Articles | Volume 19, issue 20
Atmos. Chem. Phys., 19, 13037–13052, 2019
https://doi.org/10.5194/acp-19-13037-2019
© Author(s) 2019. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Atmos. Chem. Phys., 19, 13037–13052, 2019
https://doi.org/10.5194/acp-19-13037-2019
© Author(s) 2019. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
22 Oct 2019
Research article
| 22 Oct 2019
Carboxylic acids from limonene oxidation by ozone and hydroxyl radicals: insights into mechanisms derived using a FIGAERO-CIMS
Julia Hammes et al.
Related authors
No articles found.
Aristeidis Voliotis, Mao Du, Yu Wang, Yunqi Shao, M. Rami Alfarra, Thomas J. Bannan, Dawei Hu, Kelly L. Pereira, Jaqueline F. Hamilton, Mattias Hallquist, Thomas F. Mentel, and Gordon McFiggans
Atmos. Chem. Phys., 22, 14147–14175, https://doi.org/10.5194/acp-22-14147-2022, https://doi.org/10.5194/acp-22-14147-2022, 2022
Short summary
Short summary
Mixing experiments are crucial and highly beneficial for our understanding of atmospheric chemical interactions. However, interpretation quickly becomes complex, and both the experimental design and evaluation need to be scrutinised carefully. Advanced online and offline compositional measurements can reveal substantial additional information to aid in the interpretation of yield data, including components uniquely found in mixtures and property changes in SOA formed from mixtures of VOCs.
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.
Philip T. M. Carlsson, Luc Vereecken, Anna Novelli, François Bernard, Steven S. Brown, Bellamy Brownwood, Changmin Cho, John N. Crowley, Patrick Dewald, Peter M. Edwards, Nils Friedrich, Juliane L. Fry, Mattias Hallquist, Luisa Hantschke, Thorsten Hohaus, Sungah Kang, Jonathan Liebmann, Alfred W. Mayhew, Thomas Mentel, David Reimer, Franz Rohrer, Justin Shenolikar, Ralf Tillmann, Epameinondas Tsiligiannis, Rongrong Wu, Andreas Wahner, Astrid Kiendler-Scharr, and Hendrik Fuchs
EGUsphere, https://doi.org/10.5194/egusphere-2022-587, https://doi.org/10.5194/egusphere-2022-587, 2022
Short summary
Short summary
The investigation of the bight-time oxidation of the most abundant hydrocarbon, isoprene in chamber experiments shows the importance of so far unaccounted reaction pathways leading to epoxy products, which could enhance particle formation. The chemical lifetime of organic nitrates from isoprene is long enough that the majority will be further oxidized on the next by daytime oxidants.
Jacky Yat Sing Pang, Anna Novelli, Martin Kaminski, Ismail-Hakki Acir, Birger Bohn, Philip T. M. Carlsson, Changmin Cho, Hans-Peter Dorn, Andreas Hofzumahaus, Xin Li, Anna Lutz, Sascha Nehr, David Reimer, Franz Rohrer, Ralf Tillmann, Robert Wegener, Astrid Kiendler-Scharr, Andreas Wahner, and Hendrik Fuchs
Atmos. Chem. Phys., 22, 8497–8527, https://doi.org/10.5194/acp-22-8497-2022, https://doi.org/10.5194/acp-22-8497-2022, 2022
Short summary
Short summary
This study investigates the radical chemical budget during the limonene oxidation at different atmospheric-relevant NO concentrations in chamber experiments under atmospheric conditions. It is found that the model–measurement discrepancies of HO2 and RO2 are very large at low NO concentrations that are typical for forested environments. Possible additional processes impacting HO2 and RO2 concentrations are discussed.
Najin Kim, Yafang Cheng, Nan Ma, Mira L. Pöhlker, Thomas Klimach, Thomas F. Mentel, Ovid O. Krüger, Ulrich Pöschl, and Hang Su
Atmos. Meas. Tech., 14, 6991–7005, https://doi.org/10.5194/amt-14-6991-2021, https://doi.org/10.5194/amt-14-6991-2021, 2021
Short summary
Short summary
A broad supersaturation scanning CCN (BS2-CCN) system, in which particles are exposed to a range of supersaturation simultaneously, can measure a broad range of CCN activity distribution with a high time resolution. We describe how the BS2-CCN system can be effectively calibrated and which factors can affect the calibration curve. Intercomparison experiments between typical DMA-CCN and BS2-CCN measurements to evaluate the BS2-CCN system showed high correlation and good agreement.
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.
Rongrong Wu, Luc Vereecken, Epameinondas Tsiligiannis, Sungah Kang, Sascha R. Albrecht, Luisa Hantschke, Defeng Zhao, Anna Novelli, Hendrik Fuchs, Ralf Tillmann, Thorsten Hohaus, Philip T. M. Carlsson, Justin Shenolikar, François Bernard, John N. Crowley, Juliane L. Fry, Bellamy Brownwood, Joel A. Thornton, Steven S. Brown, Astrid Kiendler-Scharr, Andreas Wahner, Mattias Hallquist, and Thomas F. Mentel
Atmos. Chem. Phys., 21, 10799–10824, https://doi.org/10.5194/acp-21-10799-2021, https://doi.org/10.5194/acp-21-10799-2021, 2021
Short summary
Short summary
Isoprene is the biogenic volatile organic compound with the largest emissions rates. The nighttime reaction of isoprene with the NO3 radical has a large potential to contribute to SOA. We classified isoprene nitrates into generations and proposed formation pathways. Considering the potential functionalization of the isoprene nitrates we propose that mainly isoprene dimers contribute to SOA formation from the isoprene NO3 reactions with at least a 5 % mass yield.
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.
Christian Mark Garcia Salvador, Rongzhi Tang, Michael Priestley, Linjie Li, Epameinondas Tsiligiannis, Michael Le Breton, Wenfei Zhu, Limin Zeng, Hui Wang, Ying Yu, Min Hu, Song Guo, and Mattias Hallquist
Atmos. Chem. Phys., 21, 1389–1406, https://doi.org/10.5194/acp-21-1389-2021, https://doi.org/10.5194/acp-21-1389-2021, 2021
Short summary
Short summary
High-frequency online measurement of gas- and particle-phase nitro-aromatic compounds (NACs) at a rural site in China, heavily influenced by biomass burning events, enabled the analysis of the production pathway of NACs, including an explanation of strong persistence in the daytime. The contribution of secondary processes was significant, even during the dominant wintertime influence of primary emissions, suggesting the important role of regional secondary chemistry, i.e. photochemical smog.
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.
Liyuan Zhou, Åsa M. Hallquist, Mattias Hallquist, Christian M. Salvador, Samuel M. Gaita, Åke Sjödin, Martin Jerksjö, Håkan Salberg, Ingvar Wängberg, Johan Mellqvist, Qianyun Liu, Berto P. Lee, and Chak K. Chan
Atmos. Chem. Phys., 20, 1701–1722, https://doi.org/10.5194/acp-20-1701-2020, https://doi.org/10.5194/acp-20-1701-2020, 2020
Short summary
Short summary
The study reports the transition in the atmospheric emission of particles and gases from on-road heavy-duty trucks (HDTs) caused by the modernisation of the fleet. We measured particle number (PN), particle mass (PM), black carbon (BC), nitrogen oxides (NOx), carbon monoxide (CO), hydrocarbon (HC), particle size distributions, and volatility in the plumes of 556 individual HDTs. Significant but different changes in emissions were evident for various pollutants with respect to emission standards.
Olga Garmash, Matti P. Rissanen, Iida Pullinen, Sebastian Schmitt, Oskari Kausiala, Ralf Tillmann, Defeng Zhao, Carl Percival, Thomas J. Bannan, Michael Priestley, Åsa M. Hallquist, Einhard Kleist, Astrid Kiendler-Scharr, Mattias Hallquist, Torsten Berndt, Gordon McFiggans, Jürgen Wildt, Thomas F. Mentel, and Mikael Ehn
Atmos. Chem. Phys., 20, 515–537, https://doi.org/10.5194/acp-20-515-2020, https://doi.org/10.5194/acp-20-515-2020, 2020
Short summary
Short summary
Highly oxygenated organic molecules (HOMs) facilitate aerosol formation in the atmosphere. Using NO3− chemical ionization mass spectrometry we investigated HOM composition and yield in oxidation of aromatic compounds at different reactant concentrations, in the presence of NOx and seed aerosol. Higher OH concentrations increased HOM yield, suggesting multiple oxidation steps, and affected HOM composition, potentially explaining in part discrepancies in published secondary organic aerosol yields.
Epameinondas Tsiligiannis, Julia Hammes, Christian Mark Salvador, Thomas F. Mentel, and Mattias Hallquist
Atmos. Chem. Phys., 19, 15073–15086, https://doi.org/10.5194/acp-19-15073-2019, https://doi.org/10.5194/acp-19-15073-2019, 2019
Short summary
Short summary
The role of anthropogenic VOCs (AVOCs) for SOA formation needs to be scrutinised. The aromatic 1,3,5-trimethylbenzene (TMB) was shown to form highly oxygenated organic molecules (HOMs) in NOx-free environments, possibly contributing to new particle formation (NPF). However, formation of HOMs and particles was suppressed in the presence of NOx, while the formation of organonitrates (ONs) was increased. Thus, aromatic AVOCs may not enhance NPF in urban air masses.
Michael Rolletter, Martin Kaminski, Ismail-Hakki Acir, Birger Bohn, Hans-Peter Dorn, Xin Li, Anna Lutz, Sascha Nehr, Franz Rohrer, Ralf Tillmann, Robert Wegener, Andreas Hofzumahaus, Astrid Kiendler-Scharr, Andreas Wahner, and Hendrik Fuchs
Atmos. Chem. Phys., 19, 11635–11649, https://doi.org/10.5194/acp-19-11635-2019, https://doi.org/10.5194/acp-19-11635-2019, 2019
Short summary
Short summary
Here we present a study of the photooxidation of alpha-pinene, the most abundant monoterpene, by hydroxyl radicals (OH) conducted in the simulation chamber SAPHIR under low NOx and atmospheric alpha-pinene concentrations. Yields of the main degradation products acetone, formaldehyde, and pinonaldehyde were determined and the HOx (OH + HO2) radical budget was investigated. Measurements were used to test current atmospheric models and a theory-based mechanism.
Yujue Wang, Min Hu, Yuchen Wang, Jing Zheng, Dongjie Shang, Yudong Yang, Ying Liu, Xiao Li, Rongzhi Tang, Wenfei Zhu, Zhuofei Du, Yusheng Wu, Song Guo, Zhijun Wu, Shengrong Lou, Mattias Hallquist, and Jian Zhen Yu
Atmos. Chem. Phys., 19, 7649–7665, https://doi.org/10.5194/acp-19-7649-2019, https://doi.org/10.5194/acp-19-7649-2019, 2019
Short summary
Short summary
Nitro-aromatic compounds (NACs), an important fraction in brown carbon, were comprehensively characterized in Beijing. The oxidation of anthropogenic VOCs represented more dominant sources of NACs than biomass burning. A transition of NO2 from low- to high-NOx regimes was observed. The contribution of aqueous-phase pathways to NAC formation increased at elevated RH. This work highlights secondary formation of NACs and influence factors in high NOx–anthropogenic VOC-dominated urban atmospheres.
Thomas J. Bannan, Michael Le Breton, Michael Priestley, Stephen D. Worrall, Asan Bacak, Nicholas A. Marsden, Archit Mehra, Julia Hammes, Mattias Hallquist, M. Rami Alfarra, Ulrich K. Krieger, Jonathan P. Reid, John Jayne, Wade Robinson, Gordon McFiggans, Hugh Coe, Carl J. Percival, and Dave Topping
Atmos. Meas. Tech., 12, 1429–1439, https://doi.org/10.5194/amt-12-1429-2019, https://doi.org/10.5194/amt-12-1429-2019, 2019
Short summary
Short summary
The Filter Inlet for Gases and AEROsols (FIGAERO) is an inlet designed to be coupled with a high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) and provides simultaneous molecular information relating to both the gas- and particle-phase samples. This method has been used to extract vapour pressures of compounds whilst giving quantitative concentrations in the particle phase. Here we detail an ideal set of benchmark compounds for characterization of the FIGAERO.
Sascha R. Albrecht, Anna Novelli, Andreas Hofzumahaus, Sungah Kang, Yare Baker, Thomas Mentel, Andreas Wahner, and Hendrik Fuchs
Atmos. Meas. Tech., 12, 891–902, https://doi.org/10.5194/amt-12-891-2019, https://doi.org/10.5194/amt-12-891-2019, 2019
Short summary
Short summary
Within this study we demonstrate reliable measurement of hydroperoxy (HO2) radicals via chemical ionisation mass spectrometry. HO2 is detected as an ion cluster with bromide ions, which allows a selective detection. This direct and sensitive measurement provides reliable data of HO2 radical concentrations in the atmosphere as demonstrated in the first application in simulation chamber experiments.
