Articles | Volume 22, issue 10
https://doi.org/10.5194/acp-22-6989-2022
© Author(s) 2022. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
https://doi.org/10.5194/acp-22-6989-2022
© Author(s) 2022. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
31 May 2022
Research article |
| 31 May 2022
| 31 May 2022
Kinetic study of the atmospheric oxidation of a series of epoxy compounds by OH radicals
Carmen Maria Tovar
CORRESPONDING AUTHOR
Institute for Atmospheric and Environmental Research, University of
Wuppertal, 42097 Wuppertal, Germany
Ian Barnes
Institute for Atmospheric and Environmental Research, University of
Wuppertal, 42097 Wuppertal, Germany
deceased, 1 January 2018
Iustinian Gabriel Bejan
CORRESPONDING AUTHOR
Faculty of Chemistry and Integrated Center of Environmental Science Studies in the North-Eastern Region – CERNESIM, “Alexandru Ioan Cuza” University of Iasi, Iasi, 700506, Romania
Peter Wiesen
Institute for Atmospheric and Environmental Research, University of
Wuppertal, 42097 Wuppertal, Germany
Related authors
No articles found.
Frank A. F. Winiberg, William J. Warman, Charlotte A. Brumby, Graham Boustead, Iustinian G. Bejan, Thomas H. Speak, Dwayne E. Heard, Daniel Stone, and Paul W. Seakins
Atmos. Meas. Tech., 16, 4375–4390, https://doi.org/10.5194/amt-16-4375-2023, https://doi.org/10.5194/amt-16-4375-2023, 2023
Short summary
Short summary
OH and HO2 are key reactive intermediates in the Earth's atmosphere. Accurate measurements in either the field or simulation chambers provide a good test for chemical mechanisms. Fluorescence techniques have the appropriate sensitivity for detection but require calibration. This paper compares different methods of calibration and specifically how calibration factors vary across a temperature range relevant to atmospheric and chamber determinations.
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.
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.
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.
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.
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.
Ralf Kurtenbach, Kai Vaupel, Jörg Kleffmann, Ulrich Klenk, Eberhard Schmidt, and Peter Wiesen
Atmos. Chem. Phys., 16, 14285–14295, https://doi.org/10.5194/acp-16-14285-2016, https://doi.org/10.5194/acp-16-14285-2016, 2016
Short summary
Short summary
Emissions from inland shipping were studied at the Rhine. Reliable NOx and PM emission indices are prerequisite for improving emission inventories. The NO2 / NOx emission ratio from the present study points to ship engines without exhaust gas aftertreatment as main emitter. The calculated NOx emissions of all motor ship types were found to be above the threshold values of national German guidelines. Accordingly, the implementation of efficient NOx reduction techniques is strongly recommended.
Related subject area
Subject: Gases | Research Activity: Laboratory Studies | Altitude Range: Troposphere | Science Focus: Chemistry (chemical composition and reactions)
Formation and temperature dependence of highly oxygenated organic molecules (HOMs) from Δ3-carene ozonolysis
Mechanistic insight into the kinetic fragmentation of norpinonic acid in the gas phase: an experimental and density functional theory (DFT) study
Secondary reactions of aromatics-derived oxygenated organic molecules lead to plentiful highly oxygenated organic molecules within an intraday OH exposure
Impact of HO2∕RO2 ratio on highly oxygenated α-pinene photooxidation products and secondary organic aerosol formation potential
Formation of Reactive Nitrogen Species Promoted by Iron Ions Through the Photochemistry of Neonicotinoid Insecticide
Negligible temperature dependence of the ozone–iodide reaction and implications for oceanic emissions of iodine
Extension, development, and evaluation of the representation of the OH-initiated dimethyl sulfide (DMS) oxidation mechanism in the Master Chemical Mechanism (MCM) v3.3.1 framework
On the potential use of highly oxygenated organic molecules (HOMs) as indicators for ozone formation sensitivity
Oxygenated organic molecules produced by low-NOx photooxidation of aromatic compounds: contributions to secondary organic aerosol and steric hindrance
Impact of temperature on the role of Criegee intermediates and peroxy radicals in dimer formation from β-pinene ozonolysis
Rate coefficients for the reactions of OH radical with C3-C11 alkanes determined by the relative rate technique
Atmospheric impact of 2-methylpentanal emissions: kinetics, photochemistry, and formation of secondary pollutants
Quantifying primary oxidation products in the OH-initiated reaction of benzyl alcohol
Technical note: Gas-phase nitrate radical generation via irradiation of aerated ceric ammonium nitrate mixtures
Direct probing of acylperoxy radicals during ozonolysis of α-pinene: constraints on radical chemistry and production of highly oxygenated organic molecules
Atmospheric photooxidation and ozonolysis of sabinene: reaction rate coefficients, product yields, and chemical budget of radicals
Compilation of Henry's law constants (version 5.0.0) for water as solvent
Measurement report: Carbonyl sulfide production during dimethyl sulfide oxidation in the atmospheric simulation chamber SAPHIR
An aldehyde as a rapid source of secondary aerosol precursors: theoretical and experimental study of hexanal autoxidation
Measuring and modeling investigation of the net photochemical ozone production rate via an improved dual-channel reaction chamber technique
Evolution of organic carbon in the laboratory oxidation of biomass-burning emissions
Atmospheric oxidation of new “green” solvents – Part 2: methyl pivalate and pinacolone
On the formation of highly oxidized pollutants by autoxidation of terpenes under low-temperature-combustion conditions: the case of limonene and α-pinene
Selective deuteration as a tool for resolving autoxidation mechanisms in α-pinene ozonolysis
Comparison of isoprene chemical mechanisms under atmospheric night-time conditions in chamber experiments: evidence of hydroperoxy aldehydes and epoxy products from NO3 oxidation
Measurement of Henry's law and liquid-phase loss rate constants of peroxypropionic nitric anhydride (PPN) in deionized water and in n-octanol
Product distribution, kinetics, and aerosol formation from the OH oxidation of dimethyl sulfide under different RO2 regimes
Atmospheric breakdown chemistry of the new “green” solvent 2,2,5,5-tetramethyloxolane via gas-phase reactions with OH and Cl radicals
Impact of cooking style and oil on semi-volatile and intermediate volatility organic compound emissions from Chinese domestic cooking
Observations of gas-phase products from the nitrate-radical-initiated oxidation of four monoterpenes
Investigation of the limonene photooxidation by OH at different NO concentrations in the atmospheric simulation chamber SAPHIR (Simulation of Atmospheric PHotochemistry In a large Reaction Chamber)
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
Yuanyuan Luo, Ditte Thomsen, Emil Mark Iversen, Pontus Roldin, Jane Tygesen Skønager, Linjie Li, Michael Priestley, Henrik B. Pedersen, Mattias Hallquist, Merete Bilde, Marianne Glasius, and Mikael Ehn
Atmos. Chem. Phys., 24, 9459–9473, https://doi.org/10.5194/acp-24-9459-2024, https://doi.org/10.5194/acp-24-9459-2024, 2024
Short summary
Short summary
∆3-carene is abundantly emitted from vegetation, but its atmospheric oxidation chemistry has received limited attention. We explored highly oxygenated organic molecule (HOM) formation from ∆3-carene ozonolysis in chambers and investigated the impact of temperature and relative humidity on HOM formation. Our findings provide new insights into ∆3-carene oxidation pathways and their potential to impact atmospheric aerosols.
