
Short summary
The present measurement report introduces the ice nucleation campaign organized in Hyytiälä, Finland, in 2018 (HyICE-2018). We provide an overview of the campaign settings, and we describe the measurement infrastructure and operating procedures used. In addition, we use results from ice nucleation instrument inter-comparison to show that the suite of these instruments deployed during the campaign reports consistent results.
Lisa J. Beck, Siegfried Schobesberger, Mikko Sipilä, Veli-Matti Kerminen, and Markku Kulmala
Atmos. Meas. Tech., 15, 1957–1965, https://doi.org/10.5194/amt-15-1957-2022, https://doi.org/10.5194/amt-15-1957-2022, 2022
Short summary
Short summary
Sulfuric acid is known to be a main compound in atmospheric new particle formation. Yet, its concentration is very low, which leads to challenges in detecting it. In our study, we derive the sulfuric acid concentration from measurements of ambient ions with a mass spectrometer. Our validation shows that the theoretical approach using the bisulfate ion and its clusters with H2SO4 captures the sulfuric acid concentration very well during daytime.
Kimmo Korhonen, Thomas Bjerring Kristensen, John Falk, Vilhelm B. Malmborg, Axel Eriksson, Louise Gren, Maja Novakovic, Sam Shamun, Panu Karjalainen, Lassi Markkula, Joakim Pagels, Birgitta Svenningsson, Martin Tunér, Mika Komppula, Ari Laaksonen, and Annele Virtanen
Atmos. Chem. Phys., 22, 1615–1631, https://doi.org/10.5194/acp-22-1615-2022, https://doi.org/10.5194/acp-22-1615-2022, 2022
Short summary
Short summary
We investigated the ice-nucleating abilities of particulate emissions from a modern diesel engine using the portable ice-nuclei counter SPIN, a continuous-flow diffusion chamber instrument. Three different fuels were studied without blending, including fossil diesel and two renewable fuels, testing different emission aftertreatment systems and photochemical aging. We found that the diesel emissions were inefficient ice nuclei, and aging had no or little effect on their ice-nucleating abilities.
Arto Heitto, Kari Lehtinen, Tuukka Petäjä, Felipe Lopez-Hilfiker, Joel A. Thornton, Markku Kulmala, and Taina Yli-Juuti
Atmos. Chem. Phys., 22, 155–171, https://doi.org/10.5194/acp-22-155-2022, https://doi.org/10.5194/acp-22-155-2022, 2022
Short summary
Short summary
For atmospheric aerosol particles to take part in cloud formation, they need to be at least a few tens of nanometers in diameter. By using a particle condensation model, we investigated how two types of chemical reactions, oligomerization and decomposition, of organic molecules inside the particle may affect the growth of secondary aerosol particles to these sizes. We show that the effect is potentially significant, which highlights the importance of increasing understanding of these processes.
Zijun Li, Angela Buchholz, Arttu Ylisirniö, Luis Barreira, Liqing Hao, Siegfried Schobesberger, Taina Yli-Juuti, and Annele Virtanen
Atmos. Chem. Phys., 21, 18283–18302, https://doi.org/10.5194/acp-21-18283-2021, https://doi.org/10.5194/acp-21-18283-2021, 2021
Short summary
Short summary
We compared the evolution of two types of secondary organic aerosol (SOA) particles during isothermal evaporation. The sesquiterpene SOA particles demonstrated higher resilience to evaporation than α-pinene SOA particles generated under comparable conditions. In-depth analysis showed that under high-relative-humidity conditions, particulate water drove the evolution of particulate constituents by reducing the particle viscosity and initiating chemical aqueous-phase processes.
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
Short summary
Short summary
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.
Janne Lampilahti, Hanna E. Manninen, Tuomo Nieminen, Sander Mirme, Mikael Ehn, Iida Pullinen, Katri Leino, Siegfried Schobesberger, Juha Kangasluoma, Jenni Kontkanen, Emma Järvinen, Riikka Väänänen, Taina Yli-Juuti, Radovan Krejci, Katrianne Lehtipalo, Janne Levula, Aadu Mirme, Stefano Decesari, Ralf Tillmann, Douglas R. Worsnop, Franz Rohrer, Astrid Kiendler-Scharr, Tuukka Petäjä, Veli-Matti Kerminen, Thomas F. Mentel, and Markku Kulmala
Atmos. Chem. Phys., 21, 12649–12663, https://doi.org/10.5194/acp-21-12649-2021, https://doi.org/10.5194/acp-21-12649-2021, 2021
Short summary
Short summary
We studied aerosol particle formation and growth in different parts of the planetary boundary layer at two different locations (Po Valley, Italy, and Hyytiälä, Finland). The observations consist of airborne measurements on board an instrumented Zeppelin and a small airplane combined with comprehensive ground-based measurements.
Luis M. F. Barreira, Arttu Ylisirniö, Iida Pullinen, Angela Buchholz, Zijun Li, Helina Lipp, Heikki Junninen, Urmas Hõrrak, Steffen M. Noe, Alisa Krasnova, Dmitrii Krasnov, Kaia Kask, Eero Talts, Ülo Niinemets, Jose Ruiz-Jimenez, and Siegfried Schobesberger
Atmos. Chem. Phys., 21, 11781–11800, https://doi.org/10.5194/acp-21-11781-2021, https://doi.org/10.5194/acp-21-11781-2021, 2021
Short summary
Short summary
We present results from PM1 atmospheric composition and concentration measurements performed in a springtime hemiboreal forest. Sesquiterpene mixing ratios and particle-phase concentrations of corresponding oxidation products were rapidly increasing on some early mornings. The particle volatility suggested that condensable sesquiterpene oxidation products are rapidly formed in the atmosphere. The results revealed the importance of sesquiterpenes for secondary organic aerosol particulate mass.
