Articles | Volume 20, issue 1
https://doi.org/10.5194/acp-20-487-2020
© 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-20-487-2020
© Author(s) 2020. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
14 Jan 2020
Research article |
| 14 Jan 2020
| 14 Jan 2020
Photolysis and oxidation by OH radicals of two carbonyl nitrates: 4-nitrooxy-2-butanone and 5-nitrooxy-2-pentanone
Bénédicte Picquet-Varrault
CORRESPONDING AUTHOR
LISA, UMR CNRS 7583, Université Paris-Est Créteil,
Université de Paris, Institut Pierre Simon Laplace (IPSL), Créteil,
France
Ricardo Suarez-Bertoa
European Commission Joint Research Centre (JRC), Ispra, Italy
Marius Duncianu
Interscience Belgium, Louvain-la-Neuve, Belgium
Mathieu Cazaunau
LISA, UMR CNRS 7583, Université Paris-Est Créteil,
Université de Paris, Institut Pierre Simon Laplace (IPSL), Créteil,
France
Edouard Pangui
LISA, UMR CNRS 7583, Université Paris-Est Créteil,
Université de Paris, Institut Pierre Simon Laplace (IPSL), Créteil,
France
Marc David
LISA, UMR CNRS 7583, Université Paris-Est Créteil,
Université de Paris, Institut Pierre Simon Laplace (IPSL), Créteil,
France
Jean-François Doussin
LISA, UMR CNRS 7583, Université Paris-Est Créteil,
Université de Paris, Institut Pierre Simon Laplace (IPSL), Créteil,
France
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Axel Fouqueau, Manuela Cirtog, Mathieu Cazaunau, Edouard Pangui, Jean-François Doussin, and Bénédicte Picquet-Varrault
Atmos. Chem. Phys., 20, 15167–15189, https://doi.org/10.5194/acp-20-15167-2020, https://doi.org/10.5194/acp-20-15167-2020, 2020
Axel Fouqueau, Manuela Cirtog, Mathieu Cazaunau, Edouard Pangui, Pascal Zapf, Guillaume Siour, Xavier Landsheere, Guillaume Méjean, Daniele Romanini, and Bénédicte Picquet-Varrault
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Clarissa Baldo, Paola Formenti, Sophie Nowak, Servanne Chevaillier, Mathieu Cazaunau, Edouard Pangui, Claudia Di Biagio, Jean-Francois Doussin, Konstantin Ignatyev, Pavla Dagsson-Waldhauserova, Olafur Arnalds, A. Robert MacKenzie, and Zongbo Shi
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Max R. McGillen, William P. L. Carter, Abdelwahid Mellouki, John J. Orlando, Bénédicte Picquet-Varrault, and Timothy J. Wallington
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Claudia Di Biagio, Paola Formenti, Yves Balkanski, Lorenzo Caponi, Mathieu Cazaunau, Edouard Pangui, Emilie Journet, Sophie Nowak, Meinrat O. Andreae, Konrad Kandler, Thuraya Saeed, Stuart Piketh, David Seibert, Earle Williams, and Jean-François Doussin
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Patrick Chazette, Cyrille Flamant, Julien Totems, Marco Gaetani, Gwendoline Smith, Alexandre Baron, Xavier Landsheere, Karine Desboeufs, Jean-François Doussin, and Paola Formenti
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Marc D. Mallet, Barbara D'Anna, Aurélie Même, Maria Chiara Bove, Federico Cassola, Giandomenico Pace, Karine Desboeufs, Claudia Di Biagio, Jean-Francois Doussin, Michel Maille, Dario Massabò, Jean Sciare, Pascal Zapf, Alcide Giorgio di Sarra, and Paola Formenti
Atmos. Chem. Phys., 19, 11123–11142, https://doi.org/10.5194/acp-19-11123-2019, https://doi.org/10.5194/acp-19-11123-2019, 2019
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Paola Formenti, Stuart John Piketh, Andreas Namwoonde, Danitza Klopper, Roelof Burger, Mathieu Cazaunau, Anaïs Feron, Cécile Gaimoz, Stephen Broccardo, Nicola Walton, Karine Desboeufs, Guillaume Siour, Mattheus Hanghome, Samuel Mafwila, Edosa Omoregie, Wolfgang Junkermann, and Willy Maenhaut
Atmos. Chem. Phys., 18, 17003–17016, https://doi.org/10.5194/acp-18-17003-2018, https://doi.org/10.5194/acp-18-17003-2018, 2018
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Three-years of continuous measurements at the Henties Bay Aerosol Observatory (HBAO; 22°S, 14°05’E), Namibia, show that during the austral wintertime, long- and medium-range transport of pollution from biomass and fossil fuel burning give rise to peaks of light-absorbing black carbon aerosols into the marine boundary layer ahead of the main biomass burning season. This could affect the cloud properties.
