Articles | Volume 25, issue 18
https://doi.org/10.5194/acp-25-11003-2025
© Author(s) 2025. 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-25-11003-2025
© Author(s) 2025. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
23 Sep 2025
Research article |
| 23 Sep 2025
| 23 Sep 2025
Highly oxygenated molecules (HOMs) and secondary organic aerosol (SOA) formation from the oxidation of α- and β-phellandrenes by NO3 radicals
Sergio Harb
CORRESPONDING AUTHOR
Univ Paris Est Creteil and Université de Paris Cité, CNRS, LISA, 94010 Créteil, France
Institut National de l'Environnement Industriel et des Risques (INERIS), 60550 Verneuil-en-Halatte, France
Manuela Cirtog
Univ Paris Est Creteil and Université de Paris Cité, CNRS, LISA, 94010 Créteil, France
Stéphanie Alage
Univ Paris Est Creteil and Université de Paris Cité, CNRS, LISA, 94010 Créteil, France
Christopher Cantrell
Univ Paris Est Creteil and Université de Paris Cité, CNRS, LISA, 94010 Créteil, France
Atmospheric and Oceanic Sciences (ATOC), University of Colorado, Boulder, CO 80309, USA
Mathieu Cazaunau
Univ Paris Est Creteil and Université de Paris Cité, CNRS, LISA, 94010 Créteil, France
Vincent Michoud
Université Paris cité and Univ Paris Est Creteil, CNRS, LISA, 75013 Paris, France
Edouard Pangui
Univ Paris Est Creteil and Université de Paris Cité, CNRS, LISA, 94010 Créteil, France
Antonin Bergé
Univ Paris Est Creteil and Université de Paris Cité, CNRS, LISA, 94010 Créteil, France
Chiara Giorio
Yusuf Hamied Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW, United Kingdom
Francesco Battaglia
Atmospheric and Oceanic Sciences (ATOC), University of Colorado, Boulder, CO 80309, USA
Bénédicte Picquet-Varrault
CORRESPONDING AUTHOR
Univ Paris Est Creteil and Université de Paris Cité, CNRS, LISA, 94010 Créteil, France
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Laura Renzi, Claudia Di Biagio, Johannes Heuser, Marco Zanatta, Mathieu Cazaunau, Antonin Bergé, Edouard Pangui, Jérôme Yon, Tommaso Isolabella, Dario Massabò, Virginia Vernocchi, Martina Mazzini, Chenjie Yu, Paola Formenti, Benedicte Picquet-Varrault, Jean-Francois Doussin, and Angela Marinoni
EGUsphere, https://doi.org/10.5194/egusphere-2025-2823, https://doi.org/10.5194/egusphere-2025-2823, 2025
This preprint is open for discussion and under review for Atmospheric Measurement Techniques (AMT).
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This study investigates how particle properties affect the accuracy of a common air pollution instrument, the dual-spot aethalometer. By combining lab experiments with real-world data from a mountain site in Italy, we found that the correction factor for this instrument varies mainly due to particle size and measurement conditions. Understanding these influences helps improve air quality monitoring, which is important for assessing pollution impacts on health and climate.
Claudia Di Biagio, Elisa Bru, Avila Orta, Servanne Chevaillier, Clarissa Baldo, Antonin Bergé, Mathieu Cazaunau, Sandra Lafon, Sophie Nowak, Edouard Pangui, Meinrat O. Andreae, Pavla Dagsson-Waldhauserova, Kebonyethata Dintwe, Konrad Kandler, James S. King, Amelie Chaput, Gregory S. Okin, Stuart Piketh, Thuraya Saeed, David Seibert, Zongbo Shi, Earle Williams, Pasquale Sellitto, and Paola Formenti
EGUsphere, https://doi.org/10.5194/egusphere-2025-3512, https://doi.org/10.5194/egusphere-2025-3512, 2025
This preprint is open for discussion and under review for Atmospheric Chemistry and Physics (ACP).
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Spectroscopy measurements show that the absorbance of dust in the far-infrared up to 25 μm is comparable in intensity to that in the mid-infrared (3–15μm) suggesting its relevance for dust direct radiative effect. Data evidence different absorption signatures for high and low/mid latitude dust, due to differences in mineralogical composition. These differences could be used to characterise the mineralogy and differentiate the origin of airborne dust based on infrared remote sensing observations.