Ana A. Piedehierro, André Welti, Angela Buchholz, Kimmo Korhonen, Iida Pullinen, Ilkka Summanen, Annele Virtanen, and Ari Laaksonen
Atmos. Chem. Phys., 21, 11069–11078, https://doi.org/10.5194/acp-21-11069-2021, https://doi.org/10.5194/acp-21-11069-2021, 2021
Short summary
Short summary
Ice crystals in cirrus clouds contain particles that start ice formation. We study whether particles forming above boreal forests can help in the making of cirrus clouds and if the water content in the particles affects this property. In the laboratory, we made boreal-forest-like particles and cooled and humidified them to measure whether an ice crystal develops. We found that only when dry can these particles form an ice crystal but no better than solution droplets.
Robin Wollesen de Jonge, Jonas Elm, Bernadette Rosati, Sigurd Christiansen, Noora Hyttinen, Dana Lüdemann, Merete Bilde, and Pontus Roldin
Atmos. Chem. Phys., 21, 9955–9976, https://doi.org/10.5194/acp-21-9955-2021, https://doi.org/10.5194/acp-21-9955-2021, 2021
Short summary
Short summary
This study presents a detailed analysis of the OH-initiated oxidation of dimethyl sulfide (DMS) based on experiments performed in the Aarhus University Research on Aerosol (AURA) smog chamber and the gas- and particle-phase chemistry kinetic multilayer model (ADCHAM). We capture the formation, growth and chemical composition of aerosols in the chamber setup by an improved multiphase oxidation mechanism and utilize our results to reproduce the important role of DMS in the marine boundary layer.
Defeng Zhao, Iida Pullinen, Hendrik Fuchs, Stephanie Schrade, Rongrong Wu, Ismail-Hakki Acir, Ralf Tillmann, Franz Rohrer, Jürgen Wildt, Yindong Guo, Astrid Kiendler-Scharr, Andreas Wahner, Sungah Kang, Luc Vereecken, and Thomas F. Mentel
Atmos. Chem. Phys., 21, 9681–9704, https://doi.org/10.5194/acp-21-9681-2021, https://doi.org/10.5194/acp-21-9681-2021, 2021
Short summary
Short summary
The reaction of isoprene, a biogenic volatile organic compound with the globally largest emission rates, with NO3, an nighttime oxidant influenced heavily by anthropogenic emissions, forms a large number of highly oxygenated organic molecules (HOM). These HOM are formed via one or multiple oxidation steps, followed by autoxidation. Their total yield is much higher than that in the daytime oxidation of isoprene. They may play an important role in nighttime organic aerosol formation and growth.
Michael Priestley, Thomas J. Bannan, Michael Le Breton, Stephen D. Worrall, Sungah Kang, Iida Pullinen, Sebastian Schmitt, Ralf Tillmann, Einhard Kleist, Defeng Zhao, Jürgen Wildt, Olga Garmash, Archit Mehra, Asan Bacak, Dudley E. Shallcross, Astrid Kiendler-Scharr, Åsa M. Hallquist, Mikael Ehn, Hugh Coe, Carl J. Percival, Mattias Hallquist, Thomas F. Mentel, and Gordon McFiggans
Atmos. Chem. Phys., 21, 3473–3490, https://doi.org/10.5194/acp-21-3473-2021, https://doi.org/10.5194/acp-21-3473-2021, 2021
Short summary
Short summary
A significant fraction of emissions from human activity consists of aromatic hydrocarbons, e.g. benzene, which oxidise to form new compounds important for particle growth. Characterisation of benzene oxidation products highlights the range of species produced as well as their chemical properties and contextualises them within relevant frameworks, e.g. MCM. Cluster analysis of the oxidation product time series distinguishes behaviours of CHON compounds that could aid in identifying functionality.
Antti Ruuskanen, Sami Romakkaniemi, Harri Kokkola, Antti Arola, Santtu Mikkonen, Harri Portin, Annele Virtanen, Kari E. J. Lehtinen, Mika Komppula, and Ari Leskinen
Atmos. Chem. Phys., 21, 1683–1695, https://doi.org/10.5194/acp-21-1683-2021, https://doi.org/10.5194/acp-21-1683-2021, 2021
Short summary
Short summary
The study focuses mainly on cloud-scavenging efficiency of absorbing particulate matter (mainly black carbon) but additionally covers cloud-scavenging efficiency of scattering particles and statistics of cloud condensation nuclei. The main findings give insight into how black carbon is distributed in different particle sizes and the sensitivity to cloud scavenged. The main findings are useful for large-scale modelling for evaluating cloud scavenging.
Arttu Ylisirniö, Luis M. F. Barreira, Iida Pullinen, Angela Buchholz, John Jayne, Jordan E. Krechmer, Douglas R. Worsnop, Annele Virtanen, and Siegfried Schobesberger
Atmos. Meas. Tech., 14, 355–367, https://doi.org/10.5194/amt-14-355-2021, https://doi.org/10.5194/amt-14-355-2021, 2021
Short summary
Short summary
FIGAERO-ToF-CIMS enables online volatility measurements of chemical compounds in ambient aerosols. Previously published volatility calibration results however differ from each other significantly. In this study we investigate the reason for this discrepancy. We found a major source of error in the widely used syringe deposition method and propose a new method for volatility calibration by using atomized calibration compounds.