Izabela Kurzydym, Agata Błaziak, Kinga Podgórniak, Karol Kułacz, and Kacper Błaziak
Atmos. Chem. Phys., 24, 9309–9322, https://doi.org/10.5194/acp-24-9309-2024, https://doi.org/10.5194/acp-24-9309-2024, 2024
Short summary
Short summary
This paper outlines a unique scientific strategy for studying the reactivity of atmospherically relevant norpinonic acid (NA). The publication offers a new toolbox, illustrating NA's fragmentation and pattern of kinetic degradation leading to the formation of new small molecules. Furthermore, the research strategy presented here demonstrates how a mass spectrometer can function as a gas-phase reactor and the quantum chemistry method can serve as a reaction model builder.
Yuwei Wang, Chuang Li, Ying Zhang, Yueyang Li, Gan Yang, Xueyan Yang, Yizhen Wu, Lei Yao, Hefeng Zhang, and Lin Wang
Atmos. Chem. Phys., 24, 7961–7981, https://doi.org/10.5194/acp-24-7961-2024, https://doi.org/10.5194/acp-24-7961-2024, 2024
Short summary
Short summary
The formation and evolution mechanisms of aromatics-derived highly oxygenated organic molecules (HOMs) are essential to understand the formation of secondary organic aerosol pollution. Our conclusion highlights an underappreciated formation pathway of aromatics-derived HOMs and elucidates detailed formation mechanisms of certain HOMs, which advances our understanding of HOMs and potentially explains the existing gap between model prediction and ambient measurement of the HOMs' concentrations.
Yarê Baker, Sungah Kang, Hui Wang, Rongrong Wu, Jian Xu, Annika Zanders, Quanfu He, Thorsten Hohaus, Till Ziehm, Veronica Geretti, Thomas J. Bannan, Simon P. O'Meara, Aristeidis Voliotis, Mattias Hallquist, Gordon McFiggans, Sören R. Zorn, Andreas Wahner, and Thomas F. Mentel
Atmos. Chem. Phys., 24, 4789–4807, https://doi.org/10.5194/acp-24-4789-2024, https://doi.org/10.5194/acp-24-4789-2024, 2024
Short summary
Short summary
Highly oxygenated organic molecules are important contributors to secondary organic aerosol. Their yield depends on detailed atmospheric chemical composition. One important parameter is the ratio of hydroperoxy radicals to organic peroxy radicals (HO2/RO2), and we show that higher HO2/RO2 ratios lower the secondary organic aerosol yield. This is of importance as laboratory studies are often biased towards organic peroxy radicals.
Zhu Ran, Yanan Hu, Yuanzhe Li, Xiaoya Gao, Can Ye, Shuai Li, Xiao Lu, Yongming Luo, Sasho Gligorovski, and Jiangping Liu
EGUsphere, https://doi.org/10.5194/egusphere-2024-1116, https://doi.org/10.5194/egusphere-2024-1116, 2024
Short summary
Short summary
We report eruptive production of nitrous acid (HONO) and NOx (NO + NO2) triggered by iron ions during the photolysis of neonicotinoid insecticide in the air-water interface. This novel previously overlooked source of atmospheric HONO and NOx, may be an important contribution to the global nitrogen cycle and affects the atmospheric oxidizing capacity as well as the climate change.
Lucy V. Brown, Ryan J. Pound, Lyndsay S. Ives, Matthew R. Jones, Stephen J. Andrews, and Lucy J. Carpenter
Atmos. Chem. Phys., 24, 3905–3923, https://doi.org/10.5194/acp-24-3905-2024, https://doi.org/10.5194/acp-24-3905-2024, 2024
Short summary
Short summary
Ozone is deposited from the lower atmosphere to the surface of the ocean; however, the chemical reactions which drive this deposition are currently not well understood. Of particular importance is the reaction between ozone and iodide, and this work measures the kinetics of this reaction and its temperature dependence, which we find to be negligible. We then investigate the subsequent emissions of iodine-containing species from the surface ocean, which can further impact ozone.
Lorrie Simone Denise Jacob, Chiara Giorio, and Alexander Thomas Archibald
Atmos. Chem. Phys., 24, 3329–3347, https://doi.org/10.5194/acp-24-3329-2024, https://doi.org/10.5194/acp-24-3329-2024, 2024
Short summary
Short summary
Recent studies on DMS have provided new challenges to our mechanistic understanding. Here we synthesise a number of recent studies to further develop and extend a state-of-the-art mechanism. Our new mechanism is shown to outperform all existing mechanisms when compared over a wide set of conditions. The development of an improved DMS mechanism will help lead the way to better the understanding the climate impacts of DMS emissions in past, present, and future atmospheric conditions.
Jiangyi Zhang, Jian Zhao, Yuanyuan Luo, Valter Mickwitz, Douglas Worsnop, and Mikael Ehn
Atmos. Chem. Phys., 24, 2885–2911, https://doi.org/10.5194/acp-24-2885-2024, https://doi.org/10.5194/acp-24-2885-2024, 2024
Short summary
Short summary
Due to the intrinsic connection between the formation pathways of O3 and HOMs, the ratio of HOM dimers or non-nitrate monomers to HOM organic nitrates could be used to determine O3 formation regimes. Owing to the fast formation and short lifetimes of HOMs, HOM-based indicating ratios can describe O3 formation in real time. Despite the success of our approach in this simple laboratory system, applicability to the much more complex atmosphere remains to be determined.
Xi Cheng, Yong Jie Li, Yan Zheng, Keren Liao, Theodore K. Koenig, Yanli Ge, Tong Zhu, Chunxiang Ye, Xinghua Qiu, and Qi Chen
Atmos. Chem. Phys., 24, 2099–2112, https://doi.org/10.5194/acp-24-2099-2024, https://doi.org/10.5194/acp-24-2099-2024, 2024
Short summary
Short summary
In this study we conducted laboratory measurements to investigate the formation of gas-phase oxygenated organic molecules (OOMs) from six aromatic volatile organic compounds (VOCs). We provide a thorough analysis on the effects of precursor structure (substituents and ring numbers) on product distribution and highlight from a laboratory perspective that heavy (e.g., double-ring) aromatic VOCs are important in initial particle growth during secondary organic aerosol formation.
