Articles | Volume 20, issue 21
https://doi.org/10.5194/acp-20-12983-2020
© Author(s) 2020. 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-20-12983-2020
© Author(s) 2020. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
06 Nov 2020
Research article |
| 06 Nov 2020
| 06 Nov 2020
Kinetics of dimethyl sulfide (DMS) reactions with isoprene-derived Criegee intermediates studied with direct UV absorption
Mei-Tsan Kuo
Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei
10617, Taiwan
Isabelle Weber
Univ. Lille, CNRS, UMR 8522 – PC2A – Physicochimie des Processus de Combustion et de l'Atmosphère, 59000 Lille, France
Present address: Department of Applied Chemistry and Institute of
Molecular Science, National Chiao Tung University, Hsinchu 30010, Taiwan
Christa Fittschen
Univ. Lille, CNRS, UMR 8522 – PC2A – Physicochimie des Processus de Combustion et de l'Atmosphère, 59000 Lille, France
Luc Vereecken
Atmospheric Chemistry Department, Max Planck Institute for Chemistry, Hahn-Meitner-Weg 1, 55128 Mainz, Germany
Institute for Energy and Climate Research, IEK-8: Troposphere,
Forschungszentrum Jülich GmbH, 52428 Jülich, Germany
Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei
10617, Taiwan
Department of Chemistry, National Taiwan University, Taipei 10617,
Taiwan
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Mei-Tsan Kuo, Isabelle Weber, Christa Fittschen, and Jim Jr-Min Lin
Atmos. Chem. Phys. Discuss., https://doi.org/10.5194/acp-2020-326, https://doi.org/10.5194/acp-2020-326, 2020
Preprint withdrawn
Short summary
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Dimethyl sulfide (DMS) is the major sulfur-containing species in the troposphere. Previous work by Newland et al. [Atmos. Chem. Phys., 15, 9521–9536, 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., suggesting these CIs would not oxidize atmospheric DMS at any substantial level.
Ernst-Peter Röth and Luc Vereecken
Atmos. Chem. Phys., 24, 2625–2638, https://doi.org/10.5194/acp-24-2625-2024, https://doi.org/10.5194/acp-24-2625-2024, 2024
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The paper presents the radical and molecular product quantum yields in the photolysis reaction of CHDO at wavelengths above 300 nm. Two different approaches based on literature data are used, with results falling within both approaches' uncertainty ranges. Simple functional forms are presented for use in photochemical models of the atmosphere.
Hao Luo, Luc Vereecken, Hongru Shen, Sungah Kang, Iida Pullinen, Mattias Hallquist, Hendrik Fuchs, Andreas Wahner, Astrid Kiendler-Scharr, Thomas F. Mentel, and Defeng Zhao
Atmos. Chem. Phys., 23, 7297–7319, https://doi.org/10.5194/acp-23-7297-2023, https://doi.org/10.5194/acp-23-7297-2023, 2023
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Oxidation of limonene, an element emitted by trees and chemical products, by OH, a daytime oxidant, forms many highly oxygenated organic molecules (HOMs), including C10-20 compounds. HOMs play an important role in new particle formation and growth. HOM formation can be explained by the chemistry of peroxy radicals. We found that a minor branching ratio initial pathway plays an unexpected, significant role. Considering this pathway enables accurate simulations of HOMs and other concentrations.
Philip T. M. Carlsson, Luc Vereecken, Anna Novelli, François Bernard, Steven S. Brown, Bellamy Brownwood, Changmin Cho, John N. Crowley, Patrick Dewald, Peter M. Edwards, Nils Friedrich, Juliane L. Fry, Mattias Hallquist, Luisa Hantschke, Thorsten Hohaus, Sungah Kang, Jonathan Liebmann, Alfred W. Mayhew, Thomas Mentel, David Reimer, Franz Rohrer, Justin Shenolikar, Ralf Tillmann, Epameinondas Tsiligiannis, Rongrong Wu, Andreas Wahner, Astrid Kiendler-Scharr, and Hendrik Fuchs
Atmos. Chem. Phys., 23, 3147–3180, https://doi.org/10.5194/acp-23-3147-2023, https://doi.org/10.5194/acp-23-3147-2023, 2023
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The investigation of the night-time oxidation of the most abundant hydrocarbon, isoprene, in chamber experiments shows the importance of reaction pathways leading to epoxy products, which could enhance particle formation, that have so far not been accounted for. The chemical lifetime of organic nitrates from isoprene is long enough for the majority to be further oxidized the next day by daytime oxidants.
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
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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.
Mike J. Newland, Camille Mouchel-Vallon, Richard Valorso, Bernard Aumont, Luc Vereecken, Michael E. Jenkin, and Andrew R. Rickard
Atmos. Chem. Phys., 22, 6167–6195, https://doi.org/10.5194/acp-22-6167-2022, https://doi.org/10.5194/acp-22-6167-2022, 2022
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Alkene ozonolysis produces Criegee intermediates, which can act as oxidants or decompose to give a range of closed-shell and radical products, including OH. Therefore it is essential to accurately represent the chemistry of Criegee intermediates in atmospheric models in order to understand their impacts on atmospheric composition. Here we provide a mechanism construction protocol by which the central features of alkene ozonolysis chemistry can be included in an automatic mechanism generator.
Philipp G. Eger, Luc Vereecken, Rolf Sander, Jan Schuladen, Nicolas Sobanski, Horst Fischer, Einar Karu, Jonathan Williams, Ville Vakkari, Tuukka Petäjä, Jos Lelieveld, Andrea Pozzer, and John N. Crowley
Atmos. Chem. Phys., 21, 14333–14349, https://doi.org/10.5194/acp-21-14333-2021, https://doi.org/10.5194/acp-21-14333-2021, 2021
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We determine the impact of pyruvic acid photolysis on the formation of acetaldehyde and peroxy radicals during summer and autumn in the Finnish boreal forest using a data-constrained box model. Our results are dependent on the chosen scenario in which the overall quantum yield and the photolysis products are varied. We highlight that pyruvic acid photolysis can be an important contributor to acetaldehyde and peroxy radical formation in remote, forested regions.
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
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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
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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.
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
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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.
Luc Vereecken and Barbara Nozière
Atmos. Chem. Phys., 20, 7429–7458, https://doi.org/10.5194/acp-20-7429-2020, https://doi.org/10.5194/acp-20-7429-2020, 2020
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Alkyl peroxy radicals, RO2, are important intermediates in the oxidation of organic material in the atmosphere. It was shown earlier that hydrogen atom migration within RO2 can be important and results in the formation of additional oxidants and large highly oxygenated molecules that lead to more and larger aerosols. In this work we propose a method for predicting the chemical rate for these H migrations in RO2, helping atmospheric models to correctly include these reactions.
Simon Rosanka, Giang H. T. Vu, Hue M. T. Nguyen, Tien V. Pham, Umar Javed, Domenico Taraborrelli, and Luc Vereecken
Atmos. Chem. Phys., 20, 6671–6686, https://doi.org/10.5194/acp-20-6671-2020, https://doi.org/10.5194/acp-20-6671-2020, 2020
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Isocyanic acid, HNCO, is a toxic chemical compound emitted to the atmosphere by biomass burning and by unwanted release in NOx mitigation systems in vehicles such as the AdBlue system. We have studied the loss processes of HNCO, finding that it is unreactive to most atmospheric oxidants and thus has a long chemical lifetime. The main removal is then by deposition on surfaces and transition to aqueous phase, such as clouds. The long lifetime also allows it to be transported to the stratosphere.
Mei-Tsan Kuo, Isabelle Weber, Christa Fittschen, and Jim Jr-Min Lin
Atmos. Chem. Phys. Discuss., https://doi.org/10.5194/acp-2020-326, https://doi.org/10.5194/acp-2020-326, 2020
Preprint withdrawn
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Dimethyl sulfide (DMS) is the major sulfur-containing species in the troposphere. Previous work by Newland et al. [Atmos. Chem. Phys., 15, 9521–9536, 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., suggesting these CIs would not oxidize atmospheric DMS at any substantial level.
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
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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.
Christa Fittschen, Mohamad Al Ajami, Sebastien Batut, Valerio Ferracci, Scott Archer-Nicholls, Alexander T. Archibald, and Coralie Schoemaecker
Atmos. Chem. Phys., 19, 349–362, https://doi.org/10.5194/acp-19-349-2019, https://doi.org/10.5194/acp-19-349-2019, 2019
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Concentrations of OH, the main oxidant in the atmosphere, were measured in biogenic environments up to a factor of 10 higher than predicted by models. This was interpreted as a major lack in our understanding of biogenic volatile organic compound chemistry. But interferences of unknown origin have also been discovered, and we present experimental and modelling evidence that the interference might be due to the unexpected decomposition of a new class of molecule, ROOOH, in the FAGE instruments.