André Welti, Kimmo Korhonen, Pasi Miettinen, Ana A. Piedehierro, Yrjö Viisanen, Annele Virtanen, and Ari Laaksonen
Atmos. Meas. Tech., 13, 7059–7067, https://doi.org/10.5194/amt-13-7059-2020, https://doi.org/10.5194/amt-13-7059-2020, 2020
Short summary
Short summary
We describe a modification of the SPectrometer for Ice Nuclei (SPIN) chamber to study ice nucleation at low temperatures, relevant for ice formation in cirrus clouds. Validation experiments of homogeneous freezing of aqueous ammonium sulfate droplets and heterogeneous ice nucleation on silver iodide particles are included to demonstrate the advantages of the modified SPIN chamber for the investigation of ice nucleation in the extended temperature range.
Liqing Hao, Eetu Kari, Ari Leskinen, Douglas R. Worsnop, and Annele Virtanen
Atmos. Chem. Phys., 20, 14393–14405, https://doi.org/10.5194/acp-20-14393-2020, https://doi.org/10.5194/acp-20-14393-2020, 2020
Short summary
Short summary
Our work presents the observational results of secondary organic aerosol (SOA) formation in the presence of ammonia. The particle-phase ammonium was continuously produced even after SOA formation had ceased. The gas-phase organic acids were observed to contribute to the formed particle-phase ammonium salts. This study suggests that the presence of ammonia may change the mass and chemical composition of large-size SOA particles and can potentially alter the aerosol impact on climate change.
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
Short summary
Short summary
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.
Santtu Mikkonen, Zoltán Németh, Veronika Varga, Tamás Weidinger, Ville Leinonen, Taina Yli-Juuti, and Imre Salma
Atmos. Chem. Phys., 20, 12247–12263, https://doi.org/10.5194/acp-20-12247-2020, https://doi.org/10.5194/acp-20-12247-2020, 2020
Short summary
Short summary
We determined decennial statistical time trends and diurnal statistical patterns of atmospheric particle number concentrations in various relevant size fractions in the city centre of Budapest in an interval of 2008–2018. The mean overall decrease rate of particles in different size fractions was approximately −5 % scaled for the 10-year measurement interval. The decline can be interpreted as a consequence of the decreased anthropogenic emissions in the city.
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
Short summary
Short summary
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.
Olli-Pekka Tikkanen, Angela Buchholz, Arttu Ylisirniö, Siegfried Schobesberger, Annele Virtanen, and Taina Yli-Juuti
Atmos. Chem. Phys., 20, 10441–10458, https://doi.org/10.5194/acp-20-10441-2020, https://doi.org/10.5194/acp-20-10441-2020, 2020
Short summary
Short summary
We compared the volatility distributions of secondary organic aerosol (SOA) constituents estimated from isothermal evaporation experiments from either particle size change data, by process modelling and global optimization, or from mass spectrometer data with positive matrix factorization analysis. Our results show that, despite the two very different estimation methods, the volatility distributions are comparable if uncertainties are taken into account.
Iida Pullinen, Sebastian Schmitt, Sungah Kang, Mehrnaz Sarrafzadeh, Patrick Schlag, Stefanie Andres, Einhard Kleist, Thomas F. Mentel, Franz Rohrer, Monika Springer, Ralf Tillmann, Jürgen Wildt, Cheng Wu, Defeng Zhao, Andreas Wahner, and Astrid Kiendler-Scharr
Atmos. Chem. Phys., 20, 10125–10147, https://doi.org/10.5194/acp-20-10125-2020, https://doi.org/10.5194/acp-20-10125-2020, 2020
Short summary
Short summary
Biogenic and anthropogenic air masses mix in the atmosphere, bringing plant-emitted monoterpenes and traffic-related nitrogen oxides together. There is debate whether the presence of nitrogen oxides reduces or increases secondary aerosol formation. This is important as secondary aerosols have cooling effects in the climate system but also constitute a health risk in populated areas. We show that the presence of NOx alone should not much affect the mass yields of secondary organic aerosols.