Dario Massabò, Silvia Giulia Danelli, Paolo Brotto, Antonio Comite, Camilla Costa, Andrea Di Cesare, Jean François Doussin, Federico Ferraro, Paola Formenti, Elena Gatta, Laura Negretti, Maddalena Oliva, Franco Parodi, Luigi Vezzulli, and Paolo Prati
Atmos. Meas. Tech., 11, 5885–5900, https://doi.org/10.5194/amt-11-5885-2018, https://doi.org/10.5194/amt-11-5885-2018, 2018
Claudia Di Biagio, Paola Formenti, Mathieu Cazaunau, Edouard Pangui, Nicolas Marchand, and Jean-François Doussin
Atmos. Meas. Tech., 10, 2923–2939, https://doi.org/10.5194/amt-10-2923-2017, https://doi.org/10.5194/amt-10-2923-2017, 2017
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Mineral dust is one of the most abundant aerosol species at the global scale and an accurate estimation of its absorption at solar wavelengths is crucial to assess its impact on climate. In this work we provide an estimate of the Aethalometer multiple scattering correction for mineral dust aerosols at 450 and 660 nm. Our results suggest that the use of an optimized correction factor can lead to up to 11 % higher absorption coefficient and to 3 % higher single scattering albedo for mineral dust.
Lorenzo Caponi, Paola Formenti, Dario Massabó, Claudia Di Biagio, Mathieu Cazaunau, Edouard Pangui, Servanne Chevaillier, Gautier Landrot, Meinrat O. Andreae, Konrad Kandler, Stuart Piketh, Thuraya Saeed, Dave Seibert, Earle Williams, Yves Balkanski, Paolo Prati, and Jean-François Doussin
Atmos. Chem. Phys., 17, 7175–7191, https://doi.org/10.5194/acp-17-7175-2017, https://doi.org/10.5194/acp-17-7175-2017, 2017
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This paper presents new laboratory measurements of the shortwave mass absorption efficiency (MAE) used by climate models for mineral dust of different origin and at different sizes. We found that small particles are more efficient, by given mass, in absorbing radiation, particularly at shorter wavelength. Because dust has high concentrations in the atmosphere, light absorption by mineral dust can be competitive to other absorbing atmospheric aerosols such as black and brown carbon.
Sebastian Laufs, Mathieu Cazaunau, Patrick Stella, Ralf Kurtenbach, Pierre Cellier, Abdelwahid Mellouki, Benjamin Loubet, and Jörg Kleffmann
Atmos. Chem. Phys., 17, 6907–6923, https://doi.org/10.5194/acp-17-6907-2017, https://doi.org/10.5194/acp-17-6907-2017, 2017
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Sources of nitrous acid (HONO), a major precursor of the OH radical, are still under controversial discussion. Since mainly ground surface sources have been proposed, HONO fluxes were measured above an agricultural field. Positive daytime fluxes were observed which showed strong correlation with the product of the NO2 concentration and J(NO2). These results indicate HONO formation by photosensitized heterogeneous conversion of NO2 on soil surfaces as observed in recent laboratory studies.