Chenjie Yu, Paola Formenti, Joel F. de Brito, Astrid Bauville, Antonin Bergé, Hichem Bouzidi, Mathieu Cazaunau, Manuela Cirtog, Claudia Di Biagio, Ludovico Di Antonio, Cécile Gaimoz, Franck Maisonneuve, Pascal Zapf, Tobias Seubert, Simone T. Andersen, Patrick Dewald, Gunther N. T. E. Türk, John N. Crowley, Alexandre Kukui, Chaoyang Xue, Cyrielle Denjean, Olivier Garrouste, Jean-Claude Etienne, Huihui Wu, James D. Allan, Dantong Liu, Yangzhou Wu, Christopher Cantrell, and Vincent Michoud
EGUsphere, https://doi.org/10.5194/egusphere-2025-2667, https://doi.org/10.5194/egusphere-2025-2667, 2025
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We presented a field measurement in a Paris suburban forest region to characterise the impacts of photochemical aging process on aerosol physical chemical properties. Photochemical production of organic aerosols increased forest fine particle mass and significantly enhanced absorption of short-wavelength sunlight. This study highlights the critical need to incorporate light absorbing carbonaceous particles formation mechanisms into models to accurately simulate their direct radiative impacts.
Johannes Heuser, Claudia Di Biagio, Jérôme Yon, Mathieu Cazaunau, Antonin Bergé, Edouard Pangui, Marco Zanatta, Laura Renzi, Angela Marinoni, Satoshi Inomata, Chenjie Yu, Vera Bernardoni, Servanne Chevaillier, Daniel Ferry, Paolo Laj, Michel Maillé, Dario Massabò, Federico Mazzei, Gael Noyalet, Hiroshi Tanimoto, Brice Temime-Roussel, Roberta Vecchi, Virginia Vernocchi, Paola Formenti, Bénédicte Picquet-Varrault, and Jean-François Doussin
Atmos. Chem. Phys., 25, 6407–6428, https://doi.org/10.5194/acp-25-6407-2025, https://doi.org/10.5194/acp-25-6407-2025, 2025
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The spectral optical properties of combustion soot aerosols with varying black (BC) and brown carbon (BrC) content were studied in an atmospheric simulation chamber. Measurements of the mass spectral absorption cross section (MAC), supplemented by literature data, allowed us to establish a generalised exponential relationship between the spectral absorption and the elemental-to-total-carbon ratio (EC / TC) in soot. This relationship can provide a useful tool for modelling the properties of soot.
Diana L. Pereira, Aline Gratien, Chiara Giorio, Emmanuelle Mebold, Thomas Bertin, Cécile Gaimoz, Jean-François Doussin, and Paola Formenti
EGUsphere, https://doi.org/10.5194/egusphere-2025-2393, https://doi.org/10.5194/egusphere-2025-2393, 2025
This preprint is open for discussion and under review for Atmospheric Measurement Techniques (AMT).
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This study provides two methods for the quantification of molecular markers to improve the description of secondary organic aerosols using chromatographic techniques coupled with mass spectrometry. Compounds from various chemical functionalities (alcohols, acids, aldehydes), from biogenic and anthropogenic origin, were identified. Improved method performance was observed for nitro compounds, which have been associated with anthropogenic activities.
Simone T. Andersen, Rolf Sander, Patrick Dewald, Laura Wüst, Tobias Seubert, Gunther N. T. E. Türk, Jan Schuladen, Max R. McGillen, Chaoyang Xue, Abdelwahid Mellouki, Alexandre Kukui, Vincent Michoud, Manuela Cirtog, Mathieu Cazaunau, Astrid Bauville, Hichem Bouzidi, Paola Formenti, Cyrielle Denjean, Jean-Claude Etienne, Olivier Garrouste, Christopher Cantrell, Jos Lelieveld, and John N. Crowley
Atmos. Chem. Phys., 25, 5893–5909, https://doi.org/10.5194/acp-25-5893-2025, https://doi.org/10.5194/acp-25-5893-2025, 2025
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Measurements and modelling of reactive nitrogen gases observed in a suburban temperate forest in Rambouillet, France, circa 50 km southwest of Paris in 2022 indicate that the biosphere rapidly scavenges organic nitrates of mixed biogenic and anthropogenic origin, resulting in short lifetimes for, for example, alkyl nitrates and peroxy nitrates.