Cited articles
Aljawhary, D., Zhao, R., Lee, A. K. Y., Wang, C., and Abbatt, J. P. D.:
Kinetics, mechanism, and secondary organic aerosol yield of aqueous phase photo-oxidation of α-pinene oxidation products,
J. Phys. Chem. A,
120, 1395–1407, https://doi.org/10.1021/acs.jpca.5b06237, 2016. a, b
Babar, Z. B., Ashraf, F., Park, J.-H., Quang Dao, P. D., Cho, C. S., and Lim, H.-J.:
Exploring Volatility Properties of Discrete Secondary Organic Aerosol Constituents of α-Pinene and Polycyclic Aromatic Hydrocarbons,
ACS Earth Space Chem.,
4, 2299–2311, https://doi.org/10.1021/acsearthspacechem.0c00210, 2020. a, b, c, d
Bannan, T. J., Booth, A. M., Jones, B. T., O'Meara, S., Barley, M. H., Riipinen, I., Percival, C. J., and Topping, D.:
Measured Saturation Vapor Pressures of Phenolic and Nitro-aromatic Compounds,
Environ. Sci. Technol.,
51, 3922–3928, https://doi.org/10.1021/acs.est.6b06364, 2017. a
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, 2018. a
Bianchi, F., Tröstl, J., Junninen, H., Frege, C., Henne, S., Hoyle, C. R., Molteni, U., Herrmann, E., Adamov, A., Bukowiecki, N., Chen, X., Duplissy, J., Gysel, M., Hutterli, M., Kangasluoma, J., Kontkanen, J., Kürten, A., Manninen, H. E., Münch, S., Peräkylä, O., Petäjä, T., Rondo, L., Williamson, C., Weingartner, E., Curtius, J., Worsnop, D. R., Kulmala, M., Dommen, J., and Baltensperger, U.:
New particle formation in the free troposphere: A question of chemistry and timing,
Science,
352, 1109–1112, https://doi.org/10.1126/science.aad5456, 2016. a
Bilde, M. and Pandis, S. N.:
Evaporation Rates and Vapor Pressures of Individual Aerosol Species Formed in the Atmospheric Oxidation of α- and β-Pinene,
Environ. Sci. Technol.,
35, 3344–3349, https://doi.org/10.1021/es001946b, 2001. a, b
Bilde, M., Barsanti, K., Booth, M., Cappa, C. D., Donahue, N. M., Emanuelsson, E. U., McFiggans, G., Krieger, U. K., Marcolli, C., Topping, D., Ziemann, P., Barley, M., Clegg, S., Dennis-Smither, B., Hallquist, M., Hallquist, r. M., Khlystov, A., Kulmala, M., Mogensen, D., Percival, C. J., Pope, F., Reid, J. P., Ribeiro da Silva, M. A. V., Rosenoern, T., Salo, K., Soonsin, V. P., Yli-Juuti, T., Prisle, N. L., Pagels, J., Rarey, J., Zardini, A. A., and Riipinen, I.:
Saturation Vapor Pressures and Transition Enthalpies of Low-Volatility Organic Molecules of Atmospheric Relevance: From Dicarboxylic Acids to Complex Mixtures,
Chem. Rev.,
115, 4115–4156, https://doi.org/10.1021/cr5005502, 2015. a, b
BIOVIA COSMOconf: 2021, Dassault Systèmes, available at: http://www.3ds.com, last access: 29 January 2021. a
BIOVIA COSMOtherm:
Release 2021, Dassault Systèmes,
available at: http://www.3ds.com, last access: 1 April 2021. a
Buchholz, A., Lambe, A. T., Ylisirniö, A., Li, Z., Tikkanen, O.-P., Faiola, C., Kari, E., Hao, L., Luoma, O., Huang, W., Mohr, C., Worsnop, D. R., Nizkorodov, S. A., Yli-Juuti, T., Schobesberger, S., and Virtanen, A.: Insights into the O:C-dependent mechanisms controlling the evaporation of α-pinene secondary organic aerosol particles, Atmos. Chem. Phys., 19, 4061–4073, https://doi.org/10.5194/acp-19-4061-2019, 2019. a
Claflin, M. S., Krechmer, J. E., Hu, W., Jimenez, J. L., and Ziemann, P. J.:
Functional group composition of secondary organic aerosol formed from ozonolysis of α-pinene under high VOC and autoxidation conditions,
ACS Earth Space Chem.,
2, 1196–1210, https://doi.org/10.1021/acsearthspacechem.8b00117, 2018. a
Compernolle, S., Ceulemans, K., and Müller, J.-F.: EVAPORATION: a new vapour pressure estimation methodfor organic molecules including non-additivity and intramolecular interactions, Atmos. Chem. Phys., 11, 9431–9450, https://doi.org/10.5194/acp-11-9431-2011, 2011. a
COSMOtherm:
version C3.0, Release 15,
COSMOlogic GmbH & Co. KG., Leverkusen, Germany, 2015. a
D'Ambro, E. L., Schobesberger, S., Zaveri, R. A., Shilling, J. E., Lee, B. H., Lopez-Hilfiker, F. D., Mohr, C., and Thornton, J. A.:
Isothermal Evaporation of α-Pinene Ozonolysis SOA: Volatility, Phase State, and Oligomeric Composition,
ACS Earth Space Chem.,
2, 1058–1067, https://doi.org/10.1021/acsearthspacechem.8b00084, 2018. a, b
D'Ambro, E. L., Schobesberger, S., Gaston, C. J., Lopez-Hilfiker, F. D., Lee, B. H., Liu, J., Zelenyuk, A., Bell, D., Cappa, C. D., Helgestad, T., Li, Z., Guenther, A., Wang, J., Wise, M., Caylor, R., Surratt, J. D., Riedel, T., Hyttinen, N., Salo, V.-T., Hasan, G., Kurtén, T., Shilling, J. E., and Thornton, J. A.: Chamber-based insights into the factors controlling epoxydiol (IEPOX) secondary organic aerosol (SOA) yield, composition, and volatility, Atmos. Chem. Phys., 19, 11253–11265, https://doi.org/10.5194/acp-19-11253-2019, 2019. a