Hendrik Fuchs, Sascha Albrecht, Ismail–Hakki Acir, Birger Bohn, Martin Breitenlechner, Hans-Peter Dorn, Georgios I. Gkatzelis, Andreas Hofzumahaus, Frank Holland, Martin Kaminski, Frank N. Keutsch, Anna Novelli, David Reimer, Franz Rohrer, Ralf Tillmann, Luc Vereecken, Robert Wegener, Alexander Zaytsev, Astrid Kiendler-Scharr, and Andreas Wahner
Atmos. Chem. Phys., 18, 8001–8016, https://doi.org/10.5194/acp-18-8001-2018, https://doi.org/10.5194/acp-18-8001-2018, 2018
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The photooxidation of methyl vinyl ketone MVK, one of the most important products of isoprene that is emitted by plants, was investigated in the atmospheric simulation chamber SAPHIR for conditions found in forested areas. The comparison of measured trace gas time series with model calculations shows a gap in the understanding of radical chemistry in the MVK oxidation scheme. The possibility of unimolecular isomerization reactions were investigated by means of quantum-chemical calculations.
Mike J. Newland, Andrew R. Rickard, Tomás Sherwen, Mathew J. Evans, Luc Vereecken, Amalia Muñoz, Milagros Ródenas, and William J. Bloss
Atmos. Chem. Phys., 18, 6095–6120, https://doi.org/10.5194/acp-18-6095-2018, https://doi.org/10.5194/acp-18-6095-2018, 2018
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Stabilised Criegee intermediates (SCIs) are formed in the reaction of alkenes with ozone, both of which are ubiquitous throughout the troposphere. We determine the fate and global distribution of SCI from monoterpene ozonolysis. One major fate of SCI is reaction with H2O, but for a fraction of SCIs, unimolecular reactions dominate. Concentrations of SCIs are high enough regionally to play a key role in the conversion of sulfur dioxide to aerosol, affecting air quality and climate.
Hendrik Fuchs, Anna Novelli, Michael Rolletter, Andreas Hofzumahaus, Eva Y. Pfannerstill, Stephan Kessel, Achim Edtbauer, Jonathan Williams, Vincent Michoud, Sebastien Dusanter, Nadine Locoge, Nora Zannoni, Valerie Gros, Francois Truong, Roland Sarda-Esteve, Danny R. Cryer, Charlotte A. Brumby, Lisa K. Whalley, Daniel Stone, Paul W. Seakins, Dwayne E. Heard, Coralie Schoemaecker, Marion Blocquet, Sebastien Coudert, Sebastien Batut, Christa Fittschen, Alexander B. Thames, William H. Brune, Cheryl Ernest, Hartwig Harder, Jennifer B. A. Muller, Thomas Elste, Dagmar Kubistin, Stefanie Andres, Birger Bohn, Thorsten Hohaus, Frank Holland, Xin Li, Franz Rohrer, Astrid Kiendler-Scharr, Ralf Tillmann, Robert Wegener, Zhujun Yu, Qi Zou, and Andreas Wahner
Atmos. Meas. Tech., 10, 4023–4053, https://doi.org/10.5194/amt-10-4023-2017, https://doi.org/10.5194/amt-10-4023-2017, 2017
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Hydroxyl radical reactivity (k(OH)) is closely related to processes that lead to the formation of oxidised, secondary pollutants such as ozone and aerosol. In order to compare the performances of instruments measuring k(OH), experiments were conducted in the simulation chamber SAPHIR. Chemical conditions were chosen either to be representative of the atmosphere or to test potential limitations of instruments. Overall, the results show that instruments are capable of measuring k(OH).
Stephan Keßel, David Cabrera-Perez, Abraham Horowitz, Patrick R. Veres, Rolf Sander, Domenico Taraborrelli, Maria Tucceri, John N. Crowley, Andrea Pozzer, Christof Stönner, Luc Vereecken, Jos Lelieveld, and Jonathan Williams
Atmos. Chem. Phys., 17, 8789–8804, https://doi.org/10.5194/acp-17-8789-2017, https://doi.org/10.5194/acp-17-8789-2017, 2017
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In this study we identify an often overlooked stable oxide of carbon, namely carbon suboxide (C3O2), in ambient air. We have made C3O2 and in the laboratory determined its absorption cross section data and the rate of reaction with two important atmospheric oxidants, OH and O3. By incorporating known sources and sinks in a global model we have generated a first global picture of the distribution of this species in the atmosphere.
Anna Novelli, Korbinian Hens, Cheryl Tatum Ernest, Monica Martinez, Anke C. Nölscher, Vinayak Sinha, Pauli Paasonen, Tuukka Petäjä, Mikko Sipilä, Thomas Elste, Christian Plass-Dülmer, Gavin J. Phillips, Dagmar Kubistin, Jonathan Williams, Luc Vereecken, Jos Lelieveld, and Hartwig Harder
Atmos. Chem. Phys., 17, 7807–7826, https://doi.org/10.5194/acp-17-7807-2017, https://doi.org/10.5194/acp-17-7807-2017, 2017
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The ambient concentration of stabilised Criegee intermediates (SCIs) was estimated for two
environments using field data. The low concentrations predicted indicate that SCIs are
unlikely to have a large impact on atmospheric chemistry. Concurrent measurements of an OH background signal using the Mainz IPI-LIF-FAGE instrument were found to be consistent with the chemistry of SCIs during the measurement campaigns.
Martin Kaminski, Hendrik Fuchs, Ismail-Hakki Acir, Birger Bohn, Theo Brauers, Hans-Peter Dorn, Rolf Häseler, Andreas Hofzumahaus, Xin Li, Anna Lutz, Sascha Nehr, Franz Rohrer, Ralf Tillmann, Luc Vereecken, Robert Wegener, and Andreas Wahner
Atmos. Chem. Phys., 17, 6631–6650, https://doi.org/10.5194/acp-17-6631-2017, https://doi.org/10.5194/acp-17-6631-2017, 2017
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Monoterpenes emitted by trees are among the volatile organic compounds with the highest global emission rates. The atmospheric degradation of the monoterpene β-pinene was investigated in the atmosphere simulation chamber SAPHIR in Jülich under low NOx and atmospheric β-pinene concentrations. While the budget of OH was balanced, both OH and HO2 concentrations were underestimated in the simulation results. These observations suggest the existence of unaccounted sources of HO2.
R. F. Hansen, M. Blocquet, C. Schoemaecker, T. Léonardis, N. Locoge, C. Fittschen, B. Hanoune, P. S. Stevens, V. Sinha, and S. Dusanter
Atmos. Meas. Tech., 8, 4243–4264, https://doi.org/10.5194/amt-8-4243-2015, https://doi.org/10.5194/amt-8-4243-2015, 2015
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This paper describes and presents results from a intercomparison, in an environment rich in NOx (i.e., NO+NO2), of two OH reactivity instruments: one based on the comparative reactivity method, and one based on the pump-probe method. Co-located measurements were made of both ambient air and standard mixtures. Ambient OH reactivity values measured by both instruments were found to be in good agreement for ambient NOx mixing ratios as high as 100 ppbv.
M. J. Newland, A. R. Rickard, L. Vereecken, A. Muñoz, M. Ródenas, and W. J. Bloss
Atmos. Chem. Phys., 15, 9521–9536, https://doi.org/10.5194/acp-15-9521-2015, https://doi.org/10.5194/acp-15-9521-2015, 2015
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Stabilised Criegee intermediates (SCIs) are formed through alkene-ozone reactions, which occur throughout the atmospheric boundary layer. Recent direct laboratory studies have shown that SCI react rapidly with SO2, NO2 and other trace gases, affecting air quality and climate. We present experimental data from the EUPHORE atmospheric simulation chamber, in which we determine the effects of the ozonolysis of isoprene, on the oxidation of SO2 as a function of H2O and dimethyl sulfide concentration.