Yiwei Gong, Feng Jiang, Yanxia Li, Thomas Leisner, and Harald Saathoff
Atmos. Chem. Phys., 24, 167–184, https://doi.org/10.5194/acp-24-167-2024, https://doi.org/10.5194/acp-24-167-2024, 2024
Short summary
Short summary
This study investigates the role of the important atmospheric reactive intermediates in the formation of dimers and aerosol in monoterpene ozonolysis at different temperatures. Through conducting a series of chamber experiments and utilizing chemical kinetic and aerosol dynamic models, the SOA formation processes are better described, especially for colder regions. The results can be used to improve the chemical mechanism modeling of monoterpenes and SOA parameterization in transport models.
Yanyan Xin, Xiaoxiu Lun, Shuyang Xie, Junfeng Liu, Chengtang Liu, and Yujing Mu
EGUsphere, https://doi.org/10.5194/egusphere-2023-2802, https://doi.org/10.5194/egusphere-2023-2802, 2023
Short summary
Short summary
The relative rate constants of OH radicals with C3-C11 alkanes under different bath gases (N2, Air, O2) were obtained, and multiple comparisons were made with previous literature and estimated values, expanding the existing database. The measured relative rate constants of air gases were found to be highly consistent with values obtained in N2, suggesting that the rate constants obtained in this experiment can reasonably represent the rate constants in the actual atmosphere.
María Asensio, Sergio Blázquez, María Antiñolo, José Albaladejo, and Elena Jiménez
Atmos. Chem. Phys., 23, 14115–14126, https://doi.org/10.5194/acp-23-14115-2023, https://doi.org/10.5194/acp-23-14115-2023, 2023
Short summary
Short summary
In this work, we focus on the atmospheric chemistry and consequences for air quality of 2-methylpentanal (2MP), which is widely used as a flavoring ingredient and as an intermediate in the synthesis of dyes, resins, and pharmaceuticals. Measurements are presented on how fast 2MP is degraded by sunlight and oxidants like hydroxyl (OH) radicals and chlorine (Cl) atoms and what products are generated. We conclude that 2MP will be degraded in a few hours, affecting local air quality.
Reina S. Buenconsejo, Sophia M. Charan, John H. Seinfeld, and Paul O. Wennberg
EGUsphere, https://doi.org/10.5194/egusphere-2023-2483, https://doi.org/10.5194/egusphere-2023-2483, 2023
Short summary
Short summary
We look at the atmospheric chemistry of a volatile chemical product (VCP), benzyl alcohol. Benzyl alcohol and other VCPs may play a significant role in the formation of urban smog. By better understanding the chemistry of VCPs like benzyl alcohol, we may better understand observed data and how VCPs affect air quality. We identify products formed from benzyl alcohol chemistry and use this chemistry to understand how benzyl alcohol forms a key component of smog, secondary organic aerosol.
Andrew T. Lambe, Bin Bai, Masayuki Takeuchi, Nicole Orwat, Paul M. Zimmerman, Mitchell W. Alton, Nga L. Ng, Andrew Freedman, Megan S. Claflin, Drew R. Gentner, Douglas R. Worsnop, and Pengfei Liu
Atmos. Chem. Phys., 23, 13869–13882, https://doi.org/10.5194/acp-23-13869-2023, https://doi.org/10.5194/acp-23-13869-2023, 2023
Short summary
Short summary
We developed a new method to generate nitrate radicals (NO3) for atmospheric chemistry applications that works by irradiating mixtures containing ceric ammonium nitrate with a UV light at room temperature. It has several advantages over traditional NO3 sources. We characterized its performance over a range of mixture and reactor conditions as well as other irradiation products. Proof of concept was demonstrated by generating and characterizing oxidation products of the β-pinene + NO3 reaction.
Han Zang, Dandan Huang, Jiali Zhong, Ziyue Li, Chenxi Li, Huayun Xiao, and Yue Zhao
Atmos. Chem. Phys., 23, 12691–12705, https://doi.org/10.5194/acp-23-12691-2023, https://doi.org/10.5194/acp-23-12691-2023, 2023
Short summary
Short summary
Acylperoxy radicals (RO2) are key intermediates in the atmospheric oxidation of organic compounds, yet our knowledge of their identities and chemistry remains poor. Using direct measurements and kinetic modeling, we identify the composition and formation pathways of acyl RO2 and quantify their contribution to highly oxygenated organic molecules during α-pinene ozonolysis, which will help to understand oxidation chemistry of monoterpenes and sources of low-volatility organics in the atmosphere.
Jacky Y. S. Pang, Florian Berg, Anna Novelli, Birger Bohn, Michelle Färber, Philip T. M. Carlsson, René Dubus, Georgios I. Gkatzelis, Franz Rohrer, Sergej Wedel, Andreas Wahner, and Hendrik Fuchs
Atmos. Chem. Phys., 23, 12631–12649, https://doi.org/10.5194/acp-23-12631-2023, https://doi.org/10.5194/acp-23-12631-2023, 2023
Short summary
Short summary
In this study, the oxidations of sabinene by OH radicals and ozone were investigated with an atmospheric simulation chamber. Reaction rate coefficients of the OH-oxidation reaction at temperatures between 284 to 340 K were determined for the first time in the laboratory by measuring the OH reactivity. Product yields determined in chamber experiments had good agreement with literature values, but discrepancies were found between experimental yields and expected yields from oxidation mechanisms.
Rolf Sander
Atmos. Chem. Phys., 23, 10901–12440, https://doi.org/10.5194/acp-23-10901-2023, https://doi.org/10.5194/acp-23-10901-2023, 2023
Short summary
Short summary
According to Henry's law, the equilibrium ratio between the abundances in the gas phase and in the aqueous phase is constant for a dilute solution. Henry’s law constants of trace gases of potential importance in environmental chemistry have been collected and converted into a uniform format. The compilation contains 46 434 values of Henry's law constants for 10 173 species, collected from 995 references. It is also available on the internet at https://www.henrys-law.org.
Marc von Hobe, Domenico Taraborrelli, Sascha Alber, Birger Bohn, Hans-Peter Dorn, Hendrik Fuchs, Yun Li, Chenxi Qiu, Franz Rohrer, Roberto Sommariva, Fred Stroh, Zhaofeng Tan, Sergej Wedel, and Anna Novelli
Atmos. Chem. Phys., 23, 10609–10623, https://doi.org/10.5194/acp-23-10609-2023, https://doi.org/10.5194/acp-23-10609-2023, 2023
Short summary
Short summary
The trace gas carbonyl sulfide (OCS) transports sulfur from the troposphere to the stratosphere, where sulfate aerosols are formed that influence climate and stratospheric chemistry. An uncertain OCS source in the troposphere is chemical production form dimethyl sulfide (DMS), a gas released in large quantities from the oceans. We carried out experiments in a large atmospheric simulation chamber to further elucidate the chemical mechanism of OCS production from DMS.