Docherty, K. S., Wu, W., Lim, Y. B., and Ziemann, P. J.:
Contributions of organic peroxides to secondary aerosol formed from reactions of monoterpenes with O3,
Environ. Sci. Technol.,
39, 4049–4059, https://doi.org/10.1021/es050228s, 2005. a
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. a, b
Eckert, F. and Klamt, A.:
Fast solvent screening via quantum chemistry: COSMO-RS approach,
AIChE J.,
48, 369–385, https://doi.org/10.1002/aic.690480220, 2002. a
Ehn, M., Kleist, E., Junninen, H., Petäjä, T., Lönn, G., Schobesberger, S., Dal Maso, M., Trimborn, A., Kulmala, M., Worsnop, D. R., Wahner, A., Wildt, J., and Mentel, Th. F.: Gas phase formation of extremely oxidized pinene reaction products in chamber and ambient air, Atmos. Chem. Phys., 12, 5113–5127, https://doi.org/10.5194/acp-12-5113-2012, 2012. a
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. a, b, c
Guenther, A., Hewitt, C. N., Erickson, D., Fall, R., Geron, C., Graedel, T., Harley, P., Klinger, L., Lerdau, M., McKay, W. A., Pierce, T., Scholes, B., Steinbrecher, R., Tallamraju, R., Taylor, J., and Zimmerman, P.:
A global model of natural volatile organic compound emissions,
J. Geophys. Res.: Atmos.,
100, 8873–8892, https://doi.org/10.1029/94JD02950, 1995. a
Halgren, T. A.:
Merck molecular force field. I. Basis, form, scope, parameterization, and performance of MMFF94,
J. Comput. Chem.,
17, 490–519, https://doi.org/10.1002/(SICI)1096-987X(199604)17:5/6<490::AID-JCC1>3.0.CO;2-P, 1996. a
Hall IV, W. A. and Johnston, M. V.:
Oligomer content of α-pinene secondary organic aerosol,
Aerosol Sci. Tech.,
45, 37–45, https://doi.org/10.1080/02786826.2010.517580, 2011. a
Hallquist, M., Wenger, J. C., Baltensperger, U., Rudich, Y., Simpson, D., Claeys, M., Dommen, J., Donahue, N. M., George, C., Goldstein, A. H., Hamilton, J. F., Herrmann, H., Hoffmann, T., Iinuma, Y., Jang, M., Jenkin, M. E., Jimenez, J. L., Kiendler-Scharr, A., Maenhaut, W., McFiggans, G., Mentel, Th. F., Monod, A., Prévôt, A. S. H., Seinfeld, J. H., Surratt, J. D., Szmigielski, R., and Wildt, J.: The formation, properties and impact of secondary organic aerosol: current and emerging issues, Atmos. Chem. Phys., 9, 5155–5236, https://doi.org/10.5194/acp-9-5155-2009, 2009. a
Hao, L. Q., Romakkaniemi, S., Yli-Pirilä, P., Joutsensaari, J., Kortelainen, A., Kroll, J. H., Miettinen, P., Vaattovaara, P., Tiitta, P., Jaatinen, A., Kajos, M. K., Holopainen, J. K., Heijari, J., Rinne, J., Kulmala, M., Worsnop, D. R., Smith, J. N., and Laaksonen, A.: Mass yields of secondary organic aerosols from the oxidation of α-pinene and real plant emissions, Atmos. Chem. Phys., 11, 1367–1378, https://doi.org/10.5194/acp-11-1367-2011, 2011. a
Huang, W., Saathoff, H., Pajunoja, A., Shen, X., Naumann, K.-H., Wagner, R., Virtanen, A., Leisner, T., and Mohr, C.: α-Pinene secondary organic aerosol at low temperature: chemical composition and implications for particle viscosity, Atmos. Chem. Phys., 18, 2883–2898, https://doi.org/10.5194/acp-18-2883-2018, 2018. a
Hyttinen, N. and Prisle, N. L.:
Improving Solubility and Activity Estimates of Multifunctional Atmospheric Organics by Selecting Conformers in COSMOtherm,
J. Phys. Chem. A,
124, 4801–4812, https://doi.org/10.1021/acs.jpca.0c04285, 2020. a, b
Hyttinen, N., Elm, J., Malila, J., Calderón, S. M., and Prisle, N. L.: Thermodynamic properties of isoprene- and monoterpene-derived organosulfates estimated with COSMOtherm, Atmos. Chem. Phys., 20, 5679–5696, https://doi.org/10.5194/acp-20-5679-2020, 2020. a
Hyttinen, N., Pullinen, I., Nissinen, A., Schobesberger, S., Virtanen, A., and Yli-Juuti, T.:
Supplementary data for the manuscript “Comparison of computational and experimental saturation vapor pressures of α-pinene + O3 oxidation products”, Version 1, Zenodo [data set], https://doi.org/10.5281/zenodo.5499485, 2021a. a
Hyttinen, N., Wolf, M., Rissanen, M. P., Ehn, M., Peräkylä, O., Kurtén, T., and Prisle, N. L.:
Gas-to-Particle Partitioning of Cyclohexene- and α-Pinene-Derived Highly Oxygenated Dimers Evaluated Using COSMOtherm,
J. Phys. Chem. A,
125, 3726–3738, https://doi.org/10.1021/acs.jpca.0c11328, 2021b. a, b, c, d, e
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. a
Iyer, S., Rissanen, M. P., Valiev, R., Barua, S., Krechmer, J. E., Thornton, J., Ehn, M., and Kurtén, T.:
Molecular mechanism for rapid autoxidation in α-pinene ozonolysis,
Nat. Commun.,
12, 878, https://doi.org/10.1038/s41467-021-21172-w, 2021. a, b
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., E., 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, 1525–1529, https://doi.org/10.1126/science.1180353, 2009. a