Related subject area
Subject: Gases | Research Activity: Laboratory Studies | Altitude Range: Troposphere | Science Focus: Chemistry (chemical composition and reactions)
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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
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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
Xi Cheng, Yong Jie Li, Yan Zheng, Keren Liao, Theodore K. Koenig, Yanli Ge, Tong Zhu, Chunxiang Ye, Xinghua Qiu, and Qi Chen
Atmos. Chem. Phys., 24, 2099–2112, https://doi.org/10.5194/acp-24-2099-2024, https://doi.org/10.5194/acp-24-2099-2024, 2024
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In this study we conducted laboratory measurements to investigate the formation of gas-phase oxygenated organic molecules (OOMs) from six aromatic volatile organic compounds (VOCs). We provide a thorough analysis on the effects of precursor structure (substituents and ring numbers) on product distribution and highlight from a laboratory perspective that heavy (e.g., double-ring) aromatic VOCs are important in initial particle growth during secondary organic aerosol formation.
Yiwei Gong, Feng Jiang, Yanxia Li, Thomas Leisner, and Harald Saathoff
Atmos. Chem. Phys., 24, 167–184, https://doi.org/10.5194/acp-24-167-2024, https://doi.org/10.5194/acp-24-167-2024, 2024
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This study investigates the role of the important atmospheric reactive intermediates in the formation of dimers and aerosol in monoterpene ozonolysis at different temperatures. Through conducting a series of chamber experiments and utilizing chemical kinetic and aerosol dynamic models, the SOA formation processes are better described, especially for colder regions. The results can be used to improve the chemical mechanism modeling of monoterpenes and SOA parameterization in transport models.
María Asensio, Sergio Blázquez, María Antiñolo, José Albaladejo, and Elena Jiménez
Atmos. Chem. Phys., 23, 14115–14126, https://doi.org/10.5194/acp-23-14115-2023, https://doi.org/10.5194/acp-23-14115-2023, 2023
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In this work, we focus on the atmospheric chemistry and consequences for air quality of 2-methylpentanal (2MP), which is widely used as a flavoring ingredient and as an intermediate in the synthesis of dyes, resins, and pharmaceuticals. Measurements are presented on how fast 2MP is degraded by sunlight and oxidants like hydroxyl (OH) radicals and chlorine (Cl) atoms and what products are generated. We conclude that 2MP will be degraded in a few hours, affecting local air quality.
Lucy V. Brown, Ryan J. Pound, Lyndsay S. Ives, Matthew R. Jones, Stephen J. Andrews, and Lucy J. Carpenter
EGUsphere, https://doi.org/10.5194/egusphere-2023-2660, https://doi.org/10.5194/egusphere-2023-2660, 2023
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Ozone is deposited from the lower atmosphere to the surface of the ocean, however the chemical reactions which drive this deposition are not currently well understood. Of particular importance is the reaction between ozone and iodide, and this work measured the kinetics of this reaction, as well as its temperature dependence, which we found to be negligible. We then investigated the subsequent emissions of iodine-containing species from the surface ocean, which can further impact ozone.
Andrew T. Lambe, Bin Bai, Masayuki Takeuchi, Nicole Orwat, Paul M. Zimmerman, Mitchell W. Alton, Nga L. Ng, Andrew Freedman, Megan S. Claflin, Drew R. Gentner, Douglas R. Worsnop, and Pengfei Liu
Atmos. Chem. Phys., 23, 13869–13882, https://doi.org/10.5194/acp-23-13869-2023, https://doi.org/10.5194/acp-23-13869-2023, 2023
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We developed a new method to generate nitrate radicals (NO3) for atmospheric chemistry applications that works by irradiating mixtures containing ceric ammonium nitrate with a UV light at room temperature. It has several advantages over traditional NO3 sources. We characterized its performance over a range of mixture and reactor conditions as well as other irradiation products. Proof of concept was demonstrated by generating and characterizing oxidation products of the β-pinene + NO3 reaction.
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 Mentel
EGUsphere, https://doi.org/10.5194/egusphere-2023-2402, https://doi.org/10.5194/egusphere-2023-2402, 2023
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Highly oxygenated organic molecules are important contributors to secondary organic aerosol. Their yield depends on detailed atmospheric chemical composition. One important parameter is the ratio of hydroperoxy radicals to organic peroxy radicals (HO2/RO2) and we show that higher HO2/RO2 ratios lower the secondary organic aerosol yield. This of importance as laboratory studies are often biased towards organic peroxy radicals.
Han Zang, Dandan Huang, Jiali Zhong, Ziyue Li, Chenxi Li, Huayun Xiao, and Yue Zhao
Atmos. Chem. Phys., 23, 12691–12705, https://doi.org/10.5194/acp-23-12691-2023, https://doi.org/10.5194/acp-23-12691-2023, 2023
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Acylperoxy radicals (RO2) are key intermediates in the atmospheric oxidation of organic compounds, yet our knowledge of their identities and chemistry remains poor. Using direct measurements and kinetic modeling, we identify the composition and formation pathways of acyl RO2 and quantify their contribution to highly oxygenated organic molecules during α-pinene ozonolysis, which will help to understand oxidation chemistry of monoterpenes and sources of low-volatility organics in the atmosphere.
Jacky Y. S. Pang, Florian Berg, Anna Novelli, Birger Bohn, Michelle Färber, Philip T. M. Carlsson, René Dubus, Georgios I. Gkatzelis, Franz Rohrer, Sergej Wedel, Andreas Wahner, and Hendrik Fuchs
Atmos. Chem. Phys., 23, 12631–12649, https://doi.org/10.5194/acp-23-12631-2023, https://doi.org/10.5194/acp-23-12631-2023, 2023
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In this study, the oxidations of sabinene by OH radicals and ozone were investigated with an atmospheric simulation chamber. Reaction rate coefficients of the OH-oxidation reaction at temperatures between 284 to 340 K were determined for the first time in the laboratory by measuring the OH reactivity. Product yields determined in chamber experiments had good agreement with literature values, but discrepancies were found between experimental yields and expected yields from oxidation mechanisms.
Lorrie Jacob, Chiara Giorio, and Alexander Thomas Archibald
EGUsphere, https://doi.org/10.5194/egusphere-2023-2223, https://doi.org/10.5194/egusphere-2023-2223, 2023
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Recent studies on DMS have provided new challenges to our mechanistic understanding. Here we synthesise a number of recent studies to further develop and extend a state-of-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 understanding the climate impacts of DMS emissions in past, present and future atmospheric conditions.
Rolf Sander
Atmos. Chem. Phys., 23, 10901–12440, https://doi.org/10.5194/acp-23-10901-2023, https://doi.org/10.5194/acp-23-10901-2023, 2023
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According to Henry's law, the equilibrium ratio between the abundances in the gas phase and in the aqueous phase is constant for a dilute solution. Henry’s law constants of trace gases of potential importance in environmental chemistry have been collected and converted into a uniform format. The compilation contains 46 434 values of Henry's law constants for 10 173 species, collected from 995 references. It is also available on the internet at https://www.henrys-law.org.
Marc von Hobe, Domenico Taraborrelli, Sascha Alber, Birger Bohn, Hans-Peter Dorn, Hendrik Fuchs, Yun Li, Chenxi Qiu, Franz Rohrer, Roberto Sommariva, Fred Stroh, Zhaofeng Tan, Sergej Wedel, and Anna Novelli
Atmos. Chem. Phys., 23, 10609–10623, https://doi.org/10.5194/acp-23-10609-2023, https://doi.org/10.5194/acp-23-10609-2023, 2023
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The trace gas carbonyl sulfide (OCS) transports sulfur from the troposphere to the stratosphere, where sulfate aerosols are formed that influence climate and stratospheric chemistry. An uncertain OCS source in the troposphere is chemical production form dimethyl sulfide (DMS), a gas released in large quantities from the oceans. We carried out experiments in a large atmospheric simulation chamber to further elucidate the chemical mechanism of OCS production from DMS.
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
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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.
Jiangyi Zhang, Jian Zhao, Yuanyuan Luo, Valter Mickwitz, Douglas Worsnop, and Mikael Ehn
EGUsphere, https://doi.org/10.5194/egusphere-2023-1959, https://doi.org/10.5194/egusphere-2023-1959, 2023
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Due to the intrinsic connection between the formation pathways of O3 and HOM, 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 HOM, the HOM-based indicating ratios can describe the O3 formation in real time. Despite the success of our approach in this simple laboratory system, the applicability to the much more complex atmosphere remains to be determined.
Yixin Hao, Jun Zhou, Jie-Ping Zhou, Yan Wang, Suxia Yang, Yibo Huangfu, Xiao-Bing Li, Chunsheng Zhang, Aiming Liu, Yanfeng Wu, Yaqing Zhou, Shuchun Yang, Yuwen Peng, Jipeng Qi, Xianjun He, Xin Song, Yubin Chen, Bin Yuan, and Min Shao
Atmos. Chem. Phys., 23, 9891–9910, https://doi.org/10.5194/acp-23-9891-2023, https://doi.org/10.5194/acp-23-9891-2023, 2023
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By employing an improved net photochemical ozone production rate (NPOPR) detection system based on the dual-channel reaction chamber technique, we measured the net photochemical ozone production rate in the Pearl River Delta in China. The photochemical ozone formation mechanisms in the reaction and reference chambers were investigated using the observation-data-constrained box model, which helped us to validate the NPOPR detection system and understand photochemical ozone formation mechanism.