Ludovico Di Antonio, Matthias Beekmann, Guillaume Siour, Vincent Michoud, Christopher Cantrell, Astrid Bauville, Antonin Bergé, Mathieu Cazaunau, Servanne Chevaillier, Manuela Cirtog, Joel F. de Brito, Paola Formenti, Cecile Gaimoz, Olivier Garret, Aline Gratien, Valérie Gros, Martial Haeffelin, Lelia N. Hawkins, Simone Kotthaus, Gael Noyalet, Diana L. Pereira, Jean-Eudes Petit, Eva Drew Pronovost, Véronique Riffault, Chenjie Yu, Gilles Foret, Jean-François Doussin, and Claudia Di Biagio
Atmos. Chem. Phys., 25, 4803–4831, https://doi.org/10.5194/acp-25-4803-2025, https://doi.org/10.5194/acp-25-4803-2025, 2025
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The summer of 2022 has been considered a proxy for future climate scenarios due to its hot and dry conditions. In this paper, we use the measurements from the Atmospheric Chemistry of the Suburban Forest (ACROSS) campaign, conducted in the Paris area in June–July 2022, along with observations from existing networks, to evaluate a 3D chemistry transport model (WRF–CHIMERE) simulation. Results are shown to be satisfactory, allowing us to explain the gas and aerosol variability at the campaign sites.
Diana L. Pereira, Chiara Giorio, Aline Gratien, Alexander Zherebker, Gael Noyalet, Servanne Chevaillier, Stéphanie Alage, Elie Almarj, Antonin Bergé, Thomas Bertin, Mathieu Cazaunau, Patrice Coll, Ludovico Di Antonio, Sergio Harb, Johannes Heuser, Cécile Gaimoz, Oscar Guillemant, Brigitte Language, Olivier Lauret, Camilo Macias, Franck Maisonneuve, Bénédicte Picquet-Varrault, Raquel Torres, Sylvain Triquet, Pascal Zapf, Lelia Hawkins, Drew Pronovost, Sydney Riley, Pierre-Marie Flaud, Emilie Perraudin, Pauline Pouyes, Eric Villenave, Alexandre Albinet, Olivier Favez, Robin Aujay-Plouzeau, Vincent Michoud, Christopher Cantrell, Manuela Cirtog, Claudia Di Biagio, Jean-François Doussin, and Paola Formenti
Atmos. Chem. Phys., 25, 4885–4905, https://doi.org/10.5194/acp-25-4885-2025, https://doi.org/10.5194/acp-25-4885-2025, 2025
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In order to study aerosols in environments influenced by anthropogenic and biogenic emissions, we performed analyses of samples collected during the ACROSS (Atmospheric Chemistry Of the Suburban Forest) campaign in summer 2022 in the greater Paris area. After analysis of the chemical composition by means of total carbon determination and high-resolution mass spectrometry, this work highlights the influence of anthropogenic inputs on the chemical composition of both urban and forested areas.
Paola Formenti, Chiara Giorio, Karine Desboeufs, Alexander Zherebker, Marco Gaetani, Clarissa Baldo, Gautier Landrot, Simona Montebello, Servanne Chevaillier, Sylvain Triquet, Guillaume Siour, Claudia Di Biagio, Francesco Battaglia, Jean-François Doussin, Anais Feron, Andreas Namwoonde, and Stuart John Piketh
EGUsphere, https://doi.org/10.5194/egusphere-2025-446, https://doi.org/10.5194/egusphere-2025-446, 2025
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The elemental composition and solubility of several metals, including iron, at a coastal site in Namibia in August–September 2017, indicate that natural and anthropogenic dust had different solubility depending on mineralogy but mostly to the processing by fluoride ions from marine emissions, pointing out to the complexity of atmospheric/oceanic interactions in this region of the world influenced by the Benguela current and significant aerosol load.
Ludovico Di Antonio, Claudia Di Biagio, Paola Formenti, Aline Gratien, Vincent Michoud, Christopher Cantrell, Astrid Bauville, Antonin Bergé, Mathieu Cazaunau, Servanne Chevaillier, Manuela Cirtog, Patrice Coll, Barbara D'Anna, Joel F. de Brito, David O. De Haan, Juliette R. Dignum, Shravan Deshmukh, Olivier Favez, Pierre-Marie Flaud, Cecile Gaimoz, Lelia N. Hawkins, Julien Kammer, Brigitte Language, Franck Maisonneuve, Griša Močnik, Emilie Perraudin, Jean-Eudes Petit, Prodip Acharja, Laurent Poulain, Pauline Pouyes, Eva Drew Pronovost, Véronique Riffault, Kanuri I. Roundtree, Marwa Shahin, Guillaume Siour, Eric Villenave, Pascal Zapf, Gilles Foret, Jean-François Doussin, and Matthias Beekmann
Atmos. Chem. Phys., 25, 3161–3189, https://doi.org/10.5194/acp-25-3161-2025, https://doi.org/10.5194/acp-25-3161-2025, 2025
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The spectral complex refractive index (CRI) and single scattering albedo were retrieved from submicron aerosol measurements at three sites within the greater Paris area during the ACROSS field campaign (June–July 2022). Measurements revealed urban emission impact on surrounding areas. CRI full period averages at 520 nm were 1.41 – 0.037i (urban), 1.52 – 0.038i (peri-urban), and 1.50 – 0.025i (rural). Organic aerosols dominated the aerosol mass and contributed up to 22 % of absorption at 370 nm.