Shawon Barua, Siddharth Iyer, Avinash Kumar, Prasenjit Seal, and Matti Rissanen
Atmos. Chem. Phys., 23, 10517–10532, https://doi.org/10.5194/acp-23-10517-2023, https://doi.org/10.5194/acp-23-10517-2023, 2023
Short summary
Short summary
This work illustrates how a common volatile hydrocarbon, hexanal, has the potential to undergo atmospheric autoxidation that leads to prompt formation of condensable material that subsequently contributes to aerosol formation, deteriorating the air quality of urban atmospheres. We used the combined state-of-the-art quantum chemical modeling and experimental flow reactor experiments under atmospheric conditions to resolve the autoxidation mechanism of hexanal initiated by a common oxidant.
Yixin Hao, Jun Zhou, Jie-Ping Zhou, Yan Wang, Suxia Yang, Yibo Huangfu, Xiao-Bing Li, Chunsheng Zhang, Aiming Liu, Yanfeng Wu, Yaqing Zhou, Shuchun Yang, Yuwen Peng, Jipeng Qi, Xianjun He, Xin Song, Yubin Chen, Bin Yuan, and Min Shao
Atmos. Chem. Phys., 23, 9891–9910, https://doi.org/10.5194/acp-23-9891-2023, https://doi.org/10.5194/acp-23-9891-2023, 2023
Short summary
Short summary
By employing an improved net photochemical ozone production rate (NPOPR) detection system based on the dual-channel reaction chamber technique, we measured the net photochemical ozone production rate in the Pearl River Delta in China. The photochemical ozone formation mechanisms in the reaction and reference chambers were investigated using the observation-data-constrained box model, which helped us to validate the NPOPR detection system and understand photochemical ozone formation mechanism.
Kevin J. Nihill, Matthew M. Coggon, Christopher Y. Lim, Abigail R. Koss, Bin Yuan, Jordan E. Krechmer, Kanako Sekimoto, Jose L. Jimenez, Joost de Gouw, Christopher D. Cappa, Colette L. Heald, Carsten Warneke, and Jesse H. Kroll
Atmos. Chem. Phys., 23, 7887–7899, https://doi.org/10.5194/acp-23-7887-2023, https://doi.org/10.5194/acp-23-7887-2023, 2023
Short summary
Short summary
In this work, we collect emissions from controlled burns of biomass fuels that can be found in the western United States into an environmental chamber in order to simulate their oxidation as they pass through the atmosphere. These findings provide a detailed characterization of the composition of the atmosphere downwind of wildfires. In turn, this will help to explore the effects of these changing emissions on downwind populations and will also directly inform atmospheric and climate models.
Caterina Mapelli, James K. Donnelly, Úna E. Hogan, Andrew R. Rickard, Abbie T. Robinson, Fergal Byrne, Con Rob McElroy, Basile F. E. Curchod, Daniel Hollas, and Terry J. Dillon
Atmos. Chem. Phys., 23, 7767–7779, https://doi.org/10.5194/acp-23-7767-2023, https://doi.org/10.5194/acp-23-7767-2023, 2023
Short summary
Short summary
Solvents are chemical compounds with countless uses in the chemical industry, and they also represent one of the main sources of pollution in the chemical sector. Scientists are trying to develop new
greensafer solvents which present favourable advantages when compared to traditional solvents. Since the assessment of these green solvents often lacks air quality considerations, this study aims to understand the behaviour of these compounds, investigating their reactivity in the troposphere.
Roland Benoit, Nesrine Belhadj, Zahraa Dbouk, Maxence Lailliau, and Philippe Dagaut
Atmos. Chem. Phys., 23, 5715–5733, https://doi.org/10.5194/acp-23-5715-2023, https://doi.org/10.5194/acp-23-5715-2023, 2023
Short summary
Short summary
We observed a surprisingly similar set of oxidation product chemical formulas from limonene and α-pinene, including oligomers, formed under cool-flame (present experiments) and simulated atmospheric oxidation (literature). Data analysis indicated that a subset of chemical formulas is common to all experiments independently of experimental conditions. Also, this study indicates that many detected chemical formulas can be ascribed to an autooxidation reaction.
Melissa Meder, Otso Peräkylä, Jonathan G. Varelas, Jingyi Luo, Runlong Cai, Yanjun Zhang, Theo Kurtén, Matthieu Riva, Matti Rissanen, Franz M. Geiger, Regan J. Thomson, and Mikael Ehn
Atmos. Chem. Phys., 23, 4373–4390, https://doi.org/10.5194/acp-23-4373-2023, https://doi.org/10.5194/acp-23-4373-2023, 2023
Short summary
Short summary
We discuss and show the viability of a method where multiple isotopically labelled precursors are used for probing the formation pathways of highly oxygenated organic molecules (HOMs) from the oxidation of the monoterpene a-pinene. HOMs are very important for secondary organic aerosol (SOA) formation in forested regions, and monoterpenes are the single largest source of SOA globally. The fast reactions forming HOMs have thus far remained elusive despite considerable efforts over the last decade.
Philip T. M. Carlsson, Luc Vereecken, Anna Novelli, François Bernard, Steven S. Brown, Bellamy Brownwood, Changmin Cho, John N. Crowley, Patrick Dewald, Peter M. Edwards, Nils Friedrich, Juliane L. Fry, Mattias Hallquist, Luisa Hantschke, Thorsten Hohaus, Sungah Kang, Jonathan Liebmann, Alfred W. Mayhew, Thomas Mentel, David Reimer, Franz Rohrer, Justin Shenolikar, Ralf Tillmann, Epameinondas Tsiligiannis, Rongrong Wu, Andreas Wahner, Astrid Kiendler-Scharr, and Hendrik Fuchs
Atmos. Chem. Phys., 23, 3147–3180, https://doi.org/10.5194/acp-23-3147-2023, https://doi.org/10.5194/acp-23-3147-2023, 2023
Short summary
Short summary
The investigation of the night-time oxidation of the most abundant hydrocarbon, isoprene, in chamber experiments shows the importance of reaction pathways leading to epoxy products, which could enhance particle formation, that have so far not been accounted for. The chemical lifetime of organic nitrates from isoprene is long enough for the majority to be further oxidized the next day by daytime oxidants.
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.
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.
Cited articles
Almatarneh, M. H., Elayan, I. A., Altarawneh, M., and Hollett, J. W.: A computational study of the ozonolysis of sabinene, Theor. Chem. Acc., 138, 30, https://doi.org/10.1007/s00214-019-2420-7, 2019a.
Almatarneh, M. H., Elayan, I. A., Abu-Saleh, A. A. A., Altarawneh, M., and Ariya, P. A.: The gas-phase ozonolysis reaction of methylbutenol: A mechanistic study, Int. J. Quantum Chem., 119, e25888,
https://doi.org/10.1002/qua.25888, 2019b.