Kevin J. Nihill, Matthew M. Coggon, Christopher Y. Lim, Abigail R. Koss, Bin Yuan, Jordan E. Krechmer, Kanako Sekimoto, Jose L. Jimenez, Joost de Gouw, Christopher D. Cappa, Colette L. Heald, Carsten Warneke, and Jesse H. Kroll
Atmos. Chem. Phys., 23, 7887–7899, https://doi.org/10.5194/acp-23-7887-2023, https://doi.org/10.5194/acp-23-7887-2023, 2023
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In this work, we collect emissions from controlled burns of biomass fuels that can be found in the western United States into an environmental chamber in order to simulate their oxidation as they pass through the atmosphere. These findings provide a detailed characterization of the composition of the atmosphere downwind of wildfires. In turn, this will help to explore the effects of these changing emissions on downwind populations and will also directly inform atmospheric and climate models.
Caterina Mapelli, James K. Donnelly, Úna E. Hogan, Andrew R. Rickard, Abbie T. Robinson, Fergal Byrne, Con Rob McElroy, Basile F. E. Curchod, Daniel Hollas, and Terry J. Dillon
Atmos. Chem. Phys., 23, 7767–7779, https://doi.org/10.5194/acp-23-7767-2023, https://doi.org/10.5194/acp-23-7767-2023, 2023
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Solvents are chemical compounds with countless uses in the chemical industry, and they also represent one of the main sources of pollution in the chemical sector. Scientists are trying to develop new
greensafer solvents which present favourable advantages when compared to traditional solvents. Since the assessment of these green solvents often lacks air quality considerations, this study aims to understand the behaviour of these compounds, investigating their reactivity in the troposphere.
Roland Benoit, Nesrine Belhadj, Zahraa Dbouk, Maxence Lailliau, and Philippe Dagaut
Atmos. Chem. Phys., 23, 5715–5733, https://doi.org/10.5194/acp-23-5715-2023, https://doi.org/10.5194/acp-23-5715-2023, 2023
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We observed a surprisingly similar set of oxidation product chemical formulas from limonene and α-pinene, including oligomers, formed under cool-flame (present experiments) and simulated atmospheric oxidation (literature). Data analysis indicated that a subset of chemical formulas is common to all experiments independently of experimental conditions. Also, this study indicates that many detected chemical formulas can be ascribed to an autooxidation reaction.
Melissa Meder, Otso Peräkylä, Jonathan G. Varelas, Jingyi Luo, Runlong Cai, Yanjun Zhang, Theo Kurtén, Matthieu Riva, Matti Rissanen, Franz M. Geiger, Regan J. Thomson, and Mikael Ehn
Atmos. Chem. Phys., 23, 4373–4390, https://doi.org/10.5194/acp-23-4373-2023, https://doi.org/10.5194/acp-23-4373-2023, 2023
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We discuss and show the viability of a method where multiple isotopically labelled precursors are used for probing the formation pathways of highly oxygenated organic molecules (HOMs) from the oxidation of the monoterpene a-pinene. HOMs are very important for secondary organic aerosol (SOA) formation in forested regions, and monoterpenes are the single largest source of SOA globally. The fast reactions forming HOMs have thus far remained elusive despite considerable efforts over the last decade.
Philip T. M. Carlsson, Luc Vereecken, Anna Novelli, François Bernard, Steven S. Brown, Bellamy Brownwood, Changmin Cho, John N. Crowley, Patrick Dewald, Peter M. Edwards, Nils Friedrich, Juliane L. Fry, Mattias Hallquist, Luisa Hantschke, Thorsten Hohaus, Sungah Kang, Jonathan Liebmann, Alfred W. Mayhew, Thomas Mentel, David Reimer, Franz Rohrer, Justin Shenolikar, Ralf Tillmann, Epameinondas Tsiligiannis, Rongrong Wu, Andreas Wahner, Astrid Kiendler-Scharr, and Hendrik Fuchs
Atmos. Chem. Phys., 23, 3147–3180, https://doi.org/10.5194/acp-23-3147-2023, https://doi.org/10.5194/acp-23-3147-2023, 2023
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The investigation of the night-time oxidation of the most abundant hydrocarbon, isoprene, in chamber experiments shows the importance of reaction pathways leading to epoxy products, which could enhance particle formation, that have so far not been accounted for. The chemical lifetime of organic nitrates from isoprene is long enough for the majority to be further oxidized the next day by daytime oxidants.
Kevin D. Easterbrook, Mitchell A. Vona, Kiana Nayebi-Astaneh, Amanda M. Miller, and Hans D. Osthoff
Atmos. Chem. Phys., 23, 311–322, https://doi.org/10.5194/acp-23-311-2023, https://doi.org/10.5194/acp-23-311-2023, 2023
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The trace gas peroxypropionyl nitrate (PPN) is generated in photochemical smog, phytotoxic, a strong eye irritant, and possibly mutagenic. Here, its solubility and reactivity in water and in octanol were investigated using a bubble flow apparatus, yielding its Henry's law constant and octanol–water partition coefficient (Kow). The results allow the fate of PPN to be more accurately constrained in atmospheric chemical transport models, including its uptake on clouds, organic aerosol, and leaves.
Qing Ye, Matthew B. Goss, Jordan E. Krechmer, Francesca Majluf, Alexander Zaytsev, Yaowei Li, Joseph R. Roscioli, Manjula Canagaratna, Frank N. Keutsch, Colette L. Heald, and Jesse H. Kroll
Atmos. Chem. Phys., 22, 16003–16015, https://doi.org/10.5194/acp-22-16003-2022, https://doi.org/10.5194/acp-22-16003-2022, 2022
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The atmospheric oxidation of dimethyl sulfide (DMS) is a major natural source of sulfate particles in the atmosphere. However, its mechanism is poorly constrained. In our work, laboratory measurements and mechanistic modeling were conducted to comprehensively investigate DMS oxidation products and key reaction rates. We find that the peroxy radical (RO2) has a controlling effect on product distribution and aerosol yield, with the isomerization of RO2 leading to the suppression of aerosol yield.
Caterina Mapelli, Juliette V. Schleicher, Alex Hawtin, Conor D. Rankine, Fiona C. Whiting, Fergal Byrne, C. Rob McElroy, Claudiu Roman, Cecilia Arsene, Romeo I. Olariu, Iustinian G. Bejan, and Terry J. Dillon
Atmos. Chem. Phys., 22, 14589–14602, https://doi.org/10.5194/acp-22-14589-2022, https://doi.org/10.5194/acp-22-14589-2022, 2022
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Solvents represent an important source of pollution from the chemical industry. New "green" solvents aim to replace toxic solvents with new molecules made from renewable sources and designed to be less harmful. Whilst these new molecules are selected according to toxicity and other characteristics, no consideration has yet been included on air quality. Studying the solvent breakdown in air, we found that TMO has a lower impact on air quality than traditional solvents with similar properties.
Kai Song, Song Guo, Yuanzheng Gong, Daqi Lv, Yuan Zhang, Zichao Wan, Tianyu Li, Wenfei Zhu, Hui Wang, Ying Yu, Rui Tan, Ruizhe Shen, Sihua Lu, Shuangde Li, Yunfa Chen, and Min Hu
Atmos. Chem. Phys., 22, 9827–9841, https://doi.org/10.5194/acp-22-9827-2022, https://doi.org/10.5194/acp-22-9827-2022, 2022
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Emissions from four typical Chinese domestic cooking and fried chicken using four kinds of oils were investigated to illustrate the impact of cooking style and oil. Of the estimated SOA, 10.2 %–32.0 % could be explained by S/IVOC oxidation. Multiway principal component analysis (MPCA) emphasizes the importance of the unsaturated fatty acid-alkadienal volatile product mechanism (oil autoxidation) accelerated by the cooking and heating procedure.