Francesco Battaglia, Paola Formenti, Chiara Giorio, Mathieu Cazaunau, Edouard Pangui, Antonin Bergé, Aline Gratien, Thomas Bertin, Joël F. de Brito, Manolis N. Romanias, Vincent Michoud, Clarissa Baldo, Servanne Chevaillier, Gaël Noyalet, Philippe Decorse, Bénédicte Picquet-Varrault, and Jean-François Doussin
EGUsphere, https://doi.org/10.5194/egusphere-2024-4073, https://doi.org/10.5194/egusphere-2024-4073, 2025
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This paper presents an experimental investigation of the interactions between glyoxal, an important volatile organic compound, and mineral dust particles of size and composition typical of natural conditions. We show that their interactions modifies in a definitive way the concentrations of the gas phase and the properties of the dust, which could have important implications of the atmospheric composition and the Earth's climate.
Chiara Giorio, Anne Monod, Valerio Di Marco, Pierre Herckes, Denise Napolitano, Amy Sullivan, Gautier Landrot, Daniel Warnes, Marika Nasti, Sara D'Aronco, Agathe Gérardin, Nicolas Brun, Karine Desboeufs, Sylvain Triquet, Servanne Chevaillier, Claudia Di Biagio, Francesco Battaglia, Frédéric Burnet, Stuart J. Piketh, Andreas Namwoonde, Jean-François Doussin, and Paola Formenti
EGUsphere, https://doi.org/10.5194/egusphere-2024-4140, https://doi.org/10.5194/egusphere-2024-4140, 2025
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A comparison between the solubility of trace metals in pairs of total suspended particulate (TSP) and fog water samples collected in Henties Bay, Namibia, during the AEROCLO-sA field campaign is presented. We found enhanced solubility of metals in fog samples which we attributed to metal-ligand complexes formation in the early stages of particle activation into droplets which can then remain in a kinetically stable form in fog or lead to the formation of colloidal nanoparticles.
Simone T. Andersen, Max R. McGillen, Chaoyang Xue, Tobias Seubert, Patrick Dewald, Gunther N. T. E. Türk, Jan Schuladen, Cyrielle Denjean, Jean-Claude Etienne, Olivier Garrouste, Marina Jamar, Sergio Harb, Manuela Cirtog, Vincent Michoud, Mathieu Cazaunau, Antonin Bergé, Christopher Cantrell, Sebastien Dusanter, Bénédicte Picquet-Varrault, Alexandre Kukui, Abdelwahid Mellouki, Lucy J. Carpenter, Jos Lelieveld, and John N. Crowley
Atmos. Chem. Phys., 24, 11603–11618, https://doi.org/10.5194/acp-24-11603-2024, https://doi.org/10.5194/acp-24-11603-2024, 2024
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Using measurements of various trace gases in a suburban forest near Paris in the summer of 2022, we were able to gain insight into the sources and sinks of NOx (NO+NO2) with a special focus on their nighttime chemical and physical loss processes. NO was observed as a result of nighttime soil emissions when O3 levels were strongly depleted by deposition. NO oxidation products were not observed at night, indicating that soil and/or foliar surfaces are an efficient sink of reactive N.