Alvarado, A., Tuazon, E. C., Aschmann, S. M., Atkinson, R., and Arey, J.:
Products of the gas-phase reactions of O (3P) atoms and O3 with
a-pinene and 1,2-dimethyl-1-cyclohexene, J. Geophys. Res.-Atmos., 103, 25541, https://doi.org/10.1029/98JD00524, 1998.
Andrea, K. A. and Kerton, F. M.: Iron-catalyzed reactions of CO2 and
epoxides to yield cyclic and polycarbonates, Polym. J., 53, 29–46,
https://doi.org/10.1038/s41428-020-00395-6, 2021.
Appaturi, J., Ramalingam, R., Gnanamani, M., Periyasami, G., Arunachalam,
P., Adnan, R., Adam, F., Wasmiah, M., and Al-Lohedan, H.: Review on Carbon
Dioxide Utilization for Cycloaddition of Epoxides by Ionic Liquid-Modified
Hybrid Catalysts: Effect of Influential Parameters and Mechanisms Insight,
Catalysts, 11, 4, https://doi.org/10.3390/catal11010004, 2021.
Atkinson, R.: Estimations of OH radical rate constants from H-atom
abstraction from C-H and O-H bonds over the temperature range 250–1000 K,
Int. J. Chem. Kinet., 18, 555–568, https://doi.org/10.1002/kin.550180506, 1986a.
Atkinson, R.: Kinetics and mechanisms of the gas-phase reactions of the
hydroxyl radical with organic compounds under atmospheric conditions,
Chem. Rev., 86, 69–201, https://doi.org/10.1021/cr00071a004, 1986b.
Atkinson, R.: A structure-activity relationship for the estimation of rate
constants for the gas-phase reactions of OH radicals with organic compounds,
Int. J. Chem. Kinet., 19, 799–828,
https://doi.org/10.1002/kin.550190903, 1987.
Atkinson, R., Arey, J., Aschmann, S. M., and Tuazon, E. C.: Formation of O
(3P) atoms and epoxides from the gas- phase reaction of O3 with
isoprene, Res. Chem. Intermediat., 20, 385–394,
https://doi.org/10.1163/156856794X00388, 1994a.
Atkinson, R., Aschmann, S. M., Arey, J., and Tuazon, E. C.: Formation yields
of epoxides and O (3P) atoms from the gas-phase reactions of O3
with a series of alkenes, Int. J. Chem. Kinet., 26,
945–950, https://doi.org/10.1002/kin.550260908, 1994b.
Bader, R. F. W., Popelier, P. L. A., and Keith, T. A.: Theoretical
Definition of a Functional Group and the Molecular Orbital Paradigm, Angew. Chem. Int. Ed., 33, 620–631, https://doi.org/10.1002/anie.199406201, 1994.
Barnes, I., Becker, K. H., and Mihalopoulos, N.: An FTIR product study of
the photooxidation of dimethyl disulfide, J. Atmos. Chem.,
18, 267–289, https://doi.org/10.1007/BF00696783, 1994.
Calvert, G., Atkinson, R., Kerr, A., Madronich, S., Moortgat, G.,
Wallington, J., and Yarwood, G.: The Mechanisms of Atmospheric Oxidation of
the Alkenes, Oxford University Press, http://n2t.net/ark:/85065/d7cc11x7 (last access: 24 May 2022), 2000.
Calvert, J., Mellouki, A., Orlando, J., Pilling, M., and Wallington, T.:
Mechanisms of Atmospheric Oxidation of the Oxygenates, Oxford University
Press, https://doi.org/10.1093/oso/9780199767076.001.0001, 2011.
Calvert, J. G., Orlando, J. J., Stockwell, W. R., and Wallington, T. J.: The
Mechanisms of Reactions Influencing Atmospheric Ozone, Oxford University
Press, https://doi.org/10.1093/oso/9780190233020.001.0001, 2015.
Christianson, M. G., Doner, A. C., Davis, M. M., Koritzke, A. L., Turney, J.
M., Schaefer III, H. F., Sheps, L., Osborn, D. L., Taatjes, C. A., and
Rotavera, B.: Reaction mechanisms of a cyclic ether intermediate:
Ethyloxirane, Int. J. Chem. Kinet., 53, 43–59, https://doi.org/10.1002/kin.21423, 2021.
Coppens, P.: Charge Densities Come of Age, Angew. Chem. Int. Ed., 44, 6810–6811, https://doi.org/10.1002/anie.200501734, 2005.
Coulson, C. A. and Moffitt, W. E.: Strain in Non-Tetrahedral Carbon Atoms,
J. Chem. Phys., 15, 151, https://doi.org/10.1063/1.1746450, 1947.
Coulson, C. A. and Moffitt, W. E.: I. The properties of certain strained
hydrocarbons, The London, Edinburgh, and Dublin Philosophical Magazine and
Journal of Science, 40, 1–35, https://doi.org/10.1080/14786444908561208,
1949.
Cromwell, N. H. and Graff, M. A.: Three-Ring carbonyl hyperconjugation in
cis and trans aryl-aroyl ethylene imines and related compounds, J. Org.
Chem., 17, 414–425, https://doi.org/10.1021/jo01137a014, 1952.
Doner, A. C., Davis, M. M., Koritzke, A. L., Christianson, M. G., Turney, J.
M., Schaefer III, H. F., Sheps, L., Osborn, D. L., Taatjes, C. A., and
Rotavera, B.: Isomer-dependent reaction mechanisms of cyclic ether
intermediates: cis-2,3-dimethyloxirane and trans-2,3-dimethyloxirane, Int. J. Chem. Kinet., 53, 127–145, https://doi.org/10.1002/kin.21429, 2021.
Ehrenberg, L. and Hussain, S.: Genetic toxicity of some important epoxides,
Mutation Research/Reviews in Genetic Toxicology, Mutat. Res./Reviews in Genetic Toxicology, 86, 1–113, https://doi.org/10.1016/0165-1110(81)90034-8, 1981.
El Othmani, H., Ren, Y., Mellouki, A., Daële, V., and McGillen, M. R.:
Gas-phase rate coefficient of OH + cyclohexene oxide measured from 251 to
373 K, Chem. Phys. Lett., 783, 139056,
https://doi.org/10.1016/j.cplett.2021.139056, 2021a.
El Othmani, H., Ren, Y., Bedjanian, Y., El Hajjaji, S., Tovar, C., Wiesen,
P., Mellouki, A., McGillen, M. R., and Daële, V.: Gas-Phase Rate
Coefficient of OH + 1,2-Epoxybutane Determined between 220 and 950 K, ACS Earth and Space Chemistry, 5, 960–968,
https://doi.org/10.1021/acsearthspacechem.1c00050, 2021b.
Fokin, V. V. and Wu, P.: Epoxides and Aziridines in Click Chemistry, in:
Aziridines and Epoxides in Organic Synthesis, John Wiley & Sons, Ltd,
443–477, https://doi.org/10.1002/3527607862.ch12, 2006.