Michelia Dam, Danielle C. Draper, Andrey Marsavin, Juliane L. Fry, and James N. Smith
Atmos. Chem. Phys., 22, 9017–9031, https://doi.org/10.5194/acp-22-9017-2022, https://doi.org/10.5194/acp-22-9017-2022, 2022
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We performed chamber experiments to measure the composition of the gas-phase reaction products of nitrate-radical-initiated oxidation of four monoterpenes. The total organic yield, effective oxygen-to-carbon ratio, and dimer-to-monomer ratio were correlated with the observed particle formation for the monoterpene systems with some exceptions. The Δ-carene system produced the most particles, followed by β-pinene, with the α-pinene and α-thujene systems producing no particles.
Jacky Yat Sing Pang, Anna Novelli, Martin Kaminski, Ismail-Hakki Acir, Birger Bohn, Philip T. M. Carlsson, Changmin Cho, Hans-Peter Dorn, Andreas Hofzumahaus, Xin Li, Anna Lutz, Sascha Nehr, David Reimer, Franz Rohrer, Ralf Tillmann, Robert Wegener, Astrid Kiendler-Scharr, Andreas Wahner, and Hendrik Fuchs
Atmos. Chem. Phys., 22, 8497–8527, https://doi.org/10.5194/acp-22-8497-2022, https://doi.org/10.5194/acp-22-8497-2022, 2022
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This study investigates the radical chemical budget during the limonene oxidation at different atmospheric-relevant NO concentrations in chamber experiments under atmospheric conditions. It is found that the model–measurement discrepancies of HO2 and RO2 are very large at low NO concentrations that are typical for forested environments. Possible additional processes impacting HO2 and RO2 concentrations are discussed.
Carmen Maria Tovar, Ian Barnes, Iustinian Gabriel Bejan, and Peter Wiesen
Atmos. Chem. Phys., 22, 6989–7004, https://doi.org/10.5194/acp-22-6989-2022, https://doi.org/10.5194/acp-22-6989-2022, 2022
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This work explores the kinetics and reactivity of epoxides towards the OH radical using two different simulation chambers. Estimation of the rate coefficients has also been made using different structure–activity relationship (SAR) approaches. The results indicate a direct influence of the structural and geometric properties of the epoxides not considered in SAR estimations, influencing the reactivity of these compounds. The outcomes of this work are in very good agreement with previous studies.
Axel Fouqueau, Manuela Cirtog, Mathieu Cazaunau, Edouard Pangui, Jean-François Doussin, and Bénédicte Picquet-Varrault
Atmos. Chem. Phys., 22, 6411–6434, https://doi.org/10.5194/acp-22-6411-2022, https://doi.org/10.5194/acp-22-6411-2022, 2022
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Biogenic volatile organic compounds are intensely emitted by forests and crops and react with the nitrate radical during the nighttime to form functionalized products. The purpose of this study is to furnish kinetic and mechanistic data for terpinolene and β-caryophyllene, using simulation chamber experiments. Rate constants have been measured using both relative and absolute methods, and mechanistic studies have been conducted in order to identify and quantify the main reaction products.
Yuanyuan Luo, Olga Garmash, Haiyan Li, Frans Graeffe, Arnaud P. Praplan, Anssi Liikanen, Yanjun Zhang, Melissa Meder, Otso Peräkylä, Josep Peñuelas, Ana María Yáñez-Serrano, and Mikael Ehn
Atmos. Chem. Phys., 22, 5619–5637, https://doi.org/10.5194/acp-22-5619-2022, https://doi.org/10.5194/acp-22-5619-2022, 2022
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Diterpenes were only recently observed in the atmosphere, and little is known of their atmospheric fates. We explored the ozonolysis of the diterpene kaurene in a chamber, and we characterized the oxidation products for the first time using chemical ionization mass spectrometry. Our findings highlight similarities and differences between diterpenes and smaller terpenes during their atmospheric oxidation.
Wenyu Sun, Matias Berasategui, Andrea Pozzer, Jos Lelieveld, and John N. Crowley
Atmos. Chem. Phys., 22, 4969–4984, https://doi.org/10.5194/acp-22-4969-2022, https://doi.org/10.5194/acp-22-4969-2022, 2022
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The reaction between OH and SO2 is a termolecular process that in the atmosphere results in the formation of H2SO4 and thus aerosols. We present the first temperature- and pressure-dependent measurements of the rate coefficients in N2. This is also the first study to examine the effects of water vapour on the kinetics of this reaction. Our results indicate the rate coefficient is larger than that recommended by evaluation panels, with deviations of up to 30 % in some parts of the atmosphere.
Haoyu Jiang, Yingyao He, Yiqun Wang, Sheng Li, Bin Jiang, Luca Carena, Xue Li, Lihua Yang, Tiangang Luan, Davide Vione, and Sasho Gligorovski
Atmos. Chem. Phys., 22, 4237–4252, https://doi.org/10.5194/acp-22-4237-2022, https://doi.org/10.5194/acp-22-4237-2022, 2022
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Heterogeneous oxidation of SO2 is suggested to be one of the most important pathways for sulfate formation during extreme haze events in China, yet the exact mechanism remains highly uncertain. Our study reveals that ubiquitous compounds at the sea surface PAHS and DMSO, when exposed to SO2 under simulated sunlight irradiation, generate abundant organic sulfur compounds, providing implications for air-sea interaction and secondary organic aerosols formation processes.
Roland Vernooij, Ulrike Dusek, Maria Elena Popa, Peng Yao, Anupam Shaikat, Chenxi Qiu, Patrik Winiger, Carina van der Veen, Thomas Callum Eames, Natasha Ribeiro, and Guido R. van der Werf
Atmos. Chem. Phys., 22, 2871–2890, https://doi.org/10.5194/acp-22-2871-2022, https://doi.org/10.5194/acp-22-2871-2022, 2022
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Landscape fires are a major source of greenhouse gases and aerosols, particularly in sub-tropical savannas. Stable carbon isotopes in emissions can be used to trace the contribution of C3 plants (e.g. trees or shrubs) and C4 plants (e.g. savanna grasses) to greenhouse gases and aerosols if the process is well understood. This helps us to link individual vegetation types to emissions, identify biomass burning emissions in the atmosphere, and improve the reconstruction of historic fire regimes.
María Asensio, María Antiñolo, Sergio Blázquez, José Albaladejo, and Elena Jiménez
Atmos. Chem. Phys., 22, 2689–2701, https://doi.org/10.5194/acp-22-2689-2022, https://doi.org/10.5194/acp-22-2689-2022, 2022
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The diurnal atmospheric degradation of 2-methylbutanal, 2 MB, emitted by sources like vegetation or the poultry industry is evaluated in this work. Sunlight and oxidants like hydroxyl (OH) radicals and chlorine (Cl) atoms initiate this degradation. Measurements of how fast 2 MB is degraded and what products are generated are presented. The lifetime of 2 MB is around 1 h at noon, when the OH reaction dominates. Thus, 2 MB will not be transported far, affecting only local air quality.
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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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A significant fraction of emissions from human activity consists of aromatic hydrocarbons, e.g. benzene, which oxidise to form new compounds important for particle growth. Characterisation of benzene oxidation products highlights the range of species produced as well as their chemical properties and contextualises them within relevant frameworks, e.g. MCM. Cluster analysis of the oxidation product time series distinguishes behaviours of CHON compounds that could aid in identifying functionality.
Cited articles
Andreae, M. O., and Crutzen, P. J.: Atmospheric aerosols: biogeochemical
sources and role in atmospheric chemistry, Science, 276, 1052–1058,
https://doi.org/10.1126/science.276.5315.1052, 1997.
Atkinson, R. and Aschmann, S. M.: Hydroxyl radical production from the
gas-phase reactions of ozone with a series of alkenes under atmospheric
conditions, Environ. Sci. Technol., 27, 1357–1363, https://doi.org/10.1021/es00044a010, 1993.
Atkinson, R., Baulch, D. L., Cox, R. A., Crowley, J. N., Hampson, R. F., Hynes, R. G., Jenkin, M. E., Rossi, M. J., and Troe, J.: Evaluated kinetic and photochemical data for atmospheric chemistry: Volume I – gas phase reactions of Ox, HOx, NOx and SOx species, Atmos. Chem. Phys., 4, 1461–1738, https://doi.org/10.5194/acp-4-1461-2004, 2004.
Atkinson, R., Baulch, D. L., Cox, R. A., Crowley, J. N., Hampson, R. F., Hynes, R. G., Jenkin, M. E., Rossi, M. J., Troe, J., and Wallington, T. J.: Evaluated kinetic and photochemical data for atmospheric chemistry: Volume IV – gas phase reactions of organic halogen species, Atmos. Chem. Phys., 8, 4141–4496, https://doi.org/10.5194/acp-8-4141-2008, 2008.