Patrick Dewald, Tobias Seubert, Simone T. Andersen, Gunther N. T. E. Türk, Jan Schuladen, Max R. McGillen, Cyrielle Denjean, Jean-Claude Etienne, Olivier Garrouste, Marina Jamar, Sergio Harb, Manuela Cirtog, Vincent Michoud, Mathieu Cazaunau, Antonin Bergé, Christopher Cantrell, Sebastien Dusanter, Bénédicte Picquet-Varrault, Alexandre Kukui, Chaoyang Xue, Abdelwahid Mellouki, Jos Lelieveld, and John N. Crowley
Atmos. Chem. Phys., 24, 8983–8997, https://doi.org/10.5194/acp-24-8983-2024, https://doi.org/10.5194/acp-24-8983-2024, 2024
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In the scope of a field campaign in a suburban forest near Paris in the summer of 2022, we measured the reactivity of the nitrate radical NO3 towards biogenic volatile organic compounds (BVOCs; e.g. monoterpenes) mainly below but also above the canopy. NO3 reactivity was the highest during nights with strong temperature inversions and decreased strongly with height. Reactions with BVOCs were the main removal process of NO3 throughout the diel cycle below the canopy.
Stéphanie Alage, Vincent Michoud, Sergio Harb, Bénédicte Picquet-Varrault, Manuela Cirtog, Avinash Kumar, Matti Rissanen, and Christopher Cantrell
Atmos. Meas. Tech., 17, 4709–4724, https://doi.org/10.5194/amt-17-4709-2024, https://doi.org/10.5194/amt-17-4709-2024, 2024
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Calibration exercises are essential for determining the accuracy of instruments. We performed calibrations on a NO3¯ ToFCIMS instrument to determine its sensitivity and linearity for detecting various organic compounds. Our findings revealed significant variability, over several orders of magnitude, in the calibration factors obtained. The results suggest that relying on a single calibration factor from H2SO4 for the quantification of all compounds detected by this technique is not appropriate.
Chenjie Yu, Edouard Pangui, Kevin Tu, Mathieu Cazaunau, Maxime Feingesicht, Landsheere Xavier, Thierry Bourrianne, Vincent Michoud, Christopher Cantrell, Timothy B. Onasch, Andrew Freedman, and Paola Formenti
Atmos. Meas. Tech., 17, 3419–3437, https://doi.org/10.5194/amt-17-3419-2024, https://doi.org/10.5194/amt-17-3419-2024, 2024
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To meet the requirements for measuring aerosol optical properties on airborne platforms and conducting dual-wavelength measurements, we introduced A2S2, an airborne dual-wavelength cavity-attenuated phase-shift single monitor. This study reports the results in the laboratory and an aircraft campaign over Paris and its surrounding regions. The results demonstrate A2S2's reliability in measuring aerosol optical properties at both wavelengths and its suitability for future aircraft campaigns.
Alice Maison, Lya Lugon, Soo-Jin Park, Alexia Baudic, Christopher Cantrell, Florian Couvidat, Barbara D'Anna, Claudia Di Biagio, Aline Gratien, Valérie Gros, Carmen Kalalian, Julien Kammer, Vincent Michoud, Jean-Eudes Petit, Marwa Shahin, Leila Simon, Myrto Valari, Jérémy Vigneron, Andrée Tuzet, and Karine Sartelet
Atmos. Chem. Phys., 24, 6011–6046, https://doi.org/10.5194/acp-24-6011-2024, https://doi.org/10.5194/acp-24-6011-2024, 2024
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This study presents the development of a bottom-up inventory of urban tree biogenic emissions. Emissions are computed for each tree based on their location and characteristics and are integrated in the regional air quality model WRF-CHIMERE. The impact of these biogenic emissions on air quality is quantified for June–July 2022. Over Paris city, urban trees increase the concentrations of particulate organic matter by 4.6 %, of PM2.5 by 0.6 %, and of ozone by 1.0 % on average over 2 months.
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.
Anil Kumar Mandariya, Junteng Wu, Anne Monod, Paola Formenti, Bénédicte Picquet-Varrault, Mathieu Cazaunau, Stephan Mertes, Laurent Poulain, Antonin Berge, Edouard Pangui, Andreas Tilgner, Thomas Schaefer, Liang Wen, Hartmut Herrmann, and Jean-François Doussin
Atmos. Meas. Tech. Discuss., https://doi.org/10.5194/amt-2023-206, https://doi.org/10.5194/amt-2023-206, 2024
Publication in AMT not foreseen
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An optimized and controlled protocol for generating quasi-adiabatic expansion clouds under simulated dark and light conditions was presented. The irradiated clouds clearly showed a gradual activation of seed particles into droplets. In contrast, non-irradiated clouds faced a flash activation. This paper will lay the foundation for multiphase photochemical studies implying water-soluble volatile organic compounds and particulate matter formation during cloud formation-evaporation cycles.