Förster, T.: Die gegenseitige Beeinflussung der Valenzen im
Kohlenstoffatom, Z. Phys. Chem., 43B, 58–78, https://doi.org/10.1515/zpch-1939-4306, 1939.
Fuzzi, S., Baltensperger, U., Carslaw, K., Decesari, S., Denier van der Gon, H., Facchini, M. C., Fowler, D., Koren, I., Langford, B., Lohmann, U., Nemitz, E., Pandis, S., Riipinen, I., Rudich, Y., Schaap, M., Slowik, J. G., Spracklen, D. V., Vignati, E., Wild, M., Williams, M., and Gilardoni, S.: Particulate matter, air quality and climate: lessons learned and future needs, Atmos. Chem. Phys., 15, 8217–8299, https://doi.org/10.5194/acp-15-8217-2015, 2015.
Gao, S., Ng, N. L., Keywood, M., Varutbangkul, V., Bahreini, R., Nenes, A.,
He, J., Yoo, K. Y., Beauchamp, J. L., Hodyss, R. P., Flagan, R. C., and
Seinfeld, J. H.: Particle Phase Acidity and Oligomer Formation in Secondary
Organic Aerosol, Environ. Sci. Technol., 38, 6582–6589,
https://doi.org/10.1021/es049125k, 2004.
Grabowsky, S., Jayatilaka, D., Mebs, S., and Luger, P.: The Electron
Localizability Indicator from X-Ray Diffraction Data – A First Application
to a Series of Epoxide Derivatives, Chem.-Eur. J., 16,
12818–12821, https://doi.org/10.1002/chem.201002061, 2010.
Guo, L., Lamb, K. J., and North, M.: Recent developments in organocatalysed
transformations of epoxides and carbon dioxide into cyclic carbonates, Green
Chem., 23, 77–118, https://doi.org/10.1039/D0GC03465G, 2021.
Hereijgers, B. P. C., Parton, R. F., and Weckhuysen, B. M.: Mechanistic
insights in the olefin epoxidation with cyclohexyl hydroperoxide, Catal.
Sci. Technol., 2, 951–960, https://doi.org/10.1039/C2CY00455K, 2012.
IUPAC Task Group on Atmospheric Chemical Kinetic Data Evaluation:
https://iupac-aeris.ipsl.fr/, last access: 26 October 2021.
Jacobs, M. I., Darer, A. I., and Elrod, M. J.: Rate Constants and Products
of the OH Reaction with Isoprene-Derived Epoxides, Environ. Sci. Technol., 47, 12868–12876, https://doi.org/10.1021/es403340g, 2013.
Jenkin, M. E., Young, J. C., and Rickard, A. R.: The MCM v3.3.1 degradation scheme for isoprene, Atmos. Chem. Phys., 15, 11433–11459, https://doi.org/10.5194/acp-15-11433-2015, 2015.
Jenkin, M. E., Valorso, R., Aumont, B., Rickard, A. R., and Wallington, T. J.: Estimation of rate coefficients and branching ratios for gas-phase reactions of OH with aliphatic organic compounds for use in automated mechanism construction, Atmos. Chem. Phys., 18, 9297–9328, https://doi.org/10.5194/acp-18-9297-2018, 2018.
Jiang, X., Tsona, N. T., Jia, L., Liu, S., Zhang, H., Xu, Y., and Du, L.: Secondary organic aerosol formation from photooxidation of furan: effects of NOx and humidity, Atmos. Chem. Phys., 19, 13591–13609, https://doi.org/10.5194/acp-19-13591-2019, 2019.
Kanakidou, M., Seinfeld, J. H., Pandis, S. N., Barnes, I., Dentener, F. J., Facchini, M. C., Van Dingenen, R., Ervens, B., Nenes, A., Nielsen, C. J., Swietlicki, E., Putaud, J. P., Balkanski, Y., Fuzzi, S., Horth, J., Moortgat, G. K., Winterhalter, R., Myhre, C. E. L., Tsigaridis, K., Vignati, E., Stephanou, E. G., and Wilson, J.: Organic aerosol and global climate modelling: a review, Atmos. Chem. Phys., 5, 1053–1123, https://doi.org/10.5194/acp-5-1053-2005, 2005.
Klotz, B., Barnes, I., Becker, K. H., and Golding, B. T.: Atmospheric
chemistry of benzeneoxide/oxepin, J. Chem. Soc. Faraday T., 93, 1507–1516, https://doi.org/10.1039/A606152D, 1997.
Klotz, B., Barnes, I., Golding, B. T., and Becker, K.-H.: Atmospheric
chemistry of toluene-1,2-oxide/2-methyloxepin, Phys. Chem. Chem. Phys., 2, 227–235, https://doi.org/10.1039/A908365K, 2000.
Kohout, M.: A measure of electron localizability, Int. J. Quantum Chem., 97, 651–658, https://doi.org/10.1002/qua.10768, 2004.
Kolb, H. C., Finn, M. G., and Sharpless, K. B.: Click Chemistry: Diverse
Chemical Function from a Few Good Reactions, Angew. Chem. Int. Edit., 40, 2004–2021, https://doi.org/10.1002/1521-3773(20010601)40:11<2004::AID-ANIE2004>3.0.CO;2-5, 2001.
Koritsanszky, T. S. and Coppens, P.: Chemical Applications of X-ray
Charge-Density Analysis, Chem. Rev., 101, 1583–1628,
https://doi.org/10.1021/cr990112c, 2001.
Kutzelnigg, W.: Book Review: Atoms in Molecules. A Quantum Theory (International Series Monographs on Chemistry, Vol. 22). By R. F. W. Bader, Angew. Chem. Int. Ed., 32, 128–129, https://doi.org/10.1002/anie.199301282, 1993.
Kwok, E. S. C. and Atkinson, R.: Estimation of hydroxyl radical reaction
rate constants for gas-phase organic compounds using a structure-reactivity
relationship: An update, Atmos. Environ., 29, 1685–1695,
https://doi.org/10.1016/1352-2310(95)00069-B, 1995.
Lal, V., Khalizov, A. F., Lin, Y., Galvan, M. D., Connell, B. T., and Zhang,
R.: Heterogeneous Reactions of Epoxides in Acidic Media, J. Phys. Chem. A, 116, 6078–6090, https://doi.org/10.1021/jp2112704, 2012.
Lelieveld, J., Gromov, S., Pozzer, A., and Taraborrelli, D.: Global tropospheric hydroxyl distribution, budget and reactivity, Atmos. Chem. Phys., 16, 12477–12493, https://doi.org/10.5194/acp-16-12477-2016, 2016.
Li, M., Liu, Y., and Wang, L.: Gas-phase ozonolysis of furans, methylfurans,
and dimethylfurans in the atmosphere, Phys. Chem. Chem. Phys.,
20, 24735–24743, https://doi.org/10.1039/C8CP04947E, 2018.