Kirkby, J., Duplissy, J., Sengupta, K., Frege, C., Gordon, H., Williamson, C., Heinritzi, M., Simon, M., Yan, C., Almeida, J., Tröstl, J., Nieminen, T., Ortega, I. K., Wagner, R., Adamov, A., Amorim, A., Bernhammer, A.-K., Bianchi, F., Breitenlechner, M., Brilke, S., Chen, X., Craven, J., Dias, A., Ehrhart, S., Flagan, R. C., Franchin, A., Fuchs, C., Guida, R., Hakala, J., Hoyle, C. R., Jokinen, T., Junninen, H., Kangasluoma, J., Kim, J., Krapf, M., Kurten, A., Laaksonen, A., Lehtipalo, K., Makhmutov, V., Mathot, S., Molteni, U., Onnela, A., Peräkylä, O., Piel, F., Petäjä, T., Praplan, A. P., Pringle, K., Rap, A., Richards, N. A. D., Riipinen, I., Rissanen, M. P., Rondo, L., Sarnela, N., Schobesberger, S., Scott, C. E., Seinfeld, J. H., Sipilä, M., Steiner, G., Stozhkov, Y., Stratmann, F., Tomé, A., Virtanen, A., Vogel, A. L., Wagner, A. C., Wagner, P. E., Weingartner, E., Wimmer, D., Winkler, P. M., Ye, P., Zhang, X., Hansel, A., Dommen, J., Donahue, N. M., Worsnop, D. R., Baltensperger, U., Kulmala, M., and Carslaw, Kenneth S.and Curtius, J.:
Ion-induced nucleation of pure biogenic particles,
Nature,
533, 521–526, https://doi.org/10.1038/nature17953, 2016. a
Klamt, A.:
Conductor-like screening model for real solvents: a new approach to the quantitative calculation of solvation phenomena,
J. Phys. Chem.,
99, 2224–2235, https://doi.org/10.1021/j100007a062, 1995. a
Klamt, A., Jonas, V., Bürger, T., and Lohrenz, J. C. W.:
Refinement and parametrization of COSMO-RS,
J. Phys. Chem. A,
102, 5074–5085, https://doi.org/10.1021/jp980017s, 1998. a
Kostenidou, E., Karnezi, E., Kolodziejczyk, A., Szmigielski, R., and Pandis, S. N.:
Physical and Chemical Properties of 3-Methyl-1,2,3-butanetricarboxylic Acid (MBTCA) Aerosol,
Environ. Sci. Technol.,
52, 1150–1155, https://doi.org/10.1021/acs.est.7b04348, 2018. a, b, c
Krieger, U. K., Siegrist, F., Marcolli, C., Emanuelsson, E. U., Gøbel, F. M., Bilde, M., Marsh, A., Reid, J. P., Huisman, A. J., Riipinen, I., Hyttinen, N., Myllys, N., Kurtén, T., Bannan, T., Percival, C. J., and Topping, D.: A reference data set for validating vapor pressure measurement techniques: homologous series of polyethylene glycols, Atmos. Meas. Tech., 11, 49–63, https://doi.org/10.5194/amt-11-49-2018, 2018. a
Kristensen, K., Cui, T., Zhang, H., Gold, A., Glasius, M., and Surratt, J. D.: Dimers in α-pinene secondary organic aerosol: effect of hydroxyl radical, ozone, relative humidity and aerosol acidity, Atmos. Chem. Phys., 14, 4201–4218, https://doi.org/10.5194/acp-14-4201-2014, 2014. a, b
Kristensen, K., Jensen, L. N., Quéléver, L. L. J., Christiansen, S., Rosati, B., Elm, J., Teiwes, R., Pedersen, H. B., Glasius, M., Ehn, M., and Bilde, M.: The Aarhus Chamber Campaign on Highly Oxygenated Organic Molecules and Aerosols (ACCHA): particle formation, organic acids, and dimer esters from α-pinene ozonolysis at different temperatures, Atmos. Chem. Phys., 20, 12549–12567, https://doi.org/10.5194/acp-20-12549-2020, 2020. a
Kurtén, T., Rissanen, M. P., Mackeprang, K., Thornton, J. A., Hyttinen, N., Jørgensen, S., Ehn, M., and Kjaergaard, H. G.:
Computational Study of Hydrogen Shifts and Ring-Opening Mechanisms in α-Pinene Ozonolysis Products,
J. Phys. Chem. A,
119, 11366–11375, https://doi.org/10.1021/acs.jpca.5b08948, 2015. a, b
Kurtén, T., Tiusanen, K., Roldin, P., Rissanen, M., Luy, J.-N., Boy, M., Ehn, M., and Donahue, N.:
α-Pinene autoxidation products may not have extremely low saturation vapor pressures despite high O:C ratios,
J. Phys. Chem. A,
120, 2569–2582, https://doi.org/10.1021/acs.jpca.6b02196, 2016. a, b, c, d, e, f, g, h, i, j, k, l, m, n
Kurtén, T., Møller, K. H., Nguyen, T. B., Schwantes, R. H., Misztal, P. K., Su, L., Wennberg, P. O., Fry, J. L., and Kjaergaard, H. G.:
Alkoxy Radical Bond Scissions Explain the Anomalously Low Secondary Organic Aerosol and Organonitrate Yields From α-Pinene + NO3,
J. Phys. Chem. Lett.,
8, 2826–2834, https://doi.org/10.1021/acs.jpclett.7b01038, 2017. a
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, 2014. a
Lienhard, D. M., Huisman, A. J., Krieger, U. K., Rudich, Y., Marcolli, C., Luo, B. P., Bones, D. L., Reid, J. P., Lambe, A. T., Canagaratna, M. R., Davidovits, P., Onasch, T. B., Worsnop, D. R., Steimer, S. S., Koop, T., and Peter, T.: Viscous organic aerosol particles in the upper troposphere: diffusivity-controlled water uptake and ice nucleation?, Atmos. Chem. Phys., 15, 13599–13613, https://doi.org/10.5194/acp-15-13599-2015, 2015. a, b, c
Lignell, H., Epstein, S. A., Marvin, M. R., Shemesh, D., Gerber, B., and Nizkorodov, S.:
Experimental and theoretical study of aqueous cis-pinonic acid photolysis,
J. Phys. Chem. A,