Michael Le Breton, Åsa M. Hallquist, Ravi Kant Pathak, David Simpson, Yujue Wang, John Johansson, Jing Zheng, Yudong Yang, Dongjie Shang, Haichao Wang, Qianyun Liu, Chak Chan, Tao Wang, Thomas J. Bannan, Michael Priestley, Carl J. Percival, Dudley E. Shallcross, Keding Lu, Song Guo, Min Hu, and Mattias Hallquist
Atmos. Chem. Phys., 18, 13013–13030, https://doi.org/10.5194/acp-18-13013-2018, https://doi.org/10.5194/acp-18-13013-2018, 2018
Short summary
Short summary
We apply state-of-the-art chemical characterization to determine the chloride radical production in Beijing via measurement of inorganic halogens at a semi-rural site. The high concentration of inorganic halogens, namely nitryl chloride, enables the production of chlorinated volatile organic compounds which are measured in both the gas and particle phases simultaneously. This enables the secondary production of aerosols via chlorine oxidation to be directly observed in ambient air.
Anna Novelli, Martin Kaminski, Michael Rolletter, Ismail-Hakki Acir, Birger Bohn, Hans-Peter Dorn, Xin Li, Anna Lutz, Sascha Nehr, Franz Rohrer, Ralf Tillmann, Robert Wegener, Frank Holland, Andreas Hofzumahaus, Astrid Kiendler-Scharr, Andreas Wahner, and Hendrik Fuchs
Atmos. Chem. Phys., 18, 11409–11422, https://doi.org/10.5194/acp-18-11409-2018, https://doi.org/10.5194/acp-18-11409-2018, 2018
Short summary
Short summary
The impact of photooxidation of 2-methyl-3-butene-2-ol (MBO) on the concentration of radical species was studied in the atmospheric simulation chamber SAPHIR. MBO is a volatile organic compound mainly emitted by ponderosa and lodgepole pines which are very abundant in forests in the central-west USA. A very good agreement between measured and modelled radical concentrations and products from the oxidation of MBO was observed in an environment with NO of ~ 200 pptv.
Eleni Karnezi, Benjamin N. Murphy, Laurent Poulain, Hartmut Herrmann, Alfred Wiedensohler, Florian Rubach, Astrid Kiendler-Scharr, Thomas F. Mentel, and Spyros N. Pandis
Atmos. Chem. Phys., 18, 10759–10772, https://doi.org/10.5194/acp-18-10759-2018, https://doi.org/10.5194/acp-18-10759-2018, 2018
Short summary
Short summary
Different parameterizations of the organic aerosol (OA) formation and evolution are evaluated using ground and airborne measurements collected in the 2012 PEGASOS field campaign in the Po Valley (Italy). Total OA concentration and O : C ratios were reproduced within experimental error by a number of schemes. Anthropogenic secondary OA (SOA) contributed 15–25 % of the total OA, 20–35 % of SOA from intermediate volatility compounds oxidation, and 15–45 % of biogenic SOA depending on the scheme.
Yujue Wang, Min Hu, Song Guo, Yuchen Wang, Jing Zheng, Yudong Yang, Wenfei Zhu, Rongzhi Tang, Xiao Li, Ying Liu, Michael Le Breton, Zhuofei Du, Dongjie Shang, Yusheng Wu, Zhijun Wu, Yu Song, Shengrong Lou, Mattias Hallquist, and Jianzhen Yu
Atmos. Chem. Phys., 18, 10693–10713, https://doi.org/10.5194/acp-18-10693-2018, https://doi.org/10.5194/acp-18-10693-2018, 2018
Short summary
Short summary
The overall characteristics and concentrations of organosulfates (OSs) and nitrooxy-OSs (NOSs) were determined in summer in Beijing. This study provided direct observational evidence that OSs form via acid-catalyzed aqueous-phase reactions in the presence of acidic sulfate aerosols, and monoterpene NOSs form via nighttime NO3 oxidation. Using OSs and NOSs as examples, this work highlights the formation pathways of SOA via anthropogenic–biogenic interactions and organic–inorganic reactions.
Michael Le Breton, Yujue Wang, Åsa M. Hallquist, Ravi Kant Pathak, Jing Zheng, Yudong Yang, Dongjie Shang, Marianne Glasius, Thomas J. Bannan, Qianyun Liu, Chak K. Chan, Carl J. Percival, Wenfei Zhu, Shengrong Lou, David Topping, Yuchen Wang, Jianzhen Yu, Keding Lu, Song Guo, Min Hu, and Mattias Hallquist
Atmos. Chem. Phys., 18, 10355–10371, https://doi.org/10.5194/acp-18-10355-2018, https://doi.org/10.5194/acp-18-10355-2018, 2018
Short summary
Short summary
This paper utilizes a chemical ionisation mass spectrometer measuring gas and particle-phase organosulfates (OS) simultaneously during a field campaign in Beijing, China, and highlights how high time frequency online measurements enable a detailed analysis of dominant production mechanisms. We find that high aerosol acidity, organic precursor concentration and relative humidity promote the production of OS. The thermogram desorption reveals the potential for semi-volatile gas-phase OS.
Xiangyu Pei, Mattias Hallquist, Axel C. Eriksson, Joakim Pagels, Neil M. Donahue, Thomas Mentel, Birgitta Svenningsson, William Brune, and Ravi Kant Pathak
Atmos. Chem. Phys., 18, 9845–9860, https://doi.org/10.5194/acp-18-9845-2018, https://doi.org/10.5194/acp-18-9845-2018, 2018
Short summary
Short summary
The findings in this study show that morphological transformation of soot occurs via two key complementary and sequential processes, i.e., void filling in the particle and its diameter growth. To quantify the state of morphological transformation, i.e., the utilization of material for filling and growth during the condensation processes, a framework was developed which can further be utilized to quantify the effect of condensed material on the optical and hygroscopic properties of soot.
Haichao Wang, Keding Lu, Song Guo, Zhijun Wu, Dongjie Shang, Zhaofeng Tan, Yujue Wang, Michael Le Breton, Shengrong Lou, Mingjin Tang, Yusheng Wu, Wenfei Zhu, Jing Zheng, Limin Zeng, Mattias Hallquist, Min Hu, and Yuanhang Zhang
Atmos. Chem. Phys., 18, 9705–9721, https://doi.org/10.5194/acp-18-9705-2018, https://doi.org/10.5194/acp-18-9705-2018, 2018
Short summary
Short summary
N2O5, ClNO2, and particulate nitrate were measured simultaneously in Beijing, China, in 2016. The elevated N2O5 uptake coefficient and ClNO2 yield were determined, which suggest fast N2O5 uptake in Beijing. We highlight that the NO3 oxidation in nocturnal VOC degradation is efficient, with fast formation of organic nitrates. More studies are needed to investigate NO3–N2O5 chemistry and its contribution to secondary organic aerosol formation.
Mingjin Wang, Tong Zhu, Defeng Zhao, Florian Rubach, Andreas Wahner, Astrid Kiendler-Scharr, and Thomas F. Mentel
Atmos. Chem. Phys., 18, 7345–7359, https://doi.org/10.5194/acp-18-7345-2018, https://doi.org/10.5194/acp-18-7345-2018, 2018
Short summary
Short summary
Organic coatings modify hygroscopicity and CCN activation of mineral dust perticles. Small amounts of oleic acid coating (volume fraction (vf) ≤ 4.1 %) decreased the CCN activity of CaCO3 particles, while more oleic acid coating (vf ≥ 14.8 %) increased the CCN activity of CaCO3 particles, while malonic acid coating (vf = 0.4−42 %) even in smallest amounts increased the CCN activity of CaCO3 particles. Our laboratory results should also hold under conditions of the atmosphere.
Cameron Faxon, Julia Hammes, Michael Le Breton, Ravi Kant Pathak, and Mattias Hallquist
Atmos. Chem. Phys., 18, 5467–5481, https://doi.org/10.5194/acp-18-5467-2018, https://doi.org/10.5194/acp-18-5467-2018, 2018
Short summary
Short summary
Nighttime oxidation of organic compounds emitted from vegetation produce aerosol particles affecting climate and human health. Here we apply state-of the-art chemical characterization for a detailed study on the oxidation of limonene initiated by the nitrate radical. We now have the identity of major nitrated products and their thermal properties. Including a cluster analysis, through this study, new knowledge supporting modeling and field observations of organic nitrates is gained.
Rongzhi Tang, Zepeng Wu, Xiao Li, Yujue Wang, Dongjie Shang, Yao Xiao, Mengren Li, Limin Zeng, Zhijun Wu, Mattias Hallquist, Min Hu, and Song Guo
Atmos. Chem. Phys., 18, 4055–4068, https://doi.org/10.5194/acp-18-4055-2018, https://doi.org/10.5194/acp-18-4055-2018, 2018
Short summary
Short summary
We used CMB and the tracer yield method to apportion organic sources in Beijing. Vehicular emissions served as the dominant source, and the contributions of all the other primary sources decreased. One interesting result is that in contrast to the SOA from other regions in the world where biogenic SOA was dominant, anthropogenic SOA was the major contributor to SOA, implying that deducting anthropogenic VOC emissions is an efficient way to reduce SOA in Beijing.
Defeng Zhao, Sebastian H. Schmitt, Mingjin Wang, Ismail-Hakki Acir, Ralf Tillmann, Zhaofeng Tan, Anna Novelli, Hendrik Fuchs, Iida Pullinen, Robert Wegener, Franz Rohrer, Jürgen Wildt, Astrid Kiendler-Scharr, Andreas Wahner, and Thomas F. Mentel
Atmos. Chem. Phys., 18, 1611–1628, https://doi.org/10.5194/acp-18-1611-2018, https://doi.org/10.5194/acp-18-1611-2018, 2018
Short summary
Short summary
Air pollutants emitted by human activities such as NOx and SO2 can influence the abundance of secondary organic aerosol (SOA) from biogenic volatile organic compounds (VOCs). We found that NOx suppressed new particle formation and SOA mass formation. When both SO2 and NOx are present, the suppressing effect of NOx on SOA mass formation was counteracted by SO2. High NOx changed SOA chemical composition, forming more organic nitrate, because NOx changed radical chemistry during VOC oxidation.
Cheng Wu, Iida Pullinen, Stefanie Andres, Astrid Kiendler-Scharr, Einhard Kleist, Andreas Wahner, Jürgen Wildt, and Thomas F. Mentel
Biogeosciences Discuss., https://doi.org/10.5194/bg-2017-260, https://doi.org/10.5194/bg-2017-260, 2017
Manuscript not accepted for further review
Short summary
Short summary
Biogenic volatile organic compounds are important for atmospheric chemistry. We showed by 13CO2 labelling experiments that biosynthesis is not restricted to the presence of light. In particular sesquiterpenes exhibit substantial de novo emissions in darkness with the carbon being delivered from alternative carbon sources. Our findings are of importance for future emissions under conditions of climate change as the response of de novo emissions to stresses differs from that of pool emissions.
Emma L. D'Ambro, Ben H. Lee, Jiumeng Liu, John E. Shilling, Cassandra J. Gaston, Felipe D. Lopez-Hilfiker, Siegfried Schobesberger, Rahul A. Zaveri, Claudia Mohr, Anna Lutz, Zhenfa Zhang, Avram Gold, Jason D. Surratt, Jean C. Rivera-Rios, Frank N. Keutsch, and Joel A. Thornton
Atmos. Chem. Phys., 17, 159–174, https://doi.org/10.5194/acp-17-159-2017, https://doi.org/10.5194/acp-17-159-2017, 2017
Short summary
Short summary
We studied the formation and properties of secondary organic aerosol produced from isoprene. We find that a significant fraction (~50 %) of the mass is composed of low-volatility, highly oxidized compounds such as C5H12O6. A significant fraction of the remainder appears to be in the form of oligomeric material. Adding NOx maintained or decreased SOA yields while increasing the fraction of low-volatility material, possibly due to oligomers.
Mehrnaz Sarrafzadeh, Jürgen Wildt, Iida Pullinen, Monika Springer, Einhard Kleist, Ralf Tillmann, Sebastian H. Schmitt, Cheng Wu, Thomas F. Mentel, Defeng Zhao, Donald R. Hastie, and Astrid Kiendler-Scharr
Atmos. Chem. Phys., 16, 11237–11248, https://doi.org/10.5194/acp-16-11237-2016, https://doi.org/10.5194/acp-16-11237-2016, 2016
Short summary
Short summary
We investigated NOx impacts on the formation of secondary organic aerosol (SOA) mass from b-pinene and we could reveal two different mechanisms of impacts. One of them was the impact of NOx on OH that could explain increasing SOA yield with increasing NOx at low NOx conditions. The other was the suppression of new particle formation limiting the condensational sink for the SOA precursors. This effect could explain a substantial fraction of the decrease of SOA yield observed at high NOx.