Lin, Y.-H., Zhang, H., Pye, H. O. T., Zhang, Z., Marth, W. J., Park, S.,
Arashiro, M., Cui, T., Budisulistiorini, S. H., Sexton, K. G., Vizuete, W.,
Xie, Y., Luecken, D. J., Piletic, I. R., Edney, E. O., Bartolotti, L. J.,
Gold, A., and Surratt, J. D.: Epoxide as a precursor to secondary organic
aerosol formation from isoprene photooxidation in the presence of nitrogen
oxides, P. Natl. Acad. Sci. USA, 110, 6718–6723,
https://doi.org/10.1073/pnas.1221150110, 2013.
McGillen, M. R., Carter, W. P. L., Mellouki, A., Orlando, J. J., Picquet-Varrault, B., and Wallington, T. J.: Database for the kinetics of the gas-phase atmospheric reactions of organic compounds, Earth Syst. Sci. Data, 12, 1203–1216, https://doi.org/10.5194/essd-12-1203-2020, 2020.
Middala, S., Campbell, S., Olea, C., Scruggs, A., and Hasson, A. S.:
Kinetics and mechanism of the reaction of propylene oxide with chlorine
atoms and hydroxy radicals, Int. J. Chem. Kinet., 43,
507–521, https://doi.org/10.1002/kin.20580, 2011.
Minerath, E. C. and Elrod, M. J.: Assessing the Potential for Diol and
Hydroxy Sulfate Ester Formation from the Reaction of Epoxides in
Tropospheric Aerosols, Environ. Sci. Technol., 43, 1386–1392, https://doi.org/10.1021/es8029076, 2009.
Minerath, E. C., Schultz, M. P., and Elrod, M. J.: Kinetics of the Reactions
of Isoprene-Derived Epoxides in Model Tropospheric Aerosol Solutions,
Environ. Sci. Technol., 43, 8133–8139, https://doi.org/10.1021/es902304p, 2009.
Oshima, T., Asahara, H., Kubo, E., Miyamoto, S., and Togaya, K.:
Conformational Effects in Acid-Mediated Ring Opening of Epoxides: A
Prominent Role of the Oxirane Walsh Orbital, Org. Lett., 10,
2413–2416, https://doi.org/10.1021/ol800535c, 2008.
Otto, H.-H. and Schirmeister, T.: Cysteine Proteases and Their Inhibitors,
Chem. Rev., 97, 133–172, https://doi.org/10.1021/cr950025u, 1997.
Parker, R. E. and Isaacs, N. S.: Mechanisms Of Epoxide Reactions, Chem.
Rev., 59, 737–799, https://doi.org/10.1021/cr50028a006, 1959.
Paulot, F., Crounse, J. D., Kjaergaard, H. G., Kürten, A., St Clair, J.
M., Seinfeld, J. H., and Wennberg, P. O.: Unexpected epoxide formation in
the gas-phase photooxidation of isoprene, Science, 325,
730—733, https://doi.org/10.1126/science.1172910, 2009.
Paulson, S. E., Flagan, R. C., and Seinfeld, J. H.: Atmospheric
photooxidation of isoprene part I: The hydroxyl radical and ground state
atomic oxygen reactions, Int. J. Chem. Kinet., 24,
79–101, https://doi.org/10.1002/kin.550240109, 1992.
Piletic, I. R., Edney, E. O., and Bartolotti, L. J.: Barrierless Reactions
with Loose Transition States Govern the Yields and Lifetimes of Organic
Nitrates Derived from Isoprene, J. Phys. Chem. A, 121, 8306–8321,
https://doi.org/10.1021/acs.jpca.7b08229, 2017.
Powers, J. C., Asgian, J. L., Ekici, Ö. D., and James, K. E.:
Irreversible Inhibitors of Serine, Cysteine, and Threonine Proteases,
Chem. Rev., 102, 4639–4750, https://doi.org/10.1021/cr010182v, 2002.
Rogers, M. T.: The Electric Moments and Ultraviolet Absorption Spectra of
Some Derivatives of Cyclopropane and of Ethylene Oxide, J. Am. Chem. Soc., 69, 2544–2548, https://doi.org/10.1021/ja01202a081, 1947.
Sandhiya, L., Kolandaivel, P., and Senthilkumar, K.: Mechanism and Kinetics
of the Atmospheric Oxidative Degradation of Dimethylphenol Isomers Initiated
by OH Radical, J. Phys. Chem. A, 117, 4611–4626,
https://doi.org/10.1021/jp3120868, 2013.
Schirmeister, T. and Klockow, A.: Cysteine Protease Inhibitors Containing
Small Rings, Mini-Rev. Med. Chem., 3, 585–596, 2003.
Searles, S. and Tamres, M.: Hydrogen Bond Formation with Saturated Cyclic
Ethers1, J. Am. Chem. Soc., 73, 3704–3706,
https://doi.org/10.1021/ja01152a041, 1951.
Searles, S., Tamres, M., and Lippincott, E. R.: Hydrogen Bonding Ability and
Structure of Ethylene Oxides, J. Am. Chem. Soc., 75,
2775–2777, https://doi.org/10.1021/ja01107a517, 1953.
Shrivastava, M., Andreae, M. O., Artaxo, P., Barbosa, H. M. J., Berg, L. K.,
Brito, J., Ching, J., Easter, R. C., Fan, J., Fast, J. D., Feng, Z.,
Fuentes, J. D., Glasius, M., Goldstein, A. H., Alves, E. G., Gomes, H., Gu,
D., Guenther, A., Jathar, S. H., Kim, S., Liu, Y., Lou, S., Martin, S. T.,
McNeill, V. F., Medeiros, A., de Sá, S. S., Shilling, J. E., Springston,
S. R., Souza, R. a. F., Thornton, J. A., Isaacman-VanWertz, G., Yee, L. D.,
Ynoue, R., Zaveri, R. A., Zelenyuk, A., and Zhao, C.: Urban pollution
greatly enhances formation of natural aerosols over the Amazon rainforest,
Nat. Commun., 10, 1046, https://doi.org/10.1038/s41467-019-08909-4, 2019.
Skov, H., Benter, T., Schindler, R. N., Hjorth, J., and Restelli, G.:
Epoxide formation in the reactions of the nitrate radical with
2,3-dimethyl-2-butene, cis- and trans-2-butene and isoprene, Atmos. Environ., 28, 1583–1592, https://doi.org/10.1016/1352-2310(94)90304-2, 1994.
Starit, L. A., Ketcham, Roger., Jambotkar, D., and Shah, V. P.:
Three-Membered Rings. I. Conjugative Properties and Electrinic Spectra of
Arylcyclopropanes, Oxiranes, and Thiiranes, J. Am. Chem. Soc., 86,
4628–4630, https://doi.org/10.1021/ja01075a022, 1964.