Bain, M., Hansen, C. S., and Ashfold, M. N. R.: Communication: Multi-mass
velocity map imaging study of the ultraviolet photodissociation of dimethyl
sulfide using single photon ionization and a PImMS2 sensor, J. Chem. Phys.,
149, 081103, https://doi.org/10.1063/1.5048838, 2018.
Barber, V. P., Pandit, S., Green, A. M., Trongsiriwat, N., Walsh, P. J.,
Klippenstein, S. J., and Lester, M. I.: Four-Carbon Criegee Intermediate
from Isoprene Ozonolysis: Methyl Vinyl Ketone Oxide Synthesis, Infrared
Spectrum, and OH Production, J. Am. Chem. Soc., 140, 10866–10880,
https://doi.org/10.1021/jacs.8b06010, 2018.
Beames, J. M., Liu, F., Lu, L., and Lester, M. I.: UV spectroscopic
characterization of an alkyl substituted Criegee intermediate CH3CHOO,
J. Chem. Phys., 138, 244307, https://doi.org/10.1063/1.4810865,
2013.
Bell, R. D. and Wilson, A. K.: SO3 revisited: Impact of tight d augmented
correlation consistent basis sets on atomization energy and structure,
Chem. Phys. Lett., 394, 105–109, https://doi.org/10.1016/j.cplett.2004.06.127, 2004.
Bonn, B., Bourtsoukidis, E., Sun, T. S., Bingemer, H., Rondo, L., Javed, U., Li, J., Axinte, R., Li, X., Brauers, T., Sonderfeld, H., Koppmann, R., Sogachev, A., Jacobi, S., and Spracklen, D. V.: The link between atmospheric radicals and newly formed particles at a spruce forest site in Germany, Atmos. Chem. Phys., 14, 10823–10843, https://doi.org/10.5194/acp-14-10823-2014, 2014.
Boy, M., Mogensen, D., Smolander, S., Zhou, L., Nieminen, T., Paasonen, P., Plass-Dülmer, C., Sipilä, M., Petäjä, T., Mauldin, L., Berresheim, H., and Kulmala, M.: Oxidation of SO2 by stabilized Criegee intermediate (sCI) radicals as a crucial source for atmospheric sulfuric acid concentrations, Atmos. Chem. Phys., 13, 3865–3879, https://doi.org/10.5194/acp-13-3865-2013, 2013.
Caravan, R. L., Vansco, M. F., Au, K., Khan, M. A. H., Li, Y.-L., Winiberg,
F. A. F., Zuraski, K., Lin, Y.-H., Chao, W., Trongsiriwat, N., Walsh, P. J.,
Osborn, D. L., Percival, C. J., Lin, J. J.-M., Shallcross, D. E., Sheps, L.,
Klippenstein, S. J., Taatjes, C. A., and Lester, M. I.: Direct kinetic
measurements and theoretical predictions of an isoprene-derived Criegee
intermediate, P. Natl. Acad. Sci. USA, 117, 9733–9740,
https://doi.org/10.1073/pnas.1916711117, 2020.
Chang, Y.-P., Chang, C.-H., Takahashi, K., and Lin, J. J.-M.: Absolute UV
absorption cross sections of dimethyl substituted Criegee intermediate
(CH3)2COO, Chem. Phys. Lett., 653, 155–160, https://doi.org/10.1016/j.cplett.2016.04.082, 2016.
Chao, W., Hsieh, J.-T., Chang, C.-H., and Lin, J. J.-M.: Direct kinetic
measurement of the reaction of the simplest Criegee intermediate with water
vapor, Science, 347, 751–754, https://doi.org/10.1126/science.1261549, 2015.
Chao, W., Lin, Y.-H., Yin, C., Lin, W.-H., Takahashi, K., and Lin, J. J.-M.:
Temperature and isotope effects in the reaction of CH3CHOO with
methanol, Phys. Chem. Chem. Phys., 21, 13633–13640, https://doi.org/10.1039/C9CP02534K, 2019.
Charlson, R. J., Lovelock, J. E., Andreae, M. O., and Warren, S. G.: Oceanic
phytoplankton, atmospheric sulphur, cloud albedo and climate, Nature, 328,
655–661, https://doi.org/10.1038/326655a0, 1987.
Chhantyal-Pun, R., Davey, A., Shallcross, D. E., Percival, C. J., and
Orr-Ewing, A. J.: A kinetic study of the CH2OO Criegee intermediate
self-reaction, reaction with SO2 and unimolecular reaction using cavity
ring-down spectroscopy, Phys. Chem. Chem. Phys., 17, 3617–3626,
https://doi.org/10.1039/c4cp04198d, 2015.
Chhantyal-Pun, R., Shannon, R. J., Tew, D. P., Caravan, R. L., Duchi, M.,
Wong, C., Ingham, A., Feldman, C., McGillen, M. R., Khan, M. A. H., Antonov,
I. O., Rotavera, B., Ramasesha, K., Osborn, D. L., Taatjes, C. A., Percival,
C. J., Shallcross, D. E., and Orr-Ewing, A. J.: Experimental and
computational studies of Criegee intermediate reactions with NH3 and
CH3NH2, Phys. Chem. Chem. Phys., 21, 14042–14052, https://doi.org/10.1039/C8CP06810K, 2019.
Cox, R. A., Ammann, M., Crowley, J. N., Herrmann, H., Jenkin, M. E., McNeill, V. F., Mellouki, A., Troe, J., and Wallington, T. J.: Evaluated kinetic and photochemical data for atmospheric chemistry: Volume VII – Criegee intermediates, Atmos. Chem. Phys. Discuss., https://doi.org/10.5194/acp-2020-472, in review, 2020.
Decker, Z. C. J., Au, K., Vereecken, L., and Sheps, L.: Direct experimental
probing and theoretical analysis of the reaction between the simplest
Criegee intermediate CH2OO and isoprene, Phys. Chem. Chem. Phys., 19,
8541–8551, https://doi.org/10.1039/C6CP08602K, 2017.
Dunning, T. H.: Gaussian basis sets for use in correlated molecular
calculations. I. The atoms boron through neon and hydrogen, J. Chem. Phys.,
90, 1007–1023, 10.1063/1.456153, 1989.
Dunning, T. H., Peterson, K. A., and Wilson, A. K.: Gaussian basis sets for
use in correlated molecular calculations. X. The atoms aluminum through
argon revisited, J. Chem. Phys., 114, 9244–9253, 10.1063/1.1367373, 2001.
Eskola, A. J., Wojcik-Pastuszka, D., Ratajczak, E., and Timonen, R. S.:
Kinetics of the reactions of CH2Br and CH2I radicals with
molecular oxygen at atmospheric temperatures, Phys. Chem. Chem. Phys., 8,
1416–1424, https://doi.org/10.1039/B516291B, 2006.
Faloona, I.: Sulfur processing in the marine atmospheric boundary layer: A
review and critical assessment of modeling uncertainties, Atmos. Environ.,
43, 2841–2854, https://doi.org/10.1016/j.atmosenv.2009.02.043,
2009.
Foreman, E. S., Kapnas, K. M., and Murray, C.: Reactions between Criegee
intermediates and the inorganic acids HCl and HNO3: kinetics and
atmospheric implications, Angew. Chem. Int. Edit., 55, 10419–10422,
https://doi.org/10.1002/anie.201604662, 2016.
Gutbrod, R., Kraka, E., Schindler, R. N., and Cremer, D.: Kinetic and
theoretical investigation of the gas-phase ozonolysis of isoprene:? carbonyl
oxides as an important source for OH radicals in the atmosphere, J. Am.
Chem. Soc., 119, 7330–7342, https://doi.org/10.1021/ja970050c,
1997.
Hatakeyama, S. and Akimoto, H.: Reactions of criegee intermediates in the
gas phase, Res. Chem. Intermediat., 20, 503–524, https://doi.org/10.1163/156856794X00432, 1994.
Huang, H.-L., Chao, W., and Lin, J. J.-M.: Kinetics of a Criegee
intermediate that would survive high humidity and may oxidize atmospheric
SO2, P. Natl. Acad. Sci. USA, 112, 10857–10862, https://doi.org/10.1073/pnas.1513149112 2015.
Jardine, K., Yañez-Serrano, A. M., Williams, J., Kunert, N., Jardine,
A., Taylor, T., Abrell, L., Artaxo, P., Guenther, A., Hewitt, C. N., House,
E., Florentino, A. P., Manzi, A., Higuchi, N., Kesselmeier, J., Behrendt,
T., Veres, P. R., Derstroff, B., Fuentes, J. D., Martin, S. T., and Andreae,
M. O.: Dimethyl sulfide in the Amazon rain forest, Global Biogeochem.
Cy., 29, 19–32, https://doi.org/10.1002/2014GB004969, 2015.