Bernadette Rosati, Martin Gysel, Florian Rubach, Thomas F. Mentel, Brigitta Goger, Laurent Poulain, Patrick Schlag, Pasi Miettinen, Aki Pajunoja, Annele Virtanen, Henk Klein Baltink, J. S. Bas Henzing, Johannes Größ, Gian Paolo Gobbi, Alfred Wiedensohler, Astrid Kiendler-Scharr, Stefano Decesari, Maria Cristina Facchini, Ernest Weingartner, and Urs Baltensperger
Atmos. Chem. Phys., 16, 7295–7315, https://doi.org/10.5194/acp-16-7295-2016, https://doi.org/10.5194/acp-16-7295-2016, 2016
Short summary
Short summary
This study presents PEGASOS project data from field campaigns in the Po Valley, Italy and the Netherlands. Vertical profiles of aerosol hygroscopicity and chemical composition were investigated with airborne measurements on board a Zeppelin NT airship. A special focus was on the evolution of different mixing layers within the PBL as a function of daytime. A closure study showed that variations in aerosol hygroscopicity can well be explained by the variations in chemical composition.
Simon Schallhart, Pekka Rantala, Eiko Nemitz, Ditte Taipale, Ralf Tillmann, Thomas F. Mentel, Benjamin Loubet, Giacomo Gerosa, Angelo Finco, Janne Rinne, and Taina M. Ruuskanen
Atmos. Chem. Phys., 16, 7171–7194, https://doi.org/10.5194/acp-16-7171-2016, https://doi.org/10.5194/acp-16-7171-2016, 2016
Short summary
Short summary
We present ecosystem exchange fluxes from a mixed oak–hornbeam forest in the Po Valley, Italy. Detectable fluxes were observed for 29 compounds, dominated by isoprene, which comprised over 60 % of the upward flux. Methanol seemed to be deposited to dew, as the deposition happened in the early morning. We estimated that up to 30 % of the upward flux of methyl vinyl ketone and methacrolein originated from atmospheric oxidation of isoprene.
Bernadette Rosati, Erik Herrmann, Silvia Bucci, Federico Fierli, Francesco Cairo, Martin Gysel, Ralf Tillmann, Johannes Größ, Gian Paolo Gobbi, Luca Di Liberto, Guido Di Donfrancesco, Alfred Wiedensohler, Ernest Weingartner, Annele Virtanen, Thomas F. Mentel, and Urs Baltensperger
Atmos. Chem. Phys., 16, 4539–4554, https://doi.org/10.5194/acp-16-4539-2016, https://doi.org/10.5194/acp-16-4539-2016, 2016
Short summary
Short summary
We present vertical profiles of aerosol optical properties, which were explored within the planetary boundary layer in a case study in 2012 in the Po Valley region. A comparison of in situ measurements recorded aboard a Zeppelin NT and ground-based remote-sensing data was performed yielding good agreement. Additionally, the role of ambient relative humidity for the aerosol particles' optical properties was investigated.
Andrea Ghirardo, Junfei Xie, Xunhua Zheng, Yuesi Wang, Rüdiger Grote, Katja Block, Jürgen Wildt, Thomas Mentel, Astrid Kiendler-Scharr, Mattias Hallquist, Klaus Butterbach-Bahl, and Jörg-Peter Schnitzler
Atmos. Chem. Phys., 16, 2901–2920, https://doi.org/10.5194/acp-16-2901-2016, https://doi.org/10.5194/acp-16-2901-2016, 2016
Short summary
Short summary
Trees can impact urban air quality. Large emissions of plant volatiles are emitted in Beijing as a stress response to the urban polluted environment, but their impacts on secondary particulate matter remain relatively low compared to those originated from anthropogenic activities. The present study highlights the importance of including stress-induced compounds when studying plant volatile emissions.
M. Dal Maso, L. Liao, J. Wildt, A. Kiendler-Scharr, E. Kleist, R. Tillmann, M. Sipilä, J. Hakala, K. Lehtipalo, M. Ehn, V.-M. Kerminen, M. Kulmala, D. Worsnop, and T. Mentel
Atmos. Chem. Phys., 16, 1955–1970, https://doi.org/10.5194/acp-16-1955-2016, https://doi.org/10.5194/acp-16-1955-2016, 2016
Short summary
Short summary
In this paper, we present the first direct laboratory observations of nanoparticle formation from sulfuric acid and realistic BVOC precursor vapour mixtures performed at atmospherically relevant concentration levels. We found that the formation rate was proportional to the product of sulphuric acid and biogenic VOC emission strength, and that the formation rates were consistent with a mechanism in which nucleating BVOC oxidation products are rapidly formed and activate with sulfuric acid.
D. F. Zhao, A. Buchholz, B. Kortner, P. Schlag, F. Rubach, H. Fuchs, A. Kiendler-Scharr, R. Tillmann, A. Wahner, Å. K. Watne, M. Hallquist, J. M. Flores, Y. Rudich, K. Kristensen, A. M. K. Hansen, M. Glasius, I. Kourtchev, M. Kalberer, and Th. F. Mentel
Atmos. Chem. Phys., 16, 1105–1121, https://doi.org/10.5194/acp-16-1105-2016, https://doi.org/10.5194/acp-16-1105-2016, 2016
Short summary
Short summary
This study investigated the cloud droplet activation behavior and hygroscopic growth of mixed anthropogenic and biogenic SOA (ABSOA) compared to pure biogenic SOA (BSOA) and pure anthropogenic SOA (ASOA). Cloud droplet activation behaviors of different types of SOA were similar. In contrast, the hygroscopicity of ASOA was higher than BSOA and ABSOA. ASOA components enhanced the hygroscopicity of the ABSOA. Yet this enhancement cannot be described by a linear mixing of pure SOA systems.
P. Roldin, L. Liao, D. Mogensen, M. Dal Maso, A. Rusanen, V.-M. Kerminen, T. F. Mentel, J. Wildt, E. Kleist, A. Kiendler-Scharr, R. Tillmann, M. Ehn, M. Kulmala, and M. Boy
Atmos. Chem. Phys., 15, 10777–10798, https://doi.org/10.5194/acp-15-10777-2015, https://doi.org/10.5194/acp-15-10777-2015, 2015
Short summary
Short summary
We used the ADCHAM model to study new particle formation events in the JPAC chamber. The model results show that the new particles may be formed by a kinetic type of nucleation involving both sulphuric acid and organic compounds formed from OH oxidation of volatile organic compounds (VOCs). The observed particle growth may either be controlled by the condensation of semi- and low-volatililty organic compounds or by the formation of low-volatility compounds (oligomers) at the particle surface.
F. D. Lopez-Hilfiker, C. Mohr, M. Ehn, F. Rubach, E. Kleist, J. Wildt, Th. F. Mentel, A. J. Carrasquillo, K. E. Daumit, J. F. Hunter, J. H. Kroll, D. R. Worsnop, and J. A. Thornton
Atmos. Chem. Phys., 15, 7765–7776, https://doi.org/10.5194/acp-15-7765-2015, https://doi.org/10.5194/acp-15-7765-2015, 2015
Short summary
Short summary
We measured a large suite organic compounds using a recently developed Filter Inlet for Gases and AEROsols (FIGAERO) coupled to a (HR-ToF-CIMS). The instrument was deployed on environmental simulation chambers to study monoterpene oxidation as a secondary organic aerosol (SOA) source. We find that approximately 50% of the detected particle phase mass is associated with compounds having effective vapor pressures 4, or more, orders of magnitude lower than commonly measured products.
T. F. Mentel, M. Springer, M. Ehn, E. Kleist, I. Pullinen, T. Kurtén, M. Rissanen, A. Wahner, and J. Wildt
Atmos. Chem. Phys., 15, 6745–6765, https://doi.org/10.5194/acp-15-6745-2015, https://doi.org/10.5194/acp-15-6745-2015, 2015
Short summary
Short summary
We studied a series of cycloalkenes and methyl-substituted alkenes in order to elucidate the structural pre-requisites and chemical pathways to the recently discovered class of highly oxidized molecules ELVOC (Ehn et al., Nature, 2014). ELVOC may totally change the view on (parts of) the mechanism of SOA formation. We present results which support recent observations of H shifts from C-H to peroxy radicals, highlighting the pivotal role of peroxyradicals in organic atmospheric chemistry.
J. Kaiser, G. M. Wolfe, B. Bohn, S. Broch, H. Fuchs, L. N. Ganzeveld, S. Gomm, R. Häseler, A. Hofzumahaus, F. Holland, J. Jäger, X. Li, I. Lohse, K. Lu, A. S. H. Prévôt, F. Rohrer, R. Wegener, R. Wolf, T. F. Mentel, A. Kiendler-Scharr, A. Wahner, and F. N. Keutsch
Atmos. Chem. Phys., 15, 1289–1298, https://doi.org/10.5194/acp-15-1289-2015, https://doi.org/10.5194/acp-15-1289-2015, 2015
Short summary
Short summary
Using measurements acquired from a Zeppelin airship during the PEGASOS 2012 campaign, we show that VOC oxidation alone cannot account for the formaldehyde concentrations observed in the morning over rural Italy. Vertical profiles suggest a ground-level source of HCHO. Incorporating this additional HCHO source into a photochemical model increases calculated O3 production by as much as 12%.
D. F. Zhao, M. Kaminski, P. Schlag, H. Fuchs, I.-H. Acir, B. Bohn, R. Häseler, A. Kiendler-Scharr, F. Rohrer, R. Tillmann, M. J. Wang, R. Wegener, J. Wildt, A. Wahner, and Th. F. Mentel
Atmos. Chem. Phys., 15, 991–1012, https://doi.org/10.5194/acp-15-991-2015, https://doi.org/10.5194/acp-15-991-2015, 2015
C. Wu, I. Pullinen, S. Andres, G. Carriero, S. Fares, H. Goldbach, L. Hacker, T. Kasal, A. Kiendler-Scharr, E. Kleist, E. Paoletti, A. Wahner, J. Wildt, and Th. F. Mentel
Biogeosciences, 12, 177–191, https://doi.org/10.5194/bg-12-177-2015, https://doi.org/10.5194/bg-12-177-2015, 2015
Short summary
Short summary
Impacts of soil moisture on de novo monoterpene emissions from several tree species were studied. Mild drought slightly increased MT emissions, but with further progressing drought the emissions decreased to almost zero. Increases of MT emissions were explainable by increases of leaf temperature due to lowered transpirational cooling. The decrease of emissions observed when soil moisture fell below certain thresholds was parameterized, allowing considering impacts of soil moisture in models.