Stropoli, S. J., Miner, C. R., Hill, D. R., and Elrod, M. J.: Assessing
Potential Oligomerization Reaction Mechanisms of Isoprene Epoxydiols on
Secondary Organic Aerosol, Environ. Sci. Technol., 53, 176–184, https://doi.org/10.1021/acs.est.8b05247, 2019.
Tamres, M., Searles, S., Leighly, E. M., and Mohrman, D. W.: Hydrogen Bond
Formation with Pyridines and Aliphatic Amines1, J. Am. Chem. Soc., 76, 3983–3985, https://doi.org/10.1021/ja01644a035, 1954.
Tovar, C. M., Haack, A., Barnes, I., Bejan, I. G., and Wiesen, P.:
Experimental and theoretical study of the reactivity of a series of epoxides
with chlorine atoms at 298 K, Phys. Chem. Chem. Phys., 23,
5176–5186, https://doi.org/10.1039/D0CP06033J, 2021.
Vereecken, L.: Reaction Mechanisms for the Atmospheric Oxidation of
Monocyclic Aromatic Compounds, in: Advances in Atmospheric Chemistry, edited by: Barker, J. R., Steiner, A. L., and Wallington, T. J., World Scientific, 377–527, https://doi.org/10.1142/9789813271838_0006, 2018.
Vereecken, L., Glowacki, D. R., and Pilling, M. J.: Theoretical Chemical
Kinetics in Tropospheric Chemistry: Methodologies and Applications, Chem.
Rev., 115, 4063–4114, https://doi.org/10.1021/cr500488p, 2015.
Vereecken, L., Aumont, B., Barnes, I., Bozzelli, J. W., Goldman, M. J.,
Green, W. H., Madronich, S., Mcgillen, M. R., Mellouki, A., Orlando, J. J.,
Picquet-Varrault, B., Rickard, A. R., Stockwell, W. R., Wallington, T. J.,
and Carter, W. P. L.: Perspective on Mechanism Development and
Structure-Activity Relationships for Gas-Phase Atmospheric Chemistry,
Int. J. Chem. Kinet., 50, 435–469, https://doi.org/10.1002/kin.21172, 2018.
Villanueva, F., Cabañas, B., Monedero, E., Salgado, S., Bejan, I., and
Martin, P.: Atmospheric degradation of alkylfurans with chlorine atoms:
Product and mechanistic study, Atmos. Environ., 43, 2804–2813,
https://doi.org/10.1016/j.atmosenv.2009.02.030, 2009.
Virmani, A., Walavalkar, M. P., Sharma, A., Sengupta, S., Saha, A., and
Kumar, A.: Kinetic studies of the gas phase reaction of 1,2-propylene oxide
with the OH radical over a temperature range of 261–335 K, Atmos. Environ., 237, 117709, https://doi.org/10.1016/j.atmosenv.2020.117709, 2020.
Wallington, T. J., Dagaut, P., and Kurylo, M. J.: Correlation between
gas-phase and solution-phase reactivities of hydroxyl radicals towards
saturated organic compounds, J. Phys. Chem., 92, 5024–5028,
https://doi.org/10.1021/j100328a039, 1988a.
Wallington, T. J., Liu, R., Dagaut, P., and Kurylo, M. J.: The gas phase
reactions of hydroxyl radicals with a series of aliphatic ethers over the
temperature range 240–440 K, 20, 41–49,
https://doi.org/10.1002/kin.550200106, 1988b.
Wallington, T. J., Dagaut, P., Liu, R., and Kurylo, M. J.: The gas phase
reactions of hydroxyl radicals with a series of esters over the temperature
range 240–440 K, Int. J. Chem. Kinet., 20, 177–186,
https://doi.org/10.1002/kin.550200210, 1988c.
Walsh, A. D.: The structures of ethylene oxide, cyclopropane, and related
molecules, T. Faraday Soc., 45, 179–190,
https://doi.org/10.1039/TF9494500179, 1949.
Wang, Q., Ni, S., Bai, F., and Pan, X.: Theoretical investigation on
atmospheric reaction mechanism, kinetics and SAR estimations of four-carbon
ketones and alcohols, Atmos. Environ., 271, 118915,
https://doi.org/10.1016/j.atmosenv.2021.118915, 2022.
Wang, X., Jacob, D. J., Eastham, S. D., Sulprizio, M. P., Zhu, L., Chen, Q., Alexander, B., Sherwen, T., Evans, M. J., Lee, B. H., Haskins, J. D., Lopez-Hilfiker, F. D., Thornton, J. A., Huey, G. L., and Liao, H.: The role of chlorine in global tropospheric chemistry, Atmos. Chem. Phys., 19, 3981–4003, https://doi.org/10.5194/acp-19-3981-2019, 2019.
Wiberg, K. B.: Bent Bonds in Organic Compounds, Acc. Chem. Res., 29,
229–234, https://doi.org/10.1021/ar950207a, 1996.
Young, C. J., Washenfelder, R. A., Edwards, P. M., Parrish, D. D., Gilman, J. B., Kuster, W. C., Mielke, L. H., Osthoff, H. D., Tsai, C., Pikelnaya, O., Stutz, J., Veres, P. R., Roberts, J. M., Griffith, S., Dusanter, S., Stevens, P. S., Flynn, J., Grossberg, N., Lefer, B., Holloway, J. S., Peischl, J., Ryerson, T. B., Atlas, E. L., Blake, D. R., and Brown, S. S.: Chlorine as a primary radical: evaluation of methods to understand its role in initiation of oxidative cycles, Atmos. Chem. Phys., 14, 3427–3440, https://doi.org/10.5194/acp-14-3427-2014, 2014.
Zhang, F., Wang, Y., Zhang, X., Zhang, X., Liu, H., and Han, B.: Recent
advances in the coupling of CO2 and epoxides into cyclic carbonates under halogen-free condition, Green Chemical Engineering, 1, 82–93,
https://doi.org/10.1016/j.gce.2020.09.008, 2020.
Zhang, Q., Jimenez, J. L., Worsnop, D. R., and Canagaratna, M.: A Case Study
of Urban Particle Acidity and Its Influence on Secondary Organic Aerosol,
Environ. Sci. Technol., 41, 3213–3219, https://doi.org/10.1021/es061812j, 2007.
Zhou, S., Yeung, L. W. Y., Forbes, M. W., Mabury, S., and Abbatt, J. P. D.:
Epoxide formation from heterogeneous oxidation of benzo[a]pyrene with
gas-phase ozone and indoor air, Environ. Sci.-Proc. Imp., 19, 1292–1299, https://doi.org/10.1039/C7EM00181A, 2017.
Zou, B. and Hu, C.: Halogen-free processes for organic carbonate synthesis
from CO2, Current Opinion in Green and Sustainable Chemistry, 3,
11–16, https://doi.org/10.1016/j.cogsc.2016.10.007, 2017.
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.
This work explores the kinetics and reactivity of epoxides towards the OH radical using two...
Altmetrics
Final-revised paper
Preprint