117, 12930–12945, https://doi.org/10.1021/jp4093018, 2013. a, b
Lopez-Hilfiker, F. D., Mohr, C., Ehn, M., Rubach, F., Kleist, E., Wildt, J., Mentel, Th. F., Lutz, A., Hallquist, M., Worsnop, D., and Thornton, J. A.: A novel method for online analysis of gas and particle composition: description and evaluation of a Filter Inlet for Gases and AEROsols (FIGAERO), Atmos. Meas. Tech., 7, 983–1001, https://doi.org/10.5194/amt-7-983-2014, 2014. a, b
Lopez-Hilfiker, F. D., Mohr, C., Ehn, M., Rubach, F., Kleist, E., Wildt, J., Mentel, Th. F., Carrasquillo, A. J., Daumit, K. E., Hunter, J. F., Kroll, J. H., Worsnop, D. R., and Thornton, J. A.: Phase partitioning and volatility of secondary organic aerosol components formed from α-pinene ozonolysis and OH oxidation: the importance of accretion products and other low volatility compounds, Atmos. Chem. Phys., 15, 7765–7776, https://doi.org/10.5194/acp-15-7765-2015, 2015. a, b, c
Lopez-Hilfiker, F. D., Mohr, C., D'Ambro, E. L., Lutz, A., Riedel, T. P., Gaston, C. J., Iyer, S., Zhang, Z., Gold, A., Surratt, J. D., Lee, B. H., Kurten, T., Hu, W., Jimenez, J., Hallquist, M., and Thornton, J. A.:
Molecular Composition and Volatility of Organic Aerosol in the Southeastern U.S.:
Implications for IEPOX Derived SOA,
Environ. Sci. Technol.,
50, 2200–2209, https://doi.org/10.1021/acs.est.5b04769, 2016. a
MATLAB:
R2019b,
The MathWorks Inc., Natick, Massachusetts, 2019. a
McVay, R. C., Zhang, X., Aumont, B., Valorso, R., Camredon, M., La, Y. S., Wennberg, P. O., and Seinfeld, J. H.: SOA formation from the photooxidation of α-pinene: systematic exploration of the simulation of chamber data, Atmos. Chem. Phys., 16, 2785–2802, https://doi.org/10.5194/acp-16-2785-2016, 2016. a
Mutzel, A., Rodigast, M., Iinuma, Y., Böge, O., and Herrmann, H.:
Monoterpene SOA–contribution of first-generation oxidation products to formation and chemical composition,
Atmos. Environ.,
130, 136–144, https://doi.org/10.1016/j.atmosenv.2015.10.080, 2016. a, b
Pankow, J. F. and Asher, W. E.: SIMPOL.1: a simple group contribution method for predicting vapor pressures and enthalpies of vaporization of multifunctional organic compounds, Atmos. Chem. Phys., 8, 2773–2796, https://doi.org/10.5194/acp-8-2773-2008, 2008. a
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. a
Räty, M., Peräkylä, O., Riva, M., Quéléver, L., Garmash, O., Rissanen, M., and Ehn, M.: Measurement report: Effects of NOx and seed aerosol on highly oxygenated organic molecules (HOMs) from cyclohexene ozonolysis, Atmos. Chem. Phys., 21, 7357–7372, https://doi.org/10.5194/acp-21-7357-2021, 2021. a
Rissanen, M. P., Kurtén, T., Sipilä, M., Thornton, J. A., Kausiala, O., Garmash, O., Kjaergaard, H. G., Petäjä, T., Worsnop, D. R., Ehn, M., and Kulmala, M.:
Effects of Chemical Complexity on the Autoxidation Mechanisms of Endocyclic Alkene Ozonolysis Products: From Methylcyclohexenes toward Understanding α-Pinene,
J. Phys. Chem. A,
119, 4633–4650, https://doi.org/10.1021/jp510966g, 2015. a
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. a, b
Schobesberger, S., D'Ambro, E. L., Lopez-Hilfiker, F. D., Mohr, C., and Thornton, J. A.: A model framework to retrieve thermodynamic and kinetic properties of organic aerosol from composition-resolved thermal desorption measurements, Atmos. Chem. Phys., 18, 14757–14785, https://doi.org/10.5194/acp-18-14757-2018, 2018. a, b
Seinfeld, J. H. and Pankow, J. F.:
Organic atmospheric particulate material,
Annu. Rev. Phys. Chem.,
54, 121–140, https://doi.org/10.1146/annurev.physchem.54.011002.103756, 2003. a
Stark, H., Yatavelli, R. L. N., Thompson, S. L., Kang, H., Krechmer, J. E., Kimmel, J. R., Palm, B. B., Hu, W., Hayes, P. L., Day, D. A., Campuzano-Jost, P., Canagaratna, M. R., Jayne, J. T., Worsnop, D. R., and Jimenez, J. L.:
Impact of Thermal Decomposition on Thermal Desorption Instruments: Advantage of Thermogram Analysis for Quantifying Volatility Distributions of Organic Species,
Environ. Sci. Technol.,
51, 8491–8500, https://doi.org/10.1021/acs.est.7b00160, 2017. a
Thornton, J. A., Mohr, C., Schobesberger, S., D'Ambro, E. L., Lee, B. H., and Lopez-Hilfiker, F. D.:
Evaluating Organic Aerosol Sources and Evolution with a Combined Molecular Composition and Volatility Framework Using the Filter Inlet for Gases and Aerosols (FIGAERO),
Accounts Chem. Res.,
53, 1415–1426, https://doi.org/10.1021/acs.accounts.0c00259, 2020. a
Wang, C., Yuan, T., Wood, S. A., Goss, K.-U., Li, J., Ying, Q., and Wania, F.: Uncertain Henry's law constants compromise equilibrium partitioning calculations of atmospheric oxidation products, Atmos. Chem. Phys., 17, 7529–7540, https://doi.org/10.5194/acp-17-7529-2017, 2017.