R. Bergström, M. Hallquist, D. Simpson, J. Wildt, and T. F. Mentel
Atmos. Chem. Phys., 14, 13643–13660, https://doi.org/10.5194/acp-14-13643-2014, https://doi.org/10.5194/acp-14-13643-2014, 2014
J. M. Flores, D. F. Zhao, L. Segev, P. Schlag, A. Kiendler-Scharr, H. Fuchs, Å. K. Watne, N. Bluvshtein, Th. F. Mentel, M. Hallquist, and Y. Rudich
Atmos. Chem. Phys., 14, 5793–5806, https://doi.org/10.5194/acp-14-5793-2014, https://doi.org/10.5194/acp-14-5793-2014, 2014
F. D. Lopez-Hilfiker, C. Mohr, M. Ehn, F. Rubach, E. Kleist, J. Wildt, Th. F. Mentel, A. Lutz, M. Hallquist, D. Worsnop, and J. A. Thornton
Atmos. Meas. Tech., 7, 983–1001, https://doi.org/10.5194/amt-7-983-2014, https://doi.org/10.5194/amt-7-983-2014, 2014
J. Wildt, T. F. Mentel, A. Kiendler-Scharr, T. Hoffmann, S. Andres, M. Ehn, E. Kleist, P. Müsgen, F. Rohrer, Y. Rudich, M. Springer, R. Tillmann, and A. Wahner
Atmos. Chem. Phys., 14, 2789–2804, https://doi.org/10.5194/acp-14-2789-2014, https://doi.org/10.5194/acp-14-2789-2014, 2014
Th. F. Mentel, E. Kleist, S. Andres, M. Dal Maso, T. Hohaus, A. Kiendler-Scharr, Y. Rudich, M. Springer, R. Tillmann, R. Uerlings, A. Wahner, and J. Wildt
Atmos. Chem. Phys., 13, 8755–8770, https://doi.org/10.5194/acp-13-8755-2013, https://doi.org/10.5194/acp-13-8755-2013, 2013
Y. P. Li, H. Elbern, K. D. Lu, E. Friese, A. Kiendler-Scharr, Th. F. Mentel, X. S. Wang, A. Wahner, and Y. H. Zhang
Atmos. Chem. Phys., 13, 6289–6304, https://doi.org/10.5194/acp-13-6289-2013, https://doi.org/10.5194/acp-13-6289-2013, 2013
H.-P. Dorn, R. L. Apodaca, S. M. Ball, T. Brauers, S. S. Brown, J. N. Crowley, W. P. Dubé, H. Fuchs, R. Häseler, U. Heitmann, R. L. Jones, A. Kiendler-Scharr, I. Labazan, J. M. Langridge, J. Meinen, T. F. Mentel, U. Platt, D. Pöhler, F. Rohrer, A. A. Ruth, E. Schlosser, G. Schuster, A. J. L. Shillings, W. R. Simpson, J. Thieser, R. Tillmann, R. Varma, D. S. Venables, and A. Wahner
Atmos. Meas. Tech., 6, 1111–1140, https://doi.org/10.5194/amt-6-1111-2013, https://doi.org/10.5194/amt-6-1111-2013, 2013
E. U. Emanuelsson, M. Hallquist, K. Kristensen, M. Glasius, B. Bohn, H. Fuchs, B. Kammer, A. Kiendler-Scharr, S. Nehr, F. Rubach, R. Tillmann, A. Wahner, H.-C. Wu, and Th. F. Mentel
Atmos. Chem. Phys., 13, 2837–2855, https://doi.org/10.5194/acp-13-2837-2013, https://doi.org/10.5194/acp-13-2837-2013, 2013
E. Kleist, T. F. Mentel, S. Andres, A. Bohne, A. Folkers, A. Kiendler-Scharr, Y. Rudich, M. Springer, R. Tillmann, and J. Wildt
Biogeosciences, 9, 5111–5123, https://doi.org/10.5194/bg-9-5111-2012, https://doi.org/10.5194/bg-9-5111-2012, 2012
Related subject area
Subject: Gases | Research Activity: Laboratory Studies | Altitude Range: Troposphere | Science Focus: Chemistry (chemical composition and reactions)
Measurement of Henry's law and liquid-phase loss rate constants of peroxypropionic nitric anhydride (PPN) in deionized water and in n-octanol
Product distribution, kinetics, and aerosol formation from the OH oxidation of dimethyl sulfide under different RO2 regimes
Atmospheric breakdown chemistry of the new “green” solvent 2,2,5,5-tetramethyloxolane via gas-phase reactions with OH and Cl radicals
Impact of cooking style and oil on semi-volatile and intermediate volatility organic compound emissions from Chinese domestic cooking
Observations of gas-phase products from the nitrate-radical-initiated oxidation of four monoterpenes
Investigation of the limonene photooxidation by OH at different NO concentrations in the atmospheric simulation chamber SAPHIR (Simulation of Atmospheric PHotochemistry In a large Reaction Chamber)
Kinetic study of the atmospheric oxidation of a series of epoxy compounds by OH radicals
An experimental study of the reactivity of terpinolene and β-caryophyllene with the nitrate radical
Oxidation product characterization from ozonolysis of the diterpene ent-kaurene
Kinetics of OH + SO2 + M: temperature-dependent rate coefficients in the fall-off regime and the influence of water vapour
Formation of organic sulfur compounds through SO2-initiated photochemistry of PAHs and dimethylsulfoxide at the air-water interface
Stable carbon isotopic composition of biomass burning emissions – implications for estimating the contribution of C3 and C4 plants
Evaluation of the daytime tropospheric loss of 2-methylbutanal
Investigations into the gas-phase photolysis and OH radical kinetics of nitrocatechols: implications of intramolecular interactions on their atmospheric behaviour
Reproducing Arctic springtime tropospheric ozone and mercury depletion events in an outdoor mesocosm sea ice facility
N2O5 uptake onto saline mineral dust: a potential missing source of tropospheric ClNO2 in inland China
NO3 chemistry of wildfire emissions: a kinetic study of the gas-phase reactions of furans with the NO3 radical
Marine gas-phase sulfur emissions during an induced phytoplankton bloom
Biomass burning plume chemistry: OH-radical-initiated oxidation of 3-penten-2-one and its main oxidation product 2-hydroxypropanal
Atmospheric photo-oxidation of myrcene: OH reaction rate constant, gas-phase oxidation products and radical budgets
Characterization of ambient volatile organic compounds, source apportionment, and the ozone–NOx–VOC sensitivities in a heavily polluted megacity of central China: effect of sporting events and emission reductions
Atmospheric oxidation of α,β-unsaturated ketones: kinetics and mechanism of the OH radical reaction
Reactions of NO3 with aromatic aldehydes: gas-phase kinetics and insights into the mechanism of the reaction
Atmospheric photooxidation and ozonolysis of Δ3-carene and 3-caronaldehyde: rate constants and product yields
Measurement report: Biogenic volatile organic compound emission profiles of rapeseed leaf litter and its secondary organic aerosol formation potential
Highly oxygenated organic molecules produced by the oxidation of benzene and toluene in a wide range of OH exposure and NOx conditions
Molecular composition and volatility of multi-generation products formed from isoprene oxidation by nitrate radical
Highly oxygenated organic molecule (HOM) formation in the isoprene oxidation by NO3 radical
Volatile organic compound emissions from solvent- and water-borne coatings – compositional differences and tracer compound identifications
Evaluated kinetic and photochemical data for atmospheric chemistry: volume VIII – gas-phase reactions of organic species with four, or more, carbon atoms ( ≥ C4)
Chemical characterisation of benzene oxidation products under high- and low-NOx conditions using chemical ionisation mass spectrometry
Emissions of non-methane volatile organic compounds from combustion of domestic fuels in Delhi, India
A comparative and experimental study of the reactivity with nitrate radical of two terpenes: α-terpinene and γ-terpinene
Photooxidation of pinonaldehyde at ambient conditions investigated in the atmospheric simulation chamber SAPHIR
Reaction between CH3C(O)OOH (peracetic acid) and OH in the gas phase: a combined experimental and theoretical study of the kinetics and mechanism
Snow heterogeneous reactivity of bromide with ozone lost during snow metamorphism
Evaluated kinetic and photochemical data for atmospheric chemistry: Volume VII – Criegee intermediates
Technical Note: Effect of varying the λ = 185 and 254 nm photon flux ratio on radical generation in oxidation flow reactors
Kinetics of dimethyl sulfide (DMS) reactions with isoprene-derived Criegee intermediates studied with direct UV absorption
Determination of the absorption cross sections of higher-order iodine oxides at 355 and 532 nm
Evolution of NO3 reactivity during the oxidation of isoprene
Rate coefficients for reactions of OH with aromatic and aliphatic volatile organic compounds determined by the multivariate relative rate technique
Atmospheric fate of two relevant unsaturated ketoethers: kinetics, products and mechanisms for the reaction of hydroxyl radicals with (E)-4-methoxy-3-buten-2-one and (1E)-1-methoxy-2-methyl-1-penten-3-one
The nitrogen budget of laboratory-simulated western US wildfires during the FIREX 2016 Fire Lab study
Importance of isomerization reactions for OH radical regeneration from the photo-oxidation of isoprene investigated in the atmospheric simulation chamber SAPHIR
Kinetics of the OH + NO2 reaction: effect of water vapour and new parameterization for global modelling
Kinetic and mechanistic study of the reaction between methane sulfonamide (CH3S(O)2NH2) and OH
Dimensionality-reduction techniques for complex mass spectrometric datasets: application to laboratory atmospheric organic oxidation experiments
Atmospheric fate of a series of saturated alcohols: kinetic and mechanistic study
Multi-generation OH oxidation as a source for highly oxygenated organic molecules from aromatics
Kevin D. Easterbrook, Mitchell A. Vona, Kiana Nayebi-Astaneh, Amanda M. Miller, and Hans D. Osthoff
Atmos. Chem. Phys., 23, 311–322, https://doi.org/10.5194/acp-23-311-2023, https://doi.org/10.5194/acp-23-311-2023, 2023
Short summary
Short summary
The trace gas peroxypropionyl nitrate (PPN) is generated in photochemical smog, phytotoxic, a strong eye irritant, and possibly mutagenic. Here, its solubility and reactivity in water and in octanol were investigated using a bubble flow apparatus, yielding its Henry's law constant and octanol–water partition coefficient (Kow). The results allow the fate of PPN to be more accurately constrained in atmospheric chemical transport models, including its uptake on clouds, organic aerosol, and leaves.
Qing Ye, Matthew B. Goss, Jordan E. Krechmer, Francesca Majluf, Alexander Zaytsev, Yaowei Li, Joseph R. Roscioli, Manjula Canagaratna, Frank N. Keutsch, Colette L. Heald, and Jesse H. Kroll
Atmos. Chem. Phys., 22, 16003–16015, https://doi.org/10.5194/acp-22-16003-2022, https://doi.org/10.5194/acp-22-16003-2022, 2022
Short summary
Short summary
The atmospheric oxidation of dimethyl sulfide (DMS) is a major natural source of sulfate particles in the atmosphere. However, its mechanism is poorly constrained. In our work, laboratory measurements and mechanistic modeling were conducted to comprehensively investigate DMS oxidation products and key reaction rates. We find that the peroxy radical (RO2) has a controlling effect on product distribution and aerosol yield, with the isomerization of RO2 leading to the suppression of aerosol yield.
Caterina Mapelli, Juliette V. Schleicher, Alex Hawtin, Conor D. Rankine, Fiona C. Whiting, Fergal Byrne, C. Rob McElroy, Claudiu Roman, Cecilia Arsene, Romeo I. Olariu, Iustinian G. Bejan, and Terry J. Dillon
Atmos. Chem. Phys., 22, 14589–14602, https://doi.org/10.5194/acp-22-14589-2022, https://doi.org/10.5194/acp-22-14589-2022, 2022
Short summary
Short summary
Solvents represent an important source of pollution from the chemical industry. New "green" solvents aim to replace toxic solvents with new molecules made from renewable sources and designed to be less harmful. Whilst these new molecules are selected according to toxicity and other characteristics, no consideration has yet been included on air quality. Studying the solvent breakdown in air, we found that TMO has a lower impact on air quality than traditional solvents with similar properties.
Kai Song, Song Guo, Yuanzheng Gong, Daqi Lv, Yuan Zhang, Zichao Wan, Tianyu Li, Wenfei Zhu, Hui Wang, Ying Yu, Rui Tan, Ruizhe Shen, Sihua Lu, Shuangde Li, Yunfa Chen, and Min Hu
Atmos. Chem. Phys., 22, 9827–9841, https://doi.org/10.5194/acp-22-9827-2022, https://doi.org/10.5194/acp-22-9827-2022, 2022
Short summary
Short summary
Emissions from four typical Chinese domestic cooking and fried chicken using four kinds of oils were investigated to illustrate the impact of cooking style and oil. Of the estimated SOA, 10.2 %–32.0 % could be explained by S/IVOC oxidation. Multiway principal component analysis (MPCA) emphasizes the importance of the unsaturated fatty acid-alkadienal volatile product mechanism (oil autoxidation) accelerated by the cooking and heating procedure.
Michelia Dam, Danielle C. Draper, Andrey Marsavin, Juliane L. Fry, and James N. Smith
Atmos. Chem. Phys., 22, 9017–9031, https://doi.org/10.5194/acp-22-9017-2022, https://doi.org/10.5194/acp-22-9017-2022, 2022
Short summary
Short summary
We performed chamber experiments to measure the composition of the gas-phase reaction products of nitrate-radical-initiated oxidation of four monoterpenes. The total organic yield, effective oxygen-to-carbon ratio, and dimer-to-monomer ratio were correlated with the observed particle formation for the monoterpene systems with some exceptions. The Δ-carene system produced the most particles, followed by β-pinene, with the α-pinene and α-thujene systems producing no particles.
Jacky Yat Sing Pang, Anna Novelli, Martin Kaminski, Ismail-Hakki Acir, Birger Bohn, Philip T. M. Carlsson, Changmin Cho, Hans-Peter Dorn, Andreas Hofzumahaus, Xin Li, Anna Lutz, Sascha Nehr, David Reimer, Franz Rohrer, Ralf Tillmann, Robert Wegener, Astrid Kiendler-Scharr, Andreas Wahner, and Hendrik Fuchs
Atmos. Chem. Phys., 22, 8497–8527, https://doi.org/10.5194/acp-22-8497-2022, https://doi.org/10.5194/acp-22-8497-2022, 2022
Short summary
Short summary
This study investigates the radical chemical budget during the limonene oxidation at different atmospheric-relevant NO concentrations in chamber experiments under atmospheric conditions. It is found that the model–measurement discrepancies of HO2 and RO2 are very large at low NO concentrations that are typical for forested environments. Possible additional processes impacting HO2 and RO2 concentrations are discussed.