Marius Duncianu, Marc David, Sakthivel Kartigueyane, Manuela Cirtog, Jean-François Doussin, and Benedicte Picquet-Varrault
Atmos. Meas. Tech., 10, 1445–1463, https://doi.org/10.5194/amt-10-1445-2017, https://doi.org/10.5194/amt-10-1445-2017, 2017
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Short summary
A commercial PTR-ToF-MS has been optimized in order to allow the measurement of individual organic nitrates in the atmosphere. This has been accomplished by shifting the distribution between different ionizing analytes. The proposed approach has been proved to be appropriate for the online detection of individual alkyl nitrates and functionalized nitrates.
Nga Lee Ng, Steven S. Brown, Alexander T. Archibald, Elliot Atlas, Ronald C. Cohen, John N. Crowley, Douglas A. Day, Neil M. Donahue, Juliane L. Fry, Hendrik Fuchs, Robert J. Griffin, Marcelo I. Guzman, Hartmut Herrmann, Alma Hodzic, Yoshiteru Iinuma, José L. Jimenez, Astrid Kiendler-Scharr, Ben H. Lee, Deborah J. Luecken, Jingqiu Mao, Robert McLaren, Anke Mutzel, Hans D. Osthoff, Bin Ouyang, Benedicte Picquet-Varrault, Ulrich Platt, Havala O. T. Pye, Yinon Rudich, Rebecca H. Schwantes, Manabu Shiraiwa, Jochen Stutz, Joel A. Thornton, Andreas Tilgner, Brent J. Williams, and Rahul A. Zaveri
Atmos. Chem. Phys., 17, 2103–2162, https://doi.org/10.5194/acp-17-2103-2017, https://doi.org/10.5194/acp-17-2103-2017, 2017
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Oxidation of biogenic volatile organic compounds by NO3 is an important interaction between anthropogenic
and natural emissions. This review results from a June 2015 workshop and includes the recent literature
on kinetics, mechanisms, organic aerosol yields, and heterogeneous chemistry; advances in analytical
instrumentation; the current state NO3-BVOC chemistry in atmospheric models; and critical needs for
future research in modeling, field observations, and laboratory studies.
Claudia Di Biagio, Paola Formenti, Yves Balkanski, Lorenzo Caponi, Mathieu Cazaunau, Edouard Pangui, Emilie Journet, Sophie Nowak, Sandrine Caquineau, Meinrat O. Andreae, Konrad Kandler, Thuraya Saeed, Stuart Piketh, David Seibert, Earle Williams, and Jean-François Doussin
Atmos. Chem. Phys., 17, 1901–1929, https://doi.org/10.5194/acp-17-1901-2017, https://doi.org/10.5194/acp-17-1901-2017, 2017
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Modeling the interaction of dust with long-wave (LW) radiation is still a challenge due to the scarcity of information on their refractive index. In this paper, we present a unique dataset of dust refractive indices obtained from in situ measurements in a large smog chamber. Our results show that the dust LW refractive index varies strongly from source to source due to particle composition changes. We recommend taking this variability into account in climate and remote sensing applications.
L. Brégonzio-Rozier, C. Giorio, F. Siekmann, E. Pangui, S. B. Morales, B. Temime-Roussel, A. Gratien, V. Michoud, M. Cazaunau, H. L. DeWitt, A. Tapparo, A. Monod, and J.-F. Doussin
Atmos. Chem. Phys., 16, 1747–1760, https://doi.org/10.5194/acp-16-1747-2016, https://doi.org/10.5194/acp-16-1747-2016, 2016
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The impact of cloud events on isoprene secondary organic aerosol (SOA) formation has been studied from an isoprene/ NOx/light system in an atmospheric simulation chamber. aqSOA formation can be linked to water soluble volatile organic compounds' dissolution in the aqueous phase and to further aqueous phase reactions. Cloud-induced SOA formation is experimentally demonstrated in this study, thus highlighting the importance of aqueous multiphase systems in atmospheric SOA formation estimations.