Johnson, D., Lewin, A. G., and Marston, G.: The Effect of
Criegee-Intermediate Scavengers on the OH Yield from the Reaction of Ozone
with 2-methylbut-2-ene, J. Phys. Chem. A, 105, 2933–2935, https://doi.org/10.1021/jp003975e,
2001.
Johnson, D. and Marston, G.: The gas-phase ozonolysis of unsaturated
volatile organic compounds in the troposphere, Chem. Soc. Rev., 37, 699–716,
https://doi.org/10.1039/B704260B, 2008.
Khan, M. A. H., Percival, C. J., Caravan, R. L., Taatjes, C. A., and
Shallcross, D. E.: Criegee intermediates and their impacts on the
troposphere, Environmental Science: Processes & Impacts, 20, 437–453,
https://doi.org/10.1039/C7EM00585G, 2018.
Kim, S., Guenther, A., Lefer, B., Flynn, J., Griffin, R., Rutter, A. P.,
Gong, L., and Cevik, B. K.: Potential role of stabilized Criegee radicals in
sulfuric acid production in a high biogenic VOC environment, Environ. Sci.
Technol., 49, 3383–3391, https://doi.org/10.1021/es505793t,
2015.
Lee, Y. P.: Perspective: Spectroscopy and kinetics of small gaseous Criegee
intermediates, J. Chem. Phys., 143, 020901, https://doi.org/10.1063/1.4923165, 2015.
Lewis, T. R., Blitz, M. A., Heard, D. E., and Seakins, P. W.: Direct
evidence for a substantive reaction between the Criegee intermediate,
CH2OO, and the water vapour dimer, Phys. Chem. Chem. Phys., 17,
4859-4863, https://doi.org/10.1039/C4CP04750H, 2015.
Li, Y.-L., Lin, Y.-H., Yin, C., Takahashi, K., Chiang, C.-Y., Chang, Y.-P.,
and Lin, J. J.-M.: Temperature-dependent rate coefficient for the reaction
of CH3SH with the simplest Criegee intermediate, J. Phys. Chem. A, 123,
4096–4103, https://doi.org/10.1021/acs.jpca.8b12553, 2019.
Li, Y.-L., Kuo, M.-T., and Lin, J. J.-M.: Unimolecular decomposition rates
of a methyl-substituted Criegee intermediate syn-CH3CHOO, RSC Advances,
10, 8518–8524, https://doi.org/10.1039/D0RA01406K, 2020.
Limão-Vieira, P., Eden, S., Kendall, P. A., Mason, N. J., and Hoffmann,
S. V.: High resolution VUV photo-absorption cross-section for
dimethylsulphide, (CH3)2S, Chem. Phys. Lett., 366, 343–349,
https://doi.org/10.1016/S0009-2614(02)01651-2, 2002.
Lin, H.-Y., Huang, Y.-H., Wang, X., Bowman, J. M., Nishimura, Y., Witek, H.
A., and Lee, Y.-P.: Infrared identification of the Criegee intermediates
syn- and anti-CH3CHOO, and their distinct conformation-dependent reactivity,
Nat. Commun., 6, 7012, https://doi.org/10.1038/ncomms8012,
2015.
Lin, J. J.-M., and Chao, W.: Structure-dependent reactivity of Criegee
intermediates studied with spectroscopic methods, Chem. Soc. Rev., 46,
7483–7497, https://doi.org/10.1039/C7CS00336F, 2017.
Lin, Y.-H., Takahashi, K., and Lin, J. J.-M.: Reactivity of Criegee
intermediates toward carbon dioxide, J. Phys. Chem. Lett., 9, 184–188,
https://doi.org/10.1021/acs.jpclett.7b03154, 2018.
Lin, Y.-H., Li, Y.-L., Chao, W., Takahashi, K., and Lin, J. J.-M.: The role
of the iodine-atom adduct in the synthesis and kinetics of methyl vinyl
ketone oxide – a resonance-stabilized Criegee intermediate, Phys. Chem.
Chem. Phys., 22, 13603–13612, https://doi.org/10.1039/D0CP02085K, 2020.
Liu, F., Beames, J. M., Green, A. M., and Lester, M. I.: UV spectroscopic
characterization of dimethyl- and ethyl-substituted carbonyl oxides, J.
Phys. Chem. A, 118, 2298–2306, https://doi.org/10.1021/jp412726z, 2014a.
Liu, F., Beames, J. M., Petit, A. S., McCoy, A. B., and Lester, M. I.:
Infrared-driven unimolecular reaction of CH3CHOO Criegee intermediates
to OH radical products, Science, 345, 1596–1598, https://doi.org/10.1126/science.1257158,
2014b.
Liu, Y., Bayes, K. D., and Sander, S. P.: Measuring Rate Constants for
Reactions of the Simplest Criegee Intermediate (CH2OO) by Monitoring
the OH Radical, J. Phys. Chem. A, 118, 741–747, 10.1021/jp407058b, 2014c.
McCarthy, M. C., Cheng, L., Crabtree, K. N., Martinez, O., Nguyen, T. L.,
Womack, C. C., and Stanton, J. F.: The simplest Criegee intermediate
(H2C-O–O): isotopic spectroscopy, equilibrium structure, and possible
formation from atmospheric lightning, J. Phys. Chem. Lett., 4, 4133–4139,
https://doi.org/10.1021/jz4023128, 2013.
Meidan, D., Holloway, J. S., Edwards, P. M., Dubé, W. P., Middlebrook,
A. M., Liao, J., Welti, A., Graus, M., Warneke, C., Ryerson, T. B., Pollack,
I. B., Brown, S. S., and Rudich, Y.: Role of Criegee intermediates in
secondary sulfate aerosol formation in nocturnal power plant plumes in the
southeast US, ACS Earth Space Chem., 3, 748–759, https://doi.org/10.1021/acsearthspacechem.8b00215, 2019.
Mir, Z. S., Lewis, T. R., Onel, L., Blitz, M. A., Seakins, P. W., and Stone,
D.: CH2OO Criegee intermediate UV absorption cross-sections and
kinetics of CH2OO + CH2OO and CH2OO + I as a function of
pressure, Phys. Chem. Chem. Phys., 22, 9448–9459, https://doi.org/10.1039/D0CP00988A, 2020.
Nakajima, M., Yue, Q., and Endo, Y.: Fourier-transform microwave
spectroscopy of an alkyl substituted Criegee intermediate
anti-CH3CHOO, J. Mol. Spectrosc., 310, 109–112, https://doi.org/10.1016/j.jms.2014.11.004, 2015.
Newland, M. J., Rickard, A. R., Vereecken, L., Muñoz, A., Ródenas, M., and Bloss, W. J.: Atmospheric isoprene ozonolysis: impacts of stabilised Criegee intermediate reactions with SO2, H2O and dimethyl sulfide, Atmos. Chem. Phys., 15, 9521–9536, https://doi.org/10.5194/acp-15-9521-2015, 2015.
Nguyen, T. B., Tyndall, G. S., Crounse, J. D., Teng, A. P., Bates, K. H.,
Schwantes, R. H., Coggon, M. M., Zhang, L., Feiner, P., Milller, D. O.,
Skog, K. M., Rivera-Rios, J. C., Dorris, M., Olson, K. F., Koss, A., Wild,
R. J., Brown, S. S., Goldstein, A. H., de Gouw, J. A., Brune, W. H.,
Keutsch, F. N., Seinfeld, J. H., and Wennberg, P. O.: Atmospheric fates of
Criegee intermediates in the ozonolysis of isoprene, Phys. Chem. Chem.
Phys., 18, 10241–10254, https://doi.org/10.1039/C6CP00053C,
2016.
Novelli, A., Vereecken, L., Lelieveld, J., and Harder, H.: Direct
observation of OH formation from stabilised Criegee intermediates, Phys.
Chem. Chem. Phys., 16, 19941–19951, 10.1039/C4CP02719A, 2014.
Novelli, A., Hens, K., Tatum Ernest, C., Martinez, M., Nölscher, A. C., Sinha, V., Paasonen, P., Petäjä, T., Sipilä, M., Elste, T., Plass-Dülmer, C., Phillips, G. J., Kubistin, D., Williams, J., Vereecken, L., Lelieveld, J., and Harder, H.: Estimating the atmospheric concentration of Criegee intermediates and their possible interference in a FAGE-LIF instrument, Atmos. Chem. Phys., 17, 7807–7826, https://doi.org/10.5194/acp-17-7807-2017, 2017.