Carmen Maria Tovar, Ian Barnes, Iustinian Gabriel Bejan, and Peter Wiesen
Atmos. Chem. Phys., 22, 6989–7004, https://doi.org/10.5194/acp-22-6989-2022, https://doi.org/10.5194/acp-22-6989-2022, 2022
Short summary
Short summary
This work explores the kinetics and reactivity of epoxides towards the OH radical using two different simulation chambers. Estimation of the rate coefficients has also been made using different structure–activity relationship (SAR) approaches. The results indicate a direct influence of the structural and geometric properties of the epoxides not considered in SAR estimations, influencing the reactivity of these compounds. The outcomes of this work are in very good agreement with previous studies.
Axel Fouqueau, Manuela Cirtog, Mathieu Cazaunau, Edouard Pangui, Jean-François Doussin, and Bénédicte Picquet-Varrault
Atmos. Chem. Phys., 22, 6411–6434, https://doi.org/10.5194/acp-22-6411-2022, https://doi.org/10.5194/acp-22-6411-2022, 2022
Short summary
Short summary
Biogenic volatile organic compounds are intensely emitted by forests and crops and react with the nitrate radical during the nighttime to form functionalized products. The purpose of this study is to furnish kinetic and mechanistic data for terpinolene and β-caryophyllene, using simulation chamber experiments. Rate constants have been measured using both relative and absolute methods, and mechanistic studies have been conducted in order to identify and quantify the main reaction products.
Yuanyuan Luo, Olga Garmash, Haiyan Li, Frans Graeffe, Arnaud P. Praplan, Anssi Liikanen, Yanjun Zhang, Melissa Meder, Otso Peräkylä, Josep Peñuelas, Ana María Yáñez-Serrano, and Mikael Ehn
Atmos. Chem. Phys., 22, 5619–5637, https://doi.org/10.5194/acp-22-5619-2022, https://doi.org/10.5194/acp-22-5619-2022, 2022
Short summary
Short summary
Diterpenes were only recently observed in the atmosphere, and little is known of their atmospheric fates. We explored the ozonolysis of the diterpene kaurene in a chamber, and we characterized the oxidation products for the first time using chemical ionization mass spectrometry. Our findings highlight similarities and differences between diterpenes and smaller terpenes during their atmospheric oxidation.
Wenyu Sun, Matias Berasategui, Andrea Pozzer, Jos Lelieveld, and John N. Crowley
Atmos. Chem. Phys., 22, 4969–4984, https://doi.org/10.5194/acp-22-4969-2022, https://doi.org/10.5194/acp-22-4969-2022, 2022
Short summary
Short summary
The reaction between OH and SO2 is a termolecular process that in the atmosphere results in the formation of H2SO4 and thus aerosols. We present the first temperature- and pressure-dependent measurements of the rate coefficients in N2. This is also the first study to examine the effects of water vapour on the kinetics of this reaction. Our results indicate the rate coefficient is larger than that recommended by evaluation panels, with deviations of up to 30 % in some parts of the atmosphere.
Haoyu Jiang, Yingyao He, Yiqun Wang, Sheng Li, Bin Jiang, Luca Carena, Xue Li, Lihua Yang, Tiangang Luan, Davide Vione, and Sasho Gligorovski
Atmos. Chem. Phys., 22, 4237–4252, https://doi.org/10.5194/acp-22-4237-2022, https://doi.org/10.5194/acp-22-4237-2022, 2022
Short summary
Short summary
Heterogeneous oxidation of SO2 is suggested to be one of the most important pathways for sulfate formation during extreme haze events in China, yet the exact mechanism remains highly uncertain. Our study reveals that ubiquitous compounds at the sea surface PAHS and DMSO, when exposed to SO2 under simulated sunlight irradiation, generate abundant organic sulfur compounds, providing implications for air-sea interaction and secondary organic aerosols formation processes.
Roland Vernooij, Ulrike Dusek, Maria Elena Popa, Peng Yao, Anupam Shaikat, Chenxi Qiu, Patrik Winiger, Carina van der Veen, Thomas Callum Eames, Natasha Ribeiro, and Guido R. van der Werf
Atmos. Chem. Phys., 22, 2871–2890, https://doi.org/10.5194/acp-22-2871-2022, https://doi.org/10.5194/acp-22-2871-2022, 2022
Short summary
Short summary
Landscape fires are a major source of greenhouse gases and aerosols, particularly in sub-tropical savannas. Stable carbon isotopes in emissions can be used to trace the contribution of C3 plants (e.g. trees or shrubs) and C4 plants (e.g. savanna grasses) to greenhouse gases and aerosols if the process is well understood. This helps us to link individual vegetation types to emissions, identify biomass burning emissions in the atmosphere, and improve the reconstruction of historic fire regimes.
María Asensio, María Antiñolo, Sergio Blázquez, José Albaladejo, and Elena Jiménez
Atmos. Chem. Phys., 22, 2689–2701, https://doi.org/10.5194/acp-22-2689-2022, https://doi.org/10.5194/acp-22-2689-2022, 2022
Short summary
Short summary
The diurnal atmospheric degradation of 2-methylbutanal, 2 MB, emitted by sources like vegetation or the poultry industry is evaluated in this work. Sunlight and oxidants like hydroxyl (OH) radicals and chlorine (Cl) atoms initiate this degradation. Measurements of how fast 2 MB is degraded and what products are generated are presented. The lifetime of 2 MB is around 1 h at noon, when the OH reaction dominates. Thus, 2 MB will not be transported far, affecting only local air quality.
Claudiu Roman, Cecilia Arsene, Iustinian Gabriel Bejan, and Romeo Iulian Olariu
Atmos. Chem. Phys., 22, 2203–2219, https://doi.org/10.5194/acp-22-2203-2022, https://doi.org/10.5194/acp-22-2203-2022, 2022
Short summary
Short summary
Gas-phase reaction rate coefficients of OH radicals with four nitrocatechols have been investigated for the first time by using ESC-Q-UAIC chamber facilities. The reactivity of all investigated nitrocatechols is influenced by the formation of the intramolecular H-bonds that are connected to the deactivating electromeric effect of the NO2 group. For the 3-nitrocatechol compounds, the electromeric effect of the
freeOH group is diminished by the deactivating E-effect of the NO2 group.
Zhiyuan Gao, Nicolas-Xavier Geilfus, Alfonso Saiz-Lopez, and Feiyue Wang
Atmos. Chem. Phys., 22, 1811–1824, https://doi.org/10.5194/acp-22-1811-2022, https://doi.org/10.5194/acp-22-1811-2022, 2022
Short summary
Short summary
Every spring in the Arctic, a series of photochemical events occur over the ice-covered ocean, known as bromine explosion events, ozone depletion events, and mercury depletion events. Here we report the re-creation of these events at an outdoor sea ice facility in Winnipeg, Canada, far away from the Arctic. The success provides a new platform with new opportunities to uncover fundamental mechanisms of these Arctic springtime phenomena and how they may change in a changing climate.
Haichao Wang, Chao Peng, Xuan Wang, Shengrong Lou, Keding Lu, Guicheng Gan, Xiaohong Jia, Xiaorui Chen, Jun Chen, Hongli Wang, Shaojia Fan, Xinming Wang, and Mingjin Tang
Atmos. Chem. Phys., 22, 1845–1859, https://doi.org/10.5194/acp-22-1845-2022, https://doi.org/10.5194/acp-22-1845-2022, 2022
Short summary
Short summary
Via combining laboratory and modeling work, we found that heterogeneous reaction of N2O5 with saline mineral dust aerosol could be an important source of tropospheric ClNO2 in inland regions.
Mike J. Newland, Yangang Ren, Max R. McGillen, Lisa Michelat, Véronique Daële, and Abdelwahid Mellouki
Atmos. Chem. Phys., 22, 1761–1772, https://doi.org/10.5194/acp-22-1761-2022, https://doi.org/10.5194/acp-22-1761-2022, 2022
Short summary
Short summary
Wildfires are increasing in extent and severity, driven by climate change. Such fires emit large amounts of volatile organic compounds (VOCs) to the atmosphere. Many of these, such as the furans studied here, are very reactive and are rapidly converted to other VOCs, which are expected to have negative health effects and to further impact the climate. Here, we establish the importance of the nitrate radical for removing these compounds both during the night and during the day.
Delaney B. Kilgour, Gordon A. Novak, Jon S. Sauer, Alexia N. Moore, Julie Dinasquet, Sarah Amiri, Emily B. Franklin, Kathryn Mayer, Margaux Winter, Clare K. Morris, Tyler Price, Francesca Malfatti, Daniel R. Crocker, Christopher Lee, Christopher D. Cappa, Allen H. Goldstein, Kimberly A. Prather, and Timothy H. Bertram
Atmos. Chem. Phys., 22, 1601–1613, https://doi.org/10.5194/acp-22-1601-2022, https://doi.org/10.5194/acp-22-1601-2022, 2022
Short summary
Short summary
We report measurements of gas-phase volatile organosulfur molecules made during a mesocosm phytoplankton bloom experiment. Dimethyl sulfide (DMS), methanethiol (MeSH), and benzothiazole accounted for on average over 90 % of total gas-phase sulfur emissions. This work focuses on factors controlling the production and emission of DMS and MeSH and the role of non-DMS molecules (such as MeSH and benzothiazole) in secondary sulfate formation in coastal marine environments.
Niklas Illmann, Iulia Patroescu-Klotz, and Peter Wiesen
Atmos. Chem. Phys., 21, 18557–18572, https://doi.org/10.5194/acp-21-18557-2021, https://doi.org/10.5194/acp-21-18557-2021, 2021
Short summary
Short summary
Understanding the chemistry of biomass burning plumes is of global interest. Within this work we investigated the OH radical reaction of 3-penten-2-one, which has been identified in biomass burning emissions. We observed the primary formation of peroxyacetyl nitrate (PAN), a key NOx reservoir species. Besides, PAN precursors were also identified as main oxidation products. 3-Penten-2-one is shown to be an example explaining rapid PAN formation within young biomass burning plumes.
Zhaofeng Tan, Luisa Hantschke, Martin Kaminski, Ismail-Hakki Acir, Birger Bohn, Changmin Cho, Hans-Peter Dorn, Xin Li, Anna Novelli, Sascha Nehr, Franz Rohrer, Ralf Tillmann, Robert Wegener, Andreas Hofzumahaus, Astrid Kiendler-Scharr, Andreas Wahner, and Hendrik Fuchs
Atmos. Chem. Phys., 21, 16067–16091, https://doi.org/10.5194/acp-21-16067-2021, https://doi.org/10.5194/acp-21-16067-2021, 2021
Short summary
Short summary
The photo-oxidation of myrcene, a monoterpene species emitted by plants, was investigated at atmospheric conditions in the outdoor simulation chamber SAPHIR. The chemical structure of myrcene is partly similar to isoprene. Therefore, it can be expected that hydrogen shift reactions could play a role as observed for isoprene. In this work, their potential impact on the regeneration efficiency of hydroxyl radicals is investigated.
Shijie Yu, Fangcheng Su, Shasha Yin, Shenbo Wang, Ruixin Xu, Bing He, Xiangge Fan, Minghao Yuan, and Ruiqin Zhang
Atmos. Chem. Phys., 21, 15239–15257, https://doi.org/10.5194/acp-21-15239-2021, https://doi.org/10.5194/acp-21-15239-2021, 2021
Short summary
Short summary
This study measured 106 VOC species using a GC-MS/FID. Meanwhile, the WRF-CMAQ model was used to investigate the nonlinearity of the O3 response to precursor reductions. This study highlights the effectiveness of stringent emission controls in relation to solvent utilization and coal combustion. However, unreasonable emission reduction may aggravate ozone pollution during control periods. It is suggested that emission-reduction ratios of the precursors (VOC : NOx) should be more than 2.
Niklas Illmann, Rodrigo Gastón Gibilisco, Iustinian Gabriel Bejan, Iulia Patroescu-Klotz, and Peter Wiesen
Atmos. Chem. Phys., 21, 13667–13686, https://doi.org/10.5194/acp-21-13667-2021, https://doi.org/10.5194/acp-21-13667-2021, 2021
Short summary
Short summary
Within this work we determined the rate coefficients and products of the reaction of unsaturated ketones with OH radicals in an effort to complete the gaps in the knowledge needed for modelling chemistry in the atmosphere. Both substances are potentially emitted by biomass burning, industrial activities or formed in the troposphere by oxidation of terpenes. As products we identified aldehydes and ketones which in turn are known to be responsible for the transportation of NOx species.