Clarissa Baldo, Paola Formenti, Claudia Di Biagio, Gongda Lu, Congbo Song, Mathieu Cazaunau, Edouard Pangui, Jean-Francois Doussin, Pavla Dagsson-Waldhauserova, Olafur Arnalds, David Beddows, A. Robert MacKenzie, and Zongbo Shi
Atmos. Chem. Phys., 23, 7975–8000, https://doi.org/10.5194/acp-23-7975-2023, https://doi.org/10.5194/acp-23-7975-2023, 2023
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This paper presents new shortwave spectral complex refractive index and single scattering albedo data for Icelandic dust. Our results show that the imaginary part of the complex refractive index of Icelandic dust is at the upper end of the range of low-latitude dust. Furthermore, we observed that Icelandic dust is more absorbing towards the near-infrared, which we attribute to its high magnetite content. These findings are important for modeling dust aerosol radiative effects in the Arctic.
Arineh Cholakian, Matthias Beekmann, Guillaume Siour, Isabelle Coll, Manuela Cirtog, Elena Ormeño, Pierre-Marie Flaud, Emilie Perraudin, and Eric Villenave
Atmos. Chem. Phys., 23, 3679–3706, https://doi.org/10.5194/acp-23-3679-2023, https://doi.org/10.5194/acp-23-3679-2023, 2023
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This article revolves around the simulation of biogenic secondary organic aerosols in the Landes forest (southwestern France). Several sensitivity cases involving biogenic emission factors, land cover data, anthropogenic emissions, and physical or meteorological parameters were performed and each compared to measurements both in the forest canopy and around the forest. The chemistry behind the formation of these aerosols and their production and transport in the forest canopy is discussed.
Axel Fouqueau, Manuela Cirtog, Mathieu Cazaunau, Edouard Pangui, Jean-François Doussin, and Bénédicte Picquet-Varrault
Atmos. Chem. Phys., 22, 6411–6434, https://doi.org/10.5194/acp-22-6411-2022, https://doi.org/10.5194/acp-22-6411-2022, 2022
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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.
Karine Desboeufs, Franck Fu, Matthieu Bressac, Antonio Tovar-Sánchez, Sylvain Triquet, Jean-François Doussin, Chiara Giorio, Patrick Chazette, Julie Disnaquet, Anaïs Feron, Paola Formenti, Franck Maisonneuve, Araceli Rodríguez-Romero, Pascal Zapf, François Dulac, and Cécile Guieu
Atmos. Chem. Phys., 22, 2309–2332, https://doi.org/10.5194/acp-22-2309-2022, https://doi.org/10.5194/acp-22-2309-2022, 2022
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This article reports the first concurrent sampling of wet deposition samples and surface seawater and was performed during the PEACETIME cruise in the remote Mediterranean (May–June 2017). Through the chemical composition of trace metals (TMs) in these samples, it emphasizes the decrease of atmospheric metal pollution in this area during the last few decades and the critical role of wet deposition as source of TMs for Mediterranean surface seawater, especially for intense dust deposition events.
Spiro D. Jorga, Kalliopi Florou, Christos Kaltsonoudis, John K. Kodros, Christina Vasilakopoulou, Manuela Cirtog, Axel Fouqueau, Bénédicte Picquet-Varrault, Athanasios Nenes, and Spyros N. Pandis
Atmos. Chem. Phys., 21, 15337–15349, https://doi.org/10.5194/acp-21-15337-2021, https://doi.org/10.5194/acp-21-15337-2021, 2021
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We test the hypothesis that significant secondary organic aerosol production can take place even during winter nights through the oxidation of the emitted organic vapors by the nitrate radicals produced during the reaction of ozone and nitrogen oxides. Our experiments, using as a starting point the ambient air of an urban area with high biomass burning activity, demonstrate that, even with sunlight, there is 20 %–70 % additional organic aerosol formed in a few hours.
Hongming Yi, Mathieu Cazaunau, Aline Gratien, Vincent Michoud, Edouard Pangui, Jean-Francois Doussin, and Weidong Chen
Atmos. Meas. Tech., 14, 5701–5715, https://doi.org/10.5194/amt-14-5701-2021, https://doi.org/10.5194/amt-14-5701-2021, 2021
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HONO and NO2 play a crucial role in the atmospheric oxidation capacity that affects the regional air quality and global climate. Accurate measurements of HONO are challenging due to the drawback of existing detection methods. Calibration-free high-sensitivity direct, simultaneous measurements of NO2, HONO and CH2O with UV-IBBCEAS provide accurate and fast quantitative analysis of their concentration variation within their lifetime by intercomparison with NOx, FTIR and NitroMAC sensors.