Osborn, D. L. and Taatjes, C. A.: The physical chemistry of Criegee
intermediates in the gas phase, Int. Rev. Phys. Chem., 34, 309–360,
10.1080/0144235x.2015.1055676, 2015.
Percival, C. J., Welz, O., Eskola, A. J., Savee, J. D., Osborn, D. L.,
Topping, D. O., Lowe, D., Utembe, S. R., Bacak, A., M c Figgans, G., Cooke,
M. C., Xiao, P., Archibald, A. T., Jenkin, M. E., Derwent, R. G., Riipinen,
I., Mok, D. W. K., Lee, E. P. F., Dyke, J. M., Taatjes, C. A., and
Shallcross, D. E.: Regional and global impacts of Criegee intermediates on
atmospheric sulphuric acid concentrations and first steps of aerosol
formation, Faraday Discuss., 165, 45–73, https://doi.org/10.1039/C3FD00048F, 2013.
Purvis, G. D., and Bartlett, R. J.: A full coupled-cluster singles and
doubles model: The inclusion of disconnected triples, J. Chem. Phys., 76,
1910–1918, https://doi.org/10.1063/1.443164, 1982.
Sander, S. P., Abbat, J., Barker, J. R., Burkholder, J. B., Friedl, R. R.,
Golden, D. M., Huie, R. E., Kolb, C. E., Kurylo, M. J., Moortgat, G. K.,
Orkin, V. L., and Wine, P. H.: Chemical kinetics and photochemical data for
use in atmospheric studies, Evaluation No. 17, in: hJPL Publication 10-6,
Pasadena, 2011.
Sheps, L.: Absolute ultraviolet absorption spectrum of a Criegee
intermediate CH2OO, J. Phys. Chem. Lett., 4, 4201–4205,
https://doi.org/10.1021/jz402191w, 2013.
Smith, M. C., Ting, W.-L., Chang, C.-H., Takahashi, K., Boering, K. A., and
Lin, J. J.-M.: UV absorption spectrum of the C2 Criegee intermediate
CH3CHOO, J. Chem. Phys., 141, 074302, https://doi.org/10.1063/1.4892582, 2014.
Smith, M. C., Chao, W., Takahashi, K., Boering, K. A., and Lin, J. J.-M.:
Unimolecular decomposition rate of the Criegee intermediate
(CH3)2COO measured directly with UV absorption spectroscopy,
J. Phys. Chem. A, 120, 4789–4798, https://doi.org/10.1021/acs.jpca.5b12124, 2016.
Stephenson, T. A. and Lester, M. I.: Unimolecular decay dynamics of Criegee
intermediates: energy-resolved rates, thermal rates, and their atmospheric
impact, Int. Rev. Phys. Chem., 39, 1–33, https://doi.org/10.1080/0144235X.2020.1688530, 2020.
Stone, D., Blitz, M., Daubney, L., Howes, N. U. M., and Seakins, P. W.:
Kinetics of CH2OO reactions with SO2, NO2, NO, H2O and
CH3CHO as a function of pressure, Phys. Chem. Chem. Phys., 16,
1139–1149, https://doi.org/10.1039/C3CP54391A, 2014.
Su, M.-N. and Lin, J. J.-M.: Note: A transient absorption spectrometer
using an ultra bright laser-driven light source, Rev. Sci. Instrum., 84,
086106, https://doi.org/10.1063/1.4818977, 2013.
Su, Y.-T., Huang, Y.-H., Witek, H. A., and Lee, Y.-P.: Infrared absorption
spectrum of the simplest Criegee intermediate CH2OO, Science, 340,
174–176, https://doi.org/10.1126/science.1234369, 2013.
Taatjes, C. A., Welz, O., Eskola, A. J., Savee, J. D., Osborn, D. L., Lee,
E. P. F., Dyke, J. M., Mok, D. W. K., Shallcross, D. E., and Percival, C.
J.: Direct measurement of Criegee intermediate (CH2OO) reactions with
acetone, acetaldehyde, and hexafluoroacetone, Phys. Chem. Chem. Phys., 14,
10391–10400, 10.1039/c2cp40294g, 2012.
Taatjes, C. A., Welz, O., Eskola, A. J., Savee, J. D., Scheer, A. M.,
Shallcross, D. E., Rotavera, B., Lee, E. P. F., Dyke, J. M., Mok, D. K. W.,
Osborn, D. L., and Percival, C. J.: Direct measurements of
conformer-dependent reactivity of the Criegee intermediate CH3CHOO,
Science, 340, 177–180, https://doi.org/10.1126/science.1234689,
2013.
Ting, W.-L., Chen, Y.-H., Chao, W., Smith, M. C., and Lin, J. J.-M.: The UV
absorption spectrum of the simplest Criegee intermediate CH2OO, Phys.
Chem. Chem. Phys., 16, 10438–10443, https://doi.org/10.1039/C4CP00877D, 2014.
Truhlar, D. G., Garrett, B. C., and Klippenstein, S. J.: Current Status of
Transition-State Theory, J. Phys. Chem., 100,
12771-12800, https://doi.org/10.1021/jp953748q, 1996.
Vansco, M. F., Marchetti, B., and Lester, M. I.: Electronic spectroscopy of
methyl vinyl ketone oxide: a four-carbon unsaturated Criegee intermediate
from isoprene ozonolysis, J. Chem. Phys., 149, 244309, https://doi.org/10.1063/1.5064716, 2018.
Vansco, M. F., Marchetti, B., Trongsiriwat, N., Bhagde, T., Wang, G., Walsh,
P. J., Klippenstein, S. J., and Lester, M. I.: Synthesis, electronic
spectroscopy, and photochemistry of methacrolein oxide: a four-carbon
unsaturated Criegee intermediate from isoprene ozonolysis, J. Am. Chem.
Soc., 141, 15058–15069, https://doi.org/10.1021/jacs.9b05193,
2019.
Vereecken, L., Novelli, A., and Taraborrelli, D.: Unimolecular decay
strongly limits the atmospheric impact of Criegee intermediates, Phys. Chem.
Chem. Phys., 19, 31599–31612, 2017.
Wang, M. Y., Yao, L., Zheng, J., Wang, X., Chen, J. M., 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.
Welz, O., Savee, J. D., Osborn, D. L., Vasu, S. S., J., P. C., Shallcross,
D. E., and Taatjes, C. A.: Direct kinetic measurements of Criegee
intermediate CH2OO formed by reaction of CH2I with O2,
Science, 335, 204–204, https://doi.org/10.1126/science.1213229,
2012.
Welz, O., Eskola, A. J., Sheps, L., Rotavera, B., Savee, J. D., Scheer, A.
M., Osborn, D. L., Lowe, D., Murray B., A., Xiao, P., Khan, M. A. H.,
Percival, C. J., Shallcross, D. E., and Taatjes, C. A.: Rate coefficients of
C1 and C2 Criegee intermediate reactions with formic and acetic acid near
the collision limit: direct kinetics measurements and atmospheric
implications, Angew. Chem., Int. Edit., 53, 4547–4550, https://doi.org/10.1002/anie.201400964, 2014.
Yvon, S. A., Saltzman, E. S., Cooper, D. J., Bates, T. S., and Thompson, A.
M.: Atmospheric sulfur cycling in the tropical Pacific marine boundary layer
(12∘ S, 135∘ W): a comparison of field data and model
results: 1. dimethylsulfide, J. Geophys. Res.-Atmos., 101, 6899–6909,
https://doi.org/10.1029/95JD03356, 1996.
Zhang, D., Lei, W., and Zhang, R.: Machanism of OH formation from ozonolysis
of isoprene: kinetics and product yield, Chem. Phys. Lett., 358, 171–179,
https://doi.org/10.1016/S0009-2614(02)00260-9, 2002.
Zhao, Y. and Truhlar, D. G.: The M06 suite of density functionals for main
group thermochemistry, thermochemical kinetics, noncovalent interactions,
excited states, and transition elements: two new functionals and systematic
testing of four M06-class functionals and 12 other functionals, Theor. Chem.
Acc., 120, 215-241, 10.1007/s00214-007-0310-x, 2008.
Zhou, X., Liu, Y., Dong, W., and Yang, X.: Unimolecular reaction rate
measurement of syn-CH3CHOO, J. Phys. Chem. Lett., 10, 4817–4821,
https://doi.org/10.1021/acs.jpclett.9b01740, 2019.
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.
Dimethyl sulfide (DMS) is the major sulfur-containing species in the troposphere. Previous work...
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