Yangang Ren, Li Zhou, Abdelwahid Mellouki, Véronique Daële, Mahmoud Idir, Steven S. Brown, Branko Ruscic, Robert S. Paton, Max R. McGillen, and A. R. Ravishankara
Atmos. Chem. Phys., 21, 13537–13551, https://doi.org/10.5194/acp-21-13537-2021, https://doi.org/10.5194/acp-21-13537-2021, 2021
Short summary
Short summary
Aromatic aldehydes are a family of compounds emitted into the atmosphere from both anthropogenic and biogenic sources that are formed from the degradation of aromatic hydrocarbons. Their atmospheric degradation may impact air quality. We report on their atmospheric degradation through reaction with NO3, which is useful to estimate their atmospheric lifetimes. We have also attempted to elucidate the mechanism of these reactions via studies of isotopic substitution and quantum chemistry.
Luisa Hantschke, Anna Novelli, Birger Bohn, Changmin Cho, David Reimer, Franz Rohrer, Ralf Tillmann, Marvin Glowania, Andreas Hofzumahaus, Astrid Kiendler-Scharr, Andreas Wahner, and Hendrik Fuchs
Atmos. Chem. Phys., 21, 12665–12685, https://doi.org/10.5194/acp-21-12665-2021, https://doi.org/10.5194/acp-21-12665-2021, 2021
Short summary
Short summary
The reactions of Δ3-carene with ozone and the hydroxyl radical (OH) and the photolysis and OH reaction of caronaldehyde were investigated in the simulation chamber SAPHIR. Reaction rate constants of these reactions were determined. Caronaldehyde yields of the ozonolysis and OH reaction were determined. The organic nitrate yield of the reaction of Δ3-carene and caronaldehyde-derived peroxy radicals with NO was determined. The ROx budget (ROx = OH+HO2+RO2) was also investigated.
Letizia Abis, Carmen Kalalian, Bastien Lunardelli, Tao Wang, Liwu Zhang, Jianmin Chen, Sébastien Perrier, Benjamin Loubet, Raluca Ciuraru, and Christian George
Atmos. Chem. Phys., 21, 12613–12629, https://doi.org/10.5194/acp-21-12613-2021, https://doi.org/10.5194/acp-21-12613-2021, 2021
Short summary
Short summary
Biogenic volatile organic compound (BVOC) emissions from rapeseed leaf litter have been investigated by means of a controlled atmospheric simulation chamber. The diversity of emitted VOCs increased also in the presence of UV light irradiation. SOA formation was observed when leaf litter was exposed to both UV light and ozone, indicating a potential contribution to particle formation or growth at local scales.
Xi Cheng, Qi Chen, Yong Jie Li, Yan Zheng, Keren Liao, and Guancong Huang
Atmos. Chem. Phys., 21, 12005–12019, https://doi.org/10.5194/acp-21-12005-2021, https://doi.org/10.5194/acp-21-12005-2021, 2021
Short summary
Short summary
In this study, we conducted laboratory studies to investigate the formation of gas-phase highly oxygenated organic molecules (HOMs). We provide a thorough analysis on the importance of multistep auto-oxidation and multigeneration OH reactions. We also give an intensive investigation on the roles of high-NO2 conditions that represent a wide range of anthropogenically influenced environments.
Rongrong Wu, Luc Vereecken, Epameinondas Tsiligiannis, Sungah Kang, Sascha R. Albrecht, Luisa Hantschke, Defeng Zhao, Anna Novelli, Hendrik Fuchs, Ralf Tillmann, Thorsten Hohaus, Philip T. M. Carlsson, Justin Shenolikar, François Bernard, John N. Crowley, Juliane L. Fry, Bellamy Brownwood, Joel A. Thornton, Steven S. Brown, Astrid Kiendler-Scharr, Andreas Wahner, Mattias Hallquist, and Thomas F. Mentel
Atmos. Chem. Phys., 21, 10799–10824, https://doi.org/10.5194/acp-21-10799-2021, https://doi.org/10.5194/acp-21-10799-2021, 2021
Short summary
Short summary
Isoprene is the biogenic volatile organic compound with the largest emissions rates. The nighttime reaction of isoprene with the NO3 radical has a large potential to contribute to SOA. We classified isoprene nitrates into generations and proposed formation pathways. Considering the potential functionalization of the isoprene nitrates we propose that mainly isoprene dimers contribute to SOA formation from the isoprene NO3 reactions with at least a 5 % mass yield.
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.
Chelsea E. Stockwell, Matthew M. Coggon, Georgios I. Gkatzelis, John Ortega, Brian C. McDonald, Jeff Peischl, Kenneth Aikin, Jessica B. Gilman, Michael Trainer, and Carsten Warneke
Atmos. Chem. Phys., 21, 6005–6022, https://doi.org/10.5194/acp-21-6005-2021, https://doi.org/10.5194/acp-21-6005-2021, 2021
Short summary
Short summary
Volatile chemical products are emerging as a large source of petrochemical organics in urban environments. We identify markers for the coatings category by linking ambient observations to laboratory measurements, investigating volatile organic compound (VOC) composition, and quantifying key VOC emissions via controlled evaporation experiments. Ingredients and sales surveys are used to confirm the prevalence and usage trends to support the assignment of water and solvent-borne coating tracers.
Abdelwahid Mellouki, Markus Ammann, R. Anthony Cox, John N. Crowley, Hartmut Herrmann, Michael E. Jenkin, V. Faye McNeill, Jürgen Troe, and Timothy J. Wallington
Atmos. Chem. Phys., 21, 4797–4808, https://doi.org/10.5194/acp-21-4797-2021, https://doi.org/10.5194/acp-21-4797-2021, 2021
Short summary
Short summary
Volatile organic compounds play an important role in atmospheric chemistry. This article, the eighth in the series, presents kinetic and photochemical data sheets evaluated by the IUPAC Task Group on Atmospheric Chemical Kinetic Data Evaluation. It covers the gas-phase reactions of organic species with four, or more, carbon atoms (≥ C4) including thermal reactions of closed-shell organic species with HO and NO3 radicals and their photolysis. These data are important for atmospheric models.
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.
Gareth J. Stewart, W. Joe F. Acton, Beth S. Nelson, Adam R. Vaughan, James R. Hopkins, Rahul Arya, Arnab Mondal, Ritu Jangirh, Sakshi Ahlawat, Lokesh Yadav, Sudhir K. Sharma, Rachel E. Dunmore, Siti S. M. Yunus, C. Nicholas Hewitt, Eiko Nemitz, Neil Mullinger, Ranu Gadi, Lokesh K. Sahu, Nidhi Tripathi, Andrew R. Rickard, James D. Lee, Tuhin K. Mandal, and Jacqueline F. Hamilton
Atmos. Chem. Phys., 21, 2383–2406, https://doi.org/10.5194/acp-21-2383-2021, https://doi.org/10.5194/acp-21-2383-2021, 2021
Short summary
Short summary
Biomass burning is a major source of trace gases to the troposphere; however, the composition and quantity of emissions vary greatly between different fuel types. This work provided near-total quantitation of non-methane volatile organic compounds from combustion of biofuels from India. Emissions from cow dung cake combustion were significantly larger than conventional fuelwood combustion, potentially indicating that this source has a disproportionately large impact on regional air quality.
Axel Fouqueau, Manuela Cirtog, Mathieu Cazaunau, Edouard Pangui, Jean-François Doussin, and Bénédicte Picquet-Varrault
Atmos. Chem. Phys., 20, 15167–15189, https://doi.org/10.5194/acp-20-15167-2020, https://doi.org/10.5194/acp-20-15167-2020, 2020
Michael Rolletter, Marion Blocquet, Martin Kaminski, Birger Bohn, Hans-Peter Dorn, Andreas Hofzumahaus, Frank Holland, Xin Li, Franz Rohrer, Ralf Tillmann, Robert Wegener, Astrid Kiendler-Scharr, Andreas Wahner, and Hendrik Fuchs
Atmos. Chem. Phys., 20, 13701–13719, https://doi.org/10.5194/acp-20-13701-2020, https://doi.org/10.5194/acp-20-13701-2020, 2020
Short summary
Short summary
The photooxidation of pinonaldehyde is investigated in a chamber study under natural sunlight and low NO conditions with and without an added hydroxyl radical (OH) scavenger. The experimentally determined pinonaldehyde photolysis frequency is faster by a factor of 3.5 than currently used parameterizations in atmospheric models. Yields of degradation products are measured in the presence and absence of OH. Measurements are compared to current atmospheric models and a theory-based mechanism.
Matias Berasategui, Damien Amedro, Luc Vereecken, Jos Lelieveld, and John N. Crowley
Atmos. Chem. Phys., 20, 13541–13555, https://doi.org/10.5194/acp-20-13541-2020, https://doi.org/10.5194/acp-20-13541-2020, 2020
Short summary
Short summary
Peracetic acid is one of the most abundant organic peroxides in the atmosphere. We combine experiments and theory to show that peracetic acid reacts orders of magnitude more slowly with OH than presently accepted, which results in a significant extension of its atmospheric lifetime.
Jacinta Edebeli, Jürg C. Trachsel, Sven E. Avak, Markus Ammann, Martin Schneebeli, Anja Eichler, and Thorsten Bartels-Rausch
Atmos. Chem. Phys., 20, 13443–13454, https://doi.org/10.5194/acp-20-13443-2020, https://doi.org/10.5194/acp-20-13443-2020, 2020
Short summary
Short summary
Earth’s snow cover is very dynamic and can change its physical properties within hours, as is well known by skiers. Snow is also a well-known host of chemical reactions – the products of which impact air composition and quality. Here, we present laboratory experiments that show how the dynamics of snow make snow essentially inert with respect to gas-phase ozone with time despite its content of reactive chemicals. Impacts on polar atmospheric chemistry are discussed.
R. Anthony Cox, Markus Ammann, John N. Crowley, Hartmut Herrmann, Michael E. Jenkin, V. Faye McNeill, Abdelwahid Mellouki, Jürgen Troe, and Timothy J. Wallington
Atmos. Chem. Phys., 20, 13497–13519, https://doi.org/10.5194/acp-20-13497-2020, https://doi.org/10.5194/acp-20-13497-2020, 2020
Short summary
Short summary
Criegee intermediates, formed from alkene–ozone reactions, play a potentially important role as tropospheric oxidants. Evaluated kinetic data are provided for reactions governing their formation and removal for use in atmospheric models. These include their formation from reactions of simple and complex alkenes and removal by decomposition and reaction with a number of atmospheric species (e.g. H2O, SO2). An overview of the tropospheric chemistry of Criegee intermediates is also provided.
Jake P. Rowe, Andrew T. Lambe, and William H. Brune
Atmos. Chem. Phys., 20, 13417–13424, https://doi.org/10.5194/acp-20-13417-2020, https://doi.org/10.5194/acp-20-13417-2020, 2020
Short summary
Short summary
We conducted a series of experiments in which the 185 to 254 nm photon flux ratio (I185 : I254) emitted by low-pressure mercury lamps installed in an oxidation flow reactor (OFR) was systematically varied using multiple novel lamp configurations. Integrated OH exposure values achieved for each lamp type were obtained as a function of OFR operating conditions. A photochemical box model was used to develop a generalized OH exposure estimation equation as a function of [H2O], [O3], and OH reactivity.
Mei-Tsan Kuo, Isabelle Weber, Christa Fittschen, Luc Vereecken, and Jim Jr-Min Lin
Atmos. Chem. Phys., 20, 12983–12993, https://doi.org/10.5194/acp-20-12983-2020, https://doi.org/10.5194/acp-20-12983-2020, 2020
Short summary
Short summary
Dimethyl sulfide (DMS) is the major sulfur-containing species in the troposphere. Previous work by Newland et al. (2015) reported very high reactivity of isoprene-derived Criegee intermediates (CIs) towards DMS. By monitoring CIs with direct UV absorption, we found CI + DMS reactions are very slow, in contrast to the results of Newland et al. (2015), suggesting these CIs would not oxidize atmospheric DMS at any substantial level.
Thomas R. Lewis, Juan Carlos Gómez Martín, Mark A. Blitz, Carlos A. Cuevas, John M. C. Plane, and Alfonso Saiz-Lopez
Atmos. Chem. Phys., 20, 10865–10887, https://doi.org/10.5194/acp-20-10865-2020, https://doi.org/10.5194/acp-20-10865-2020, 2020
Short summary
Short summary
Iodine-bearing gasses emitted from the sea surface are chemically processed in the atmosphere, leading to iodine accumulation in aerosol and transport to continental ecosystems. Such processing involves light-induced break-up of large, particle-forming iodine oxides into smaller, ozone-depleting molecules. We combine experiments and theory to report the photolysis efficiency of iodine oxides required to assess the impact of iodine on ozone depletion and particle formation.