Vincent Michoud, Elise Hallemans, Laura Chiappini, Eva Leoz-Garziandia, Aurélie Colomb, Sébastien Dusanter, Isabelle Fronval, François Gheusi, Jean-Luc Jaffrezo, Thierry Léonardis, Nadine Locoge, Nicolas Marchand, Stéphane Sauvage, Jean Sciare, and Jean-François Doussin
Atmos. Chem. Phys., 21, 8067–8088, https://doi.org/10.5194/acp-21-8067-2021, https://doi.org/10.5194/acp-21-8067-2021, 2021
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A multiphasic molecular characterization of oxygenated compounds has been carried out during the ChArMEx field campaign using offline analysis. It leads to the identification of 97 different compounds in the gas and aerosol phases and reveals the important contribution of organic acids to organic aerosol. In addition, comparison between experimental and theoretical partitioning coefficients revealed in most cases a large underestimation by the theory reaching 1 to 7 orders of magnitude.
Danitza Klopper, Paola Formenti, Andreas Namwoonde, Mathieu Cazaunau, Servanne Chevaillier, Anaïs Feron, Cécile Gaimoz, Patrick Hease, Fadi Lahmidi, Cécile Mirande-Bret, Sylvain Triquet, Zirui Zeng, and Stuart J. Piketh
Atmos. Chem. Phys., 20, 15811–15833, https://doi.org/10.5194/acp-20-15811-2020, https://doi.org/10.5194/acp-20-15811-2020, 2020
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The chemical composition of aerosol particles is very important as it determines to which extent they can affect the Earth's climate by acting with solar light and modifying the properties of clouds. The South Atlantic region is a remote and under-explored region to date where these effects could be important. The measurements presented in this paper consist in the analysis of samples collected at a coastal site in Namibia. The first long-term source apportionment is presented and discussed.
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
Atmos. Meas. Tech., 13, 6311–6323, https://doi.org/10.5194/amt-13-6311-2020, https://doi.org/10.5194/amt-13-6311-2020, 2020
Short summary
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An incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS) technique has been developed for the in situ monitoring of NO3 radicals in the CSA simulation chamber at LISA. The optical cavity allows a high sensitivity for NO3 detection up to 6 ppt for an integration time of 10 s. The technique is now fully operational and can be used to determine rate constants for fast reactions involving complex volatile organic compounds (with rate constants up to 10−10 cm3 molecule−1 s−1).
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
Atmos. Chem. Phys., 20, 13521–13539, https://doi.org/10.5194/acp-20-13521-2020, https://doi.org/10.5194/acp-20-13521-2020, 2020
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We showed that Icelandic dust has a fundamentally different chemical and mineralogical composition from low-latitude dust. In particular, magnetite is as high as 1 %–2 % of the total dust mass. Our results suggest that Icelandic dust may have an important impact on the radiation balance in the subpolar and polar regions.
Cited articles
Alage, S., Michoud, V., Harb, S., Picquet-Varrault, B., Cirtog, M., Kumar, A., Rissanen, M., and Cantrell, C.: A nitrate ion chemical-ionization atmospheric-pressure-interface time-of-flight mass spectrometer (NO
Bates, K. H., Burke, G. J. P., Cope, J. D., and Nguyen, T. B.: Secondary organic aerosol and organic nitrogen yields from the nitrate radical (NO3) oxidation of alpha-pinene from various RO2 fates, Atmos. Chem. Phys., 22, 1467–1482, https://doi.org/10.5194/acp-22-1467-2022, 2022.
Bell, D. M., Wu, C., Bertrand, A., Graham, E., Schoonbaert, J., Giannoukos, S., Baltensperger, U., Prevot, A. S. H., Riipinen, I., El Haddad, I., and Mohr, C.: Particle-phase processing of α-pinene NO3 secondary organic aerosol in the dark, Atmos. Chem. Phys., 22, 13167–13182, https://doi.org/10.5194/acp-22-13167-2022, 2022.
Berndt, T., Mentler, B., Scholz, W., Fischer, L., Herrmann, H., Kulmala, M., and Hansel, A.: Accretion product formation from ozonolysis and OH radical reaction of α-pinene: mechanistic insight and the influence of isoprene and ethylene, Environ. Sci. Technol., 52, 11069–11077, https://doi.org/10.1021/acs.est.8b02210, 2018a.