S. Mailler, L. Menut, A. G. di Sarra, S. Becagli, T. Di Iorio, B. Bessagnet, R. Briant, P. Formenti, J.-F. Doussin, J. L. Gómez-Amo, M. Mallet, G. Rea, G. Siour, D. M. Sferlazzo, R. Traversi, R. Udisti, and S. Turquety
Atmos. Chem. Phys., 16, 1219–1244, https://doi.org/10.5194/acp-16-1219-2016, https://doi.org/10.5194/acp-16-1219-2016, 2016
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We studied the impact of aerosols on tropospheric photolysis rates at Lampedusa during the CharMEx/ADRIMED campaign in June 2013. It is shown by using the CHIMERE chemistry-transport model (CTM) as well as in situ and remote-sensing measurements that taking into account the radiative effect of the tropospheric aerosols improves the ability of the model to reproduce the observed photolysis rates. It is hence important for CTMs to include the radiative effect of aerosols on photochemistry.
M. Mallet, F. Dulac, P. Formenti, P. Nabat, J. Sciare, G. Roberts, J. Pelon, G. Ancellet, D. Tanré, F. Parol, C. Denjean, G. Brogniez, A. di Sarra, L. Alados-Arboledas, J. Arndt, F. Auriol, L. Blarel, T. Bourrianne, P. Chazette, S. Chevaillier, M. Claeys, B. D'Anna, Y. Derimian, K. Desboeufs, T. Di Iorio, J.-F. Doussin, P. Durand, A. Féron, E. Freney, C. Gaimoz, P. Goloub, J. L. Gómez-Amo, M. J. Granados-Muñoz, N. Grand, E. Hamonou, I. Jankowiak, M. Jeannot, J.-F. Léon, M. Maillé, S. Mailler, D. Meloni, L. Menut, G. Momboisse, J. Nicolas, T. Podvin, V. Pont, G. Rea, J.-B. Renard, L. Roblou, K. Schepanski, A. Schwarzenboeck, K. Sellegri, M. Sicard, F. Solmon, S. Somot, B Torres, J. Totems, S. Triquet, N. Verdier, C. Verwaerde, F. Waquet, J. Wenger, and P. Zapf
Atmos. Chem. Phys., 16, 455–504, https://doi.org/10.5194/acp-16-455-2016, https://doi.org/10.5194/acp-16-455-2016, 2016
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The aim of this article is to present an experimental campaign over the Mediterranean focused on aerosol-radiation measurements and modeling. Results indicate an important atmospheric loading associated with a moderate absorbing ability of mineral dust. Observations suggest a complex vertical structure and size distributions characterized by large aerosols within dust plumes. The radiative effect is highly variable, with negative forcing over the Mediterranean and positive over northern Africa.
I. Kourtchev, J.-F. Doussin, C. Giorio, B. Mahon, E. M. Wilson, N. Maurin, E. Pangui, D. S. Venables, J. C. Wenger, and M. Kalberer
Atmos. Chem. Phys., 15, 5683–5695, https://doi.org/10.5194/acp-15-5683-2015, https://doi.org/10.5194/acp-15-5683-2015, 2015
C. Denjean, P. Formenti, B. Picquet-Varrault, E. Pangui, P. Zapf, Y. Katrib, C. Giorio, A. Tapparo, A. Monod, B. Temime-Roussel, P. Decorse, C. Mangeney, and J. F. Doussin
Atmos. Chem. Phys., 15, 3339–3358, https://doi.org/10.5194/acp-15-3339-2015, https://doi.org/10.5194/acp-15-3339-2015, 2015
L. Brégonzio-Rozier, F. Siekmann, C. Giorio, E. Pangui, S. B. Morales, B. Temime-Roussel, A. Gratien, V. Michoud, S. Ravier, M. Cazaunau, A. Tapparo, A. Monod, and J.-F. Doussin
Atmos. Chem. Phys., 15, 2953–2968, https://doi.org/10.5194/acp-15-2953-2015, https://doi.org/10.5194/acp-15-2953-2015, 2015
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First- and higher order -generation products formed from the oxidation of isoprene and methacrolein with OH radicals in the presence of NOx have been studied in a simulation chamber. Differences in light source are proposed to partially explain the discrepancies observed between different studies in the literature for both isoprene- and methacrolein-SOA mass yields. According to our results, these SOA yields in the atmosphere could be lower than suggested by most of the current chamber studies.