Patrick Dewald, Jonathan M. Liebmann, Nils Friedrich, Justin Shenolikar, Jan Schuladen, Franz Rohrer, David Reimer, Ralf Tillmann, Anna Novelli, Changmin Cho, Kangming Xu, Rupert Holzinger, François Bernard, Li Zhou, Wahid Mellouki, Steven S. Brown, Hendrik Fuchs, Jos Lelieveld, and John N. Crowley
Atmos. Chem. Phys., 20, 10459–10475, https://doi.org/10.5194/acp-20-10459-2020, https://doi.org/10.5194/acp-20-10459-2020, 2020
Short summary
Short summary
We present direct measurements of NO3 reactivity resulting from the oxidation of isoprene by NO3 during an intensive simulation chamber study. Measurements were in excellent agreement with values calculated from measured isoprene amounts and the rate coefficient for the reaction of NO3 with isoprene. Comparison of the measurement with NO3 reactivities from non-steady-state and model calculations suggests that isoprene-derived RO2 and HO2 radicals account to ~ 50 % of overall NO3 losses.
Jacob T. Shaw, Andrew R. Rickard, Mike J. Newland, and Terry J. Dillon
Atmos. Chem. Phys., 20, 9725–9736, https://doi.org/10.5194/acp-20-9725-2020, https://doi.org/10.5194/acp-20-9725-2020, 2020
Short summary
Short summary
This work expands upon the recently developed multivariate relative rate technique, presented in Shaw et al. (2019), for the measurement of rates of reaction between aromatic and aliphatic volatile organic compounds (VOCs) and OH. Knowledge of the rates of such reactions are important for understanding air quality in urban environments. This work also provides a key validation of structure–activity relationship models, which provide a theoretical method for estimating OH + VOC kinetics.
Rodrigo Gastón Gibilisco, Ian Barnes, Iustinian Gabriel Bejan, and Peter Wiesen
Atmos. Chem. Phys., 20, 8939–8951, https://doi.org/10.5194/acp-20-8939-2020, https://doi.org/10.5194/acp-20-8939-2020, 2020
Short summary
Short summary
Environmental chamber studies were performed to evaluate atmospheric degradation initiated by OH radicals for two unsaturated methoxy ketones. The main gas-phase oxidation products identified and quantified from these reactions are carbonyls and long-lived nitrogen-containing compounds such as peroxyacetyl nitrate and peroxypropionyl nitrate. The kinetic rate constants and atmospheric lifetimes were estimated, degradation mechanisms were developed, and atmospheric implications were assessed.
James M. Roberts, Chelsea E. Stockwell, Robert J. Yokelson, Joost de Gouw, Yong Liu, Vanessa Selimovic, Abigail R. Koss, Kanako Sekimoto, Matthew M. Coggon, Bin Yuan, Kyle J. Zarzana, Steven S. Brown, Cristina Santin, Stefan H. Doerr, and Carsten Warneke
Atmos. Chem. Phys., 20, 8807–8826, https://doi.org/10.5194/acp-20-8807-2020, https://doi.org/10.5194/acp-20-8807-2020, 2020
Short summary
Short summary
We measured total reactive nitrogen, Nr, in lab fires from western North American fuels, along with measurements of individual nitrogen compounds. We measured the amount of N that gets converted to inactive compounds (avg. 70 %), and the amount that is accounted for by individual species (85 % of remaining N). We provide guidelines for how the reactive nitrogen is distributed among individual compounds such as NOx and ammonia. This will help estimates and predictions of wildfire emissions.
Anna Novelli, Luc Vereecken, Birger Bohn, Hans-Peter Dorn, Georgios I. Gkatzelis, Andreas Hofzumahaus, Frank Holland, David Reimer, Franz Rohrer, Simon Rosanka, Domenico Taraborrelli, Ralf Tillmann, Robert Wegener, Zhujun Yu, Astrid Kiendler-Scharr, Andreas Wahner, and Hendrik Fuchs
Atmos. Chem. Phys., 20, 3333–3355, https://doi.org/10.5194/acp-20-3333-2020, https://doi.org/10.5194/acp-20-3333-2020, 2020
Short summary
Short summary
Experimental evidence from a simulation chamber study shows that the regeneration efficiency of the hydroxyl radical is maintained globally at values higher than 0.5 for a wide range of nitrogen oxide concentrations as a result of isomerizations of peroxy radicals originating from the OH oxidation of isoprene. The available models were tested, and suggestions on how to improve their ability to reproduce the measured radical and oxygenated volatile organic compound concentrations are provided.
Damien Amedro, Matias Berasategui, Arne J. C. Bunkan, Andrea Pozzer, Jos Lelieveld, and John N. Crowley
Atmos. Chem. Phys., 20, 3091–3105, https://doi.org/10.5194/acp-20-3091-2020, https://doi.org/10.5194/acp-20-3091-2020, 2020
Short summary
Short summary
Our laboratory experiments show that the rate coefficient for the termolecular reaction between OH and NO2 is enhanced in the presence of water vapour. Using a chemistry transport model we show that our new parameterization of the temperature, pressure, and bath-gas dependence of this reaction has a significant impact on, for example, NOx and the HNO2 / NO2 ratio when compared to present recommendations.
Matias Berasategui, Damien Amedro, Achim Edtbauer, Jonathan Williams, Jos Lelieveld, and John N. Crowley
Atmos. Chem. Phys., 20, 2695–2707, https://doi.org/10.5194/acp-20-2695-2020, https://doi.org/10.5194/acp-20-2695-2020, 2020
Short summary
Short summary
We have determined the rate coefficient and mechanism for the reaction of the OH radical with methane sulphonamide, a trace gas which has recently been found in the atmosphere. The rate coefficient is 1.4 × 10−13 cm3 molec.−1 s−1, which indicates a tropospheric lifetime of > 2 months. The observation of CO, CO2, SO2, HNO3, HCOOH, and N2O products enabled us to derive a detailed reaction mechanism for the reaction, which proceeds predominantly by H abstraction from the CH3 group.
Abigail R. Koss, Manjula R. Canagaratna, Alexander Zaytsev, Jordan E. Krechmer, Martin Breitenlechner, Kevin J. Nihill, Christopher Y. Lim, James C. Rowe, Joseph R. Roscioli, Frank N. Keutsch, and Jesse H. Kroll
Atmos. Chem. Phys., 20, 1021–1041, https://doi.org/10.5194/acp-20-1021-2020, https://doi.org/10.5194/acp-20-1021-2020, 2020
Short summary
Short summary
Oxidation chemistry of organic compounds in the atmosphere produces a diverse spectrum of products. This diversity is difficult to represent in air quality and climate models, and in laboratory experiments it results in large and complex datasets. This work evaluates several methods to simplify the chemistry of oxidation systems in environmental chambers, including positive matrix factorization, hierarchical clustering analysis, and gamma kinetics parameterization.
Inmaculada Colmenar, Pilar Martin, Beatriz Cabañas, Sagrario Salgado, Araceli Tapia, and Inmaculada Aranda
Atmos. Chem. Phys., 20, 699–720, https://doi.org/10.5194/acp-20-699-2020, https://doi.org/10.5194/acp-20-699-2020, 2020
Short summary
Short summary
Saturated alcohols (SAs), such as (E)-4-methylcyclohexanol, 3,3-dimethyl-1-butanol, and 3,3-dimethyl-2-butanol, could be used as biofuels. The atmospheric reactivity of these compounds must be established in order to understand the consequences of the presence of these compounds in the atmosphere. The experimental results obtained in this work reveal that uncontrolled emissions of these saturated alcohols could have important atmospheric implications.
Olga Garmash, Matti P. Rissanen, Iida Pullinen, Sebastian Schmitt, Oskari Kausiala, Ralf Tillmann, Defeng Zhao, Carl Percival, Thomas J. Bannan, Michael Priestley, Åsa M. Hallquist, Einhard Kleist, Astrid Kiendler-Scharr, Mattias Hallquist, Torsten Berndt, Gordon McFiggans, Jürgen Wildt, Thomas F. Mentel, and Mikael Ehn
Atmos. Chem. Phys., 20, 515–537, https://doi.org/10.5194/acp-20-515-2020, https://doi.org/10.5194/acp-20-515-2020, 2020
Short summary
Short summary
Highly oxygenated organic molecules (HOMs) facilitate aerosol formation in the atmosphere. Using NO3− chemical ionization mass spectrometry we investigated HOM composition and yield in oxidation of aromatic compounds at different reactant concentrations, in the presence of NOx and seed aerosol. Higher OH concentrations increased HOM yield, suggesting multiple oxidation steps, and affected HOM composition, potentially explaining in part discrepancies in published secondary organic aerosol yields.
Cited articles
Atkinson, R., Aschmann, S. M., Arey, J., and Shorees, B.: Formation of OH
radicals in the gas phase reactions of O3 with a series of terpenes, J. Geophys. Res., 97, 6065–6073, https://doi.org/10.1029/92jd00062, 1992.
Barley, M. H., Topping, D., Lowe, D., Utembe, S., and McFiggans, G.: The sensitivity of secondary organic aerosol (SOA) component partitioning to the predictions of component properties – Part 3: Investigation of condensed compounds generated by a near-explicit model of VOC oxidation, Atmos. Chem. Phys., 11, 13145–13159, https://doi.org/10.5194/acp-11-13145-2011, 2011.
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.
Brown, S. K., Sim, M. R., Abramson, M. J., and Gray, C. N.: Concentrations
of Volatile Organic-Compounds in Indoor Air – a Review, Indoor Air, 4, 123–134, https://doi.org/10.1111/j.1600-0668.1994.t01-2-00007.x, 1994.
Carslaw, N.: A mechanistic study of limonene oxidation products and pathways
following cleaning activities, Atmos. Environ., 80, 507–513, https://doi.org/10.1016/j.atmosenv.2013.08.034, 2013.
Chen, J. J. and Griffin, R. J.: Modeling secondary organic aerosol
formation from oxidation of alpha-pinene, beta-pinene, and d-limonene,
Atmos. Environ., 39, 7731–7744, https://doi.org/10.1016/j.atmosenv.2005.05.049, 2005.
Chen, X. and Hopke, P. K.: A chamber study of secondary organic aerosol
formation by limonene ozonolysis, Indoor Air, 20, 320–328, https://doi.org/10.1111/j.1600-0668.2010.00656.x, 2010.
Ehn, M., Thornton, J. A., Kleist, E., Sipila, M., Junninen, H., Pullinen,
I., Springer, M., Rubach, F., Tillmann, R., Lee, B., Lopez-Hilfiker, F.,
Andres, S., Acir, I. H., Rissanen, M., Jokinen, T., Schobesberger, S.,
Kangasluoma, J., Kontkanen, J., Nieminen, T., Kurten, T., Nielsen, L. B.,
Jorgensen, S., Kjaergaard, H. G., Canagaratna, M., Maso, M. D., Berndt, T.,
Petaja, T., Wahner, A., Kerminen, V. M., Kulmala, M., Worsnop, D. R., Wildt,
J., and Mentel, T. F.: A large source of low-volatility secondary organic
aerosol, Nature, 506, 476–479, https://doi.org/10.1038/nature13032, 2014.
Faxon, C., Hammes, J., Le Breton, M., Pathak, R. K., and Hallquist, M.: Characterization of organic nitrate constituents of secondary organic aerosol (SOA) from nitrate-radical-initiated oxidation of limonene using high-resolution chemical ionization mass spectrometry, Atmos. Chem. Phys., 18, 5467–5481, https://doi.org/10.5194/acp-18-5467-2018, 2018.
Foley, J. P., and Dorsey, J. G.: A Review of the Exponentially Modified
Gaussian (Emg) Function – Evaluation and Subsequent Calculation of Universal
Data, J. Chromatogr. Sci., 22, 40–46, https://doi.org/10.1093/chromsci/22.1.40, 1984.
Glasius, M., Lahaniati, M., Calogirou, A., Di Bella, D., Jensen, N. R.,
Hjorth, J., Kotzias, D., and Larsen, B. R.: Carboxylic Acids in Secondary
Aerosols from Oxidation of Cyclic Monoterpenes by Ozone, Environ. Sci. Technol., 34, 1001–1010, 2000.
Glasius, M. and Goldstein, A. H.: Recent Discoveries and Future Challenges
in Atmospheric Organic Chemistry, Environ. Sci. Technol., 50, 2754–2764, https://doi.org/10.1021/acs.est.5b05105, 2016.
Gong, Y., Chen, Z., and Li, H.: The oxidation regime and SOA composition in limonene ozonolysis: roles of different double bonds, radicals, and water, Atmos. Chem. Phys., 18, 15105–15123, https://doi.org/10.5194/acp-18-15105-2018, 2018.
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.
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.
Jaoui, M., Kleindienst, T. E., Lewandowski, M., Offenberg, J. H., and Edney,
E. O.: Identification and quantification of aerosol polar oxygenated
compounds bearing carboxylic or hydroxyl groups. 2. Organic tracer compounds
from monoterpenes, Environ. Sci. Technol., 39, 5661–5673, 2005.