a
Wania, F., Lei, Y. D., Wang, C., Abbatt, J. P. D., and Goss, K.-U.: Novel methods for predicting gas–particle partitioning during the formation of secondary organic aerosol, Atmos. Chem. Phys., 14, 13189–13204, https://doi.org/10.5194/acp-14-13189-2014, 2014. a, b
Wania, F., Lei, Y. D., Wang, C., Abbatt, J. P. D., and Goss, K.-U.: Using the chemical equilibrium partitioning space to explore factors influencing the phase distribution of compounds involved in secondary organic aerosol formation, Atmos. Chem. Phys., 15, 3395–3412, https://doi.org/10.5194/acp-15-3395-2015, 2015. a
Wania, F., Awonaike, B., and Goss, K.-U.:
Comment on “Measured Saturation Vapor Pressures of Phenolic and Nitro-Aromatic Compounds”,
Environ. Sci. Technol.,
51, 7742–7743, https://doi.org/10.1021/acs.est.7b02079, 2017. a
Wavefunction Inc.:
Spartan'14,
Irvine, CA, 2014. a
Yang, L. H., Takeuchi, M., Chen, Y., and Ng, N. L.:
Characterization of Thermal Decomposition of Oxygenated Organic Compounds in FIGAERO-CIMS,
Aerosol Sci. Tech.,
55, 1321–1342, https://doi.org/10.1080/02786826.2021.1945529, 2021. a, b, c, d
Ye, Q., Wang, M., Hofbauer, V., Stolzenburg, D., Chen, D., Schervish, M., Vogel, A., Mauldin, R. L., Baalbaki, R., Brilke, S., Dada, L., Dias, A., Duplissy, J., El Haddad, I., Finkenzeller, H., Fischer, L., He, X., Kim, C., Kürten, A., Lamkaddam, H., Lee, C. P., Lehtipalo, K., Leiminger, M., Manninen, H. E., Marten, R., Mentler, B., Partoll, E., Petäjä, T., Rissanen, M. P., Schobesberger, S., Schuchmann, S., Simon, M., Tham, Y. J., Vazquez-Pufleau, M., Wagner, A. C., Wang, Y., Wu, Y., Xiao, M., Baltensperger, U., Curtius, J., Flagan, R., Kirkby, J., Kulmala, M., Volkamer, R., Winkler, P. M., Worsnop, D., and Donahue, N. M.:
Molecular Composition and Volatility of Nucleated Particles from α-Pinene Oxidation between −50 ∘C and +25 ∘C,
Environ. Sci. Technol.,
53, 12357–12365, https://doi.org/10.1021/acs.est.9b03265, 2019. a
Yli-Juuti, T., Mielonen, T., Heikkinen, L., Arola, A., Ehn, M., Isokääntä, S., Keskinen, H.-M., Kulmala, M., Laakso, A., Lipponen, A., Luoma, K., Mikkonen, S., Nieminen, T., Paasonen, P., Petäjä, T., Romakkaniemi, S., Tonttila, J., Kokkola, H., and Virtanen, A.:
Significance of the organic aerosol driven climate feedback in the boreal area,
Nat. Commun.,
12, 5637, https://doi.org/10.1038/s41467-021-25850-7, 2021. a
Ylisirniö, A., Barreira, L. M. F., Pullinen, I., Buchholz, A., Jayne, J., Krechmer, J. E., Worsnop, D. R., Virtanen, A., and Schobesberger, S.: On the calibration of FIGAERO-ToF-CIMS: importance and impact of calibrant delivery for the particle-phase calibration, Atmos. Meas. Tech., 14, 355–367, https://doi.org/10.5194/amt-14-355-2021, 2021. a, b, c, d, e, f, g, h
Short summary
Accurate saturation vapor pressure estimates of atmospherically relevant organic compounds are critical for modeling secondary organic aerosol (SOA) formation. We investigated vapor pressures of highly oxygenated SOA constituents using state-of-the-art computational and experimental methods. We found a good agreement between low and extremely low vapor pressures estimated using the two methods, and the smallest molecules detected in our experiment were likely products of thermal decomposition.
Accurate saturation vapor pressure estimates of atmospherically relevant organic compounds are...
Altmetrics
Final-revised paper
Preprint