C. Denjean, P. Formenti, B. Picquet-Varrault, M. Camredon, E. Pangui, P. Zapf, Y. Katrib, C. Giorio, A. Tapparo, B. Temime-Roussel, A. Monod, B. Aumont, and J. F. Doussin
Atmos. Chem. Phys., 15, 883–897, https://doi.org/10.5194/acp-15-883-2015, https://doi.org/10.5194/acp-15-883-2015, 2015
W. Ait-Helal, A. Borbon, S. Sauvage, J. A. de Gouw, A. Colomb, V. Gros, F. Freutel, M. Crippa, C. Afif, U. Baltensperger, M. Beekmann, J.-F. Doussin, R. Durand-Jolibois, I. Fronval, N. Grand, T. Leonardis, M. Lopez, V. Michoud, K. Miet, S. Perrier, A. S. H. Prévôt, J. Schneider, G. Siour, P. Zapf, and N. Locoge
Atmos. Chem. Phys., 14, 10439–10464, https://doi.org/10.5194/acp-14-10439-2014, https://doi.org/10.5194/acp-14-10439-2014, 2014
C. Denjean, P. Formenti, B. Picquet-Varrault, Y. Katrib, E. Pangui, P. Zapf, and J. F. Doussin
Atmos. Meas. Tech., 7, 183–197, https://doi.org/10.5194/amt-7-183-2014, https://doi.org/10.5194/amt-7-183-2014, 2014
J.-F. Doussin and A. Monod
Atmos. Chem. Phys., 13, 11625–11641, https://doi.org/10.5194/acp-13-11625-2013, https://doi.org/10.5194/acp-13-11625-2013, 2013
Q. J. Zhang, M. Beekmann, F. Drewnick, F. Freutel, J. Schneider, M. Crippa, A. S. H. Prevot, U. Baltensperger, L. Poulain, A. Wiedensohler, J. Sciare, V. Gros, A. Borbon, A. Colomb, V. Michoud, J.-F. Doussin, H. A. C. Denier van der Gon, M. Haeffelin, J.-C. Dupont, G. Siour, H. Petetin, B. Bessagnet, S. N. Pandis, A. Hodzic, O. Sanchez, C. Honoré, and O. Perrussel
Atmos. Chem. Phys., 13, 5767–5790, https://doi.org/10.5194/acp-13-5767-2013, https://doi.org/10.5194/acp-13-5767-2013, 2013
Related subject area
Subject: Gases | Research Activity: Laboratory Studies | Altitude Range: Troposphere | Science Focus: Chemistry (chemical composition and reactions)
Impact of HO2∕RO2 ratio on highly oxygenated α-pinene photooxidation products and secondary organic aerosol formation potential
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
Atmospheric impact of 2-methylpentanal emissions: kinetics, photochemistry, and formation of secondary pollutants
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)
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
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
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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 is of importance as laboratory studies are often biased towards organic peroxy radicals.
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
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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 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
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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-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
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Due to the intrinsic connection between the formation pathways of O3 and HOMs, the ratio of HOM dimers or non-nitrate monomers to HOM organic nitrates could be used to determine O3 formation regimes. Owing to the fast formation and short lifetimes of HOMs, HOM-based indicating ratios can describe O3 formation in real time. Despite the success of our approach in this simple laboratory system, applicability to the much more complex atmosphere remains to be determined.
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.
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.
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.
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.
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.
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Short summary
Multifunctional organic nitrates are important atmospheric species that are known to play a key role in the transport of reactive nitrogen and in aerosol composition. However, very little is known about their atmospheric reactivity. Here we provide an experimental study on the photolysis and reaction of two carbonyl nitrates with OH radicals. Atmospheric implications and the influence of the chemical structure on the reactivity are discussed.
Multifunctional organic nitrates are important atmospheric species that are known to play a key...
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