Jaoui, M., Corse, E., Kleindienst, T. E., Offenberg, J. H., Lewandowski, M.,
and Edney, E. O.: Analysis of Secondary Organic Aerosol Compounds from the
Photooxidation ofd-Limonene in the Presence of NOx and their Detection in
Ambient PM2.5, Environ. Sci. Technol., 40, 3819–3828, https://doi.org/10.1021/es052566z, 2006.
Jenkin, M. E.: Modelling the formation and composition of secondary organic aerosol from α- and β-pinene ozonolysis using MCM v3, Atmos. Chem. Phys., 4, 1741–1757, https://doi.org/10.5194/acp-4-1741-2004, 2004.
Jenkin, M. E., Valorso, R., Aumont, B., and Rickard, A. R.: Estimation of rate coefficients and branching ratios for reactions of organic peroxy radicals for use in automated mechanism construction, Atmos. Chem. Phys., 19, 7691–7717, https://doi.org/10.5194/acp-19-7691-2019, 2019.
Jokinen, T., Sipila, M., Richters, S., Kerminen, V. M., Paasonen, P.,
Stratmann, F., Worsnop, D., Kulmala, M., Ehn, M., Herrmann, H., and Berndt,
T.: Rapid autoxidation forms highly oxidized RO2 radicals in the atmosphere,
Angew. Chem. Int. Edit., 53, 14596–14600, https://doi.org/10.1002/anie.201408566, 2014.
Jonsson, Å. M., Hallquist, M., and Ljungström, E.: Impact of
Humidity on the Ozone Initiated Oxidation of Limonene, Δ3-Carene,
and α-Pinene, Environ. Sci. Technol., 40, 188–194, https://doi.org/10.1021/es051163w, 2006.
Jonsson, Å. M., Hallquist, M., and Ljungström, E.: The effect of temperature and water on secondary organic aerosol formation from ozonolysis of limonene, Δ3-carene and α-pinene, Atmos. Chem. Phys., 8, 6541–6549, https://doi.org/10.5194/acp-8-6541-2008, 2008a.
Jonsson, Å. M., Hallquist, M., and Ljungström, E.:
Influence of OH Scavenger on the Water Effect on Secondary Organic Aerosol
Formation from Ozonolysis of Limonene, Δ3-Carene, and α-Pinene, Environ. Sci. Technol., 42, 5938–5944, https://doi.org/10.1021/es702508y, 2008b.
Keywood, M. D., Kroll, J. H., Varutbangkul, V., Bahreini, R., Flagan, R. C.,
and Seinfeld, J. H.: Secondary Organic Aerosol Formation from Cyclohexene
Ozonolysis: Effect of OH Scavenger and the Role of Radical Chemistry,
Environ. Sci. Technol., 38, 3343–3350, https://doi.org/10.1021/es049725j,
2004.
Koch, S., Winterhalter, R., Uherek, E., Kolloff, A., Neeb, P., and Moortgat,
G. K.: Formation of new particles in the gas-phase ozonolysis of
monoterpenes, Atmos. Environ., 34, 4031–4042, 2000.
Kristensen, K., Enggrob, K. L., King, S. M., Worton, D. R., Platt, S. M., Mortensen, R., Rosenoern, T., Surratt, J. D., Bilde, M., Goldstein, A. H., and Glasius, M.: Formation and occurrence of dimer esters of pinene oxidation products in atmospheric aerosols, Atmos. Chem. Phys., 13, 3763–3776, https://doi.org/10.5194/acp-13-3763-2013, 2013.
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.
Kristensen, K., Watne, Å. K., Hammes, J., Lutz, A., Petäjä, T.,
Hallquist, M., Bilde, M., and Glasius, M.: High-Molecular Weight Dimer
Esters Are Major Products in Aerosols from α-Pinene Ozonolysis and
the Boreal Forest, Environ. Sci. Technol. Lett., 3,
280–285, https://doi.org/10.1021/acs.estlett.6b00152, 2016.
Langer, S., Moldanova, J., Arrhenius, K., Ljungstrom, E., and Ekberg, L.:
Ultrafine particles produced by ozone/limonene reactions in indoor air under
low/closed ventilation conditions, Atmos. Environ., 42, 4149–4159, https://doi.org/10.1016/j.atmosenv.2008.01.034, 2008.
Le Breton, M., Psichoudaki, M., Hallquist, M., Watne, A. K., Lutz, A., and
Hallquist, A. M.: Application of a FIGAERO ToF CIMS for on-line
characterization of real-world fresh and aged particle emissions from buses,
Aerosol Sci. Technol., 53, 244–259, https://doi.org/10.1080/02786826.2019.1566592, 2019.
Leungsakul, S., Jaoui, M., and Kamens, R. M.: Kinetic mechanism for
predicting secondary organic aerosol formation from the reaction of
d-limonene with ozone, Environ. Sci. Technol., 39, 9583–9594,
2005a.
Leungsakul, S., Jeffries, H. E., and Kamens, R. M.: A kinetic mechanism for
predicting secondary aerosol formation from the reactions of d-limonene in
the presence of oxides of nitrogen and natural sunlight, Atmos. Environ.,
39, 7063–7082, 2005b.
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.
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.
Maksymiuk, C. S., Gayahtri, C., Gil, R. R., and Donahue, N. M.: Secondary
organic aerosol formation from multiphase oxidation of limonene by ozone:
mechanistic constraints via two-dimensional heteronuclear NMR spectroscopy,
Phys. Chem. Chem. Phys., 11, 7810–7818, https://doi.org/10.1039/b820005j,
2009.
McFiggans, G., Mentel, T. F., Wildt, J., Pullinen, I., Kang, S., Kleist, E.,
Schmitt, S., Springer, M., Tillmann, R., Wu, C., Zhao, D., Hallquist, M.,
Faxon, C., Le Breton, M., Hallquist, Å. M., Simpson, D., Bergström,
R., Jenkin, M. E., Ehn, M., Thornton, J. A., Alfarra, M. R., Bannan, T. J.,
Percival, C. J., Priestley, M., Topping, D., and Kiendler-Scharr, A.:
Secondary organic aerosol reduced by mixture of atmospheric vapours, Nature,
565, 587–593, https://doi.org/10.1038/s41586-018-0871-y, 2019.
Mohr, C., Lopez-Hilfiker, F. D., Zotter, P., Prévôt, A. S. H., Xu,
L., Ng, N. L., Herndon, S. C., Williams, L. R., Franklin, J. P., Zahniser,
M. S., Worsnop, D. R., Knighton, W. B., Aiken, A. C., Gorkowski, K. J.,
Dubey, M. K., Allan, J. D., and Thornton, J. A.: Contribution of Nitrated
Phenols to Wood Burning Brown Carbon Light Absorption in Detling, United
Kingdom during Winter Time, Environ. Sci. Technol., 47, 6316–6324, https://doi.org/10.1021/es400683v, 2013.
Mohr, C., Lopez-Hilfiker, F. D., Yli-Juuti, T., Heitto, A., Lutz, A.,
Hallquist, M., D'Ambro, E. L., Rissanen, M. P., Hao, L. Q., Schobesberger,
S., Kulmala, M., Mauldin, R. L., Makkonen, U., Sipila, M., Petaja, T., and
Thornton, J. A.: Ambient observations of dimers from terpene oxidation in
the gas phase: Implications for new particle formation and growth, Geophys.
Res. Lett., 44, 2958–2966, https://doi.org/10.1002/2017gl072718, 2017.
Orlando, J. J. and Tyndall, G. S.: Laboratory studies of organic peroxy
radical chemistry: an overview with emphasis on recent issues of atmospheric
significance, Chem. Soc. Rev., 41, 6294–6317, https://doi.org/10.1039/c2cs35166h,
2012.
Pathak, R. K., Salo, K., Emanuelsson, E. U., Cai, C., Lutz, A., Hallquist,
A. M., and Hallquist, M.: Influence of ozone and radical chemistry on
limonene organic aerosol production and thermal characteristics,
Environ. Sci. Technol., 46, 11660–11669, https://doi.org/10.1021/es301750r,
2012.
Rossignol, S., Chiappini, L., Perraudin, E., Rio, C., Fable, S., Valorso, R., and Doussin, J. F.: Development of a parallel sampling and analysis method for the elucidation of gas/particle partitioning of oxygenated semi-volatile organics: a limonene ozonolysis study, Atmos. Meas. Tech., 5, 1459–1489, https://doi.org/10.5194/amt-5-1459-2012, 2012.
Rossignol, S., Rio, C., Ustache, A., Fable, S., Nicolle, J., Meme, A.,
D'Anna, B., Nicolas, M., Leoz, E., and Chiappini, L.: The use of a
housecleaning product in an indoor environment leading to oxygenated polar
compounds and SOA formation: Gas and particulate phase chemical
characterization, Atmos. Environ., 75, 196–205, https://doi.org/10.1016/j.atmosenv.2013.03.045, 2013.
Saathoff, H., Naumann, K.-H., Möhler, O., Jonsson, Å. M., Hallquist, M., Kiendler-Scharr, A., Mentel, Th. F., Tillmann, R., and Schurath, U.: Temperature dependence of yields of secondary organic aerosols from the ozonolysis of α-pinene and limonene, Atmos. Chem. Phys., 9, 1551–1577, https://doi.org/10.5194/acp-9-1551-2009, 2009.
Salo, K., Jonsson, A. M., Andersson, P. U., and Hallquist, M.: Aerosol
volatility and enthalpy of sublimation of carboxylic acids, J.
Phys. Chem. A, 114, 4586–4594, https://doi.org/10.1021/jp910105h, 2010.
Shrivastava, M., Cappa, C. D., Fan, J. W., Goldstein, A. H., Guenther, A.
B., Jimenez, J. L., Kuang, C., Laskin, A., Martin, S. T., Ng, N. L., Petaja,
T., Pierce, J. R., Rasch, P. J., Roldin, P., Seinfeld, J. H., Shilling, J.,
Smith, J. N., Thornton, J. A., Volkamer, R., Wang, J., Worsnop, D. R.,
Zaveri, R. A., Zelenyuk, A., and Zhang, Q.: Recent advances in understanding
secondary organic aerosol: Implications for global climate forcing, Rev. Geophys., 55, 509–559, https://doi.org/10.1002/2016rg000540, 2017.
Vereecken, L. and Francisco, J. S.: Theoretical studies of atmospheric
reaction mechanisms in the troposphere, Chem. Soc. Rev., 41,
6259–6293, https://doi.org/10.1039/c2cs35070j, 2012.
Walser, M. L., Desyaterik, Y., Laskin, J., Laskin, A., and Nizkorodov, S.
A.: High-resolution mass spectrometric analysis of secondary organic aerosol
produced by ozonation of limonene, Phys. Chem. Chem. Phys.
10, 1009–1022, https://doi.org/10.1039/b712620d, 2008.
Wang, M., Yao, L., Zheng, J., Wang, X., Chen, J., Yang, X., Worsnop, D. R.,
Donahue, N. M., and Wang, L.: Reactions of Atmospheric Particulate
Stabilized Criegee Intermediates Lead to High-Molecular-Weight Aerosol
Components, Environ. Sci. Technol., 50, 5702–5710, https://doi.org/10.1021/acs.est.6b02114, 2016.
Watne, A. K., Westerlund, J., Hallquist, A. M., Brune, W. H., and Hallquist,
M.: Ozone and OH-induced oxidation of monoterpenes: Changes in the thermal
properties of secondary organic aerosol (SOA), J. Aerosol Sci.,
114, 31–41, https://doi.org/10.1016/j.jaerosci.2017.08.011, 2017.
Witkowski, B. and Gierczak, T.: Early stage composition of SOA produced by
α-pinene/ozone reaction: α-Acyloxyhydroperoxy aldehydes and
acidic dimers, Atmos. Environ., 95, 59–70, https://doi.org/10.1016/j.atmosenv.2014.06.018, 2014.
Youssefi, S. and Waring, M. S.: Transient Secondary Organic Aerosol
Formation from Limonene Ozonolysis in Indoor Environments: Impacts of Air
Exchange Rates and Initial Concentration Ratios, Environ. Sci. Technol., 48,
7899–7908, https://doi.org/10.1021/es5009906, 2014.
Ziemann, P. J. and Atkinson, R.: Kinetics, products, and mechanisms of
secondary organic aerosol formation, Chem. Soc. Rev., 41, 6582–6605, 2012.
Short summary
Identifying the chemical pathways of condensable products such as carboxylic acids is essential for predicting SOA formation. This identification is inherently difficult, as such products reside in both the gas and particulate phases. We measured acids, produced from atmospheric oxidation of limonene, in both phases and scrutinised the mechanistic understanding of their formation. The mechanisms explain nearly 75 % of the gas-phase signal at the lowest concentration (8.4 ppb, 23 % acid yield).
Identifying the chemical pathways of condensable products such as carboxylic acids is essential...
Altmetrics
Final-revised paper
Preprint