Berndt, T., Scholz, W., Mentler, B., Fischer, L., Herrmann, H., Kulmala, M., and Hansel, A.: Accretion product formation from self- and cross-reactions of RO2 radicals in the atmosphere, Angew. Chem. Int. Edit., 57, 3820–3824, https://doi.org/10.1002/anie.201710989, 2018b.
Bianchi, F., Kurtén, T., Riva, M., Mohr, C., Rissanen, M. P., Roldin, P., Berndt, T., Crounse, J. D., Wennberg, P. O., Mentel, T. F., Wildt, J., Junninen, H., Jokinen, T., Kulmala, M., Worsnop, D. R., Thornton, J. A., Donahue, N., Kjaergaard, H. G., and Ehn, M.: Highly oxygenated organic molecules (HOM) from gas-phase autoxidation involving peroxy radicals: a key contributor to atmospheric aerosol, Chem. Rev., 119, 3472–3509, https://doi.org/10.1021/acs.chemrev.8b00395, 2019.
Boyd, C. M., Sanchez, J., Xu, L., Eugene, A. J., Nah, T., Tuet, W. Y., Guzman, M. I., and Ng, N. L.: Secondary organic aerosol formation from the β-pinene + NO3 system: effect of humidity and peroxy radical fate, Atmos. Chem. Phys., 15, 7497–7522, https://doi.org/10.5194/acp-15-7497-2015, 2015.
Brown, S. S., deGouw, J. A., Warneke, C., Ryerson, T. B., Dubé, W. P., Atlas, E., Weber, R. J., Peltier, R. E., Neuman, J. A., Roberts, J. M., Swanson, A., Flocke, F., McKeen, S. A., Brioude, J., Sommariva, R., Trainer, M., Fehsenfeld, F. C., and Ravishankara, A. R.: Nocturnal isoprene oxidation over the Northeast United States in summer and its impact on reactive nitrogen partitioning and secondary organic aerosol, Atmos. Chem. Phys., 9, 3027–3042, https://doi.org/10.5194/acp-9-3027-2009, 2009.
Brown, S. S., Dubé, W. P., Peischl, J., Ryerson, T. B., Atlas, E., Warneke, C., de Gouw, J. A., te Lintel Hekkert, S., Brock, C. A., Flocke, F., Trainer, M., Parrish, D. D., Fehsenfeld, F. C., and Ravishankara, A. R.: Budgets for nocturnal VOC oxidation by nitrate radicals aloft during the 2006 Texas Air Quality Study, J. Geophys. Res.-Atmos., 116, D24303, https://doi.org/10.1029/2011JD016544, 2011.
Brown, S. S. and Stutz, J.: Nighttime radical observations and chemistry, Chem. Soc. Rev., 41, 6405–6447, https://doi.org/10.1039/C2CS35181A, 2012.
Bruns, E. A., Perraud, V., Zelenyuk, A., Ezell, M. J., Johnson, S. N., Yu, Y., Imre, D., Finlayson-Pitts, B. J., and Alexander, M. L.: Comparison of FTIR and particle mass spectrometry for the measurement of particulate organic nitrates, Environ. Sci. Technol., 44, 1056–1061, https://doi.org/10.1021/es9029864, 2010.
Claflin, M. S. and Ziemann, P. J.: Identification and quantitation of aerosol products of the reaction of β-pinene with NO3 radicals and implications for gas- and particle-phase reaction mechanisms, J. Phys. Chem. A, 122, 3640–3652, https://doi.org/10.1021/acs.jpca.8b00692, 2018.
Crounse, J. D., Nielsen, L. B., Jørgensen, S., Kjaergaard, H. G., and Wennberg, P. O.: Autoxidation of organic compounds in the atmosphere, J. Phys. Chem. Lett., 4, 3513–3520, https://doi.org/10.1021/jz4019207, 2013.
Curtis, A. R.: The FACSIMILE numerical integrator for stiff initial value problems, AERE Report R-9352, UK Atomic Energy Research Establishment, Harwell, 1979.
Dam, M., Draper, D. C., Marsavin, A., Fry, J. L., and Smith, J. N.: Observations of gas-phase products from the nitrate-radical-initiated oxidation of four monoterpenes, Atmos. Chem. Phys., 22, 9017–9031, https://doi.org/10.5194/acp-22-9017-2022, 2022.
Day, D. A., Fry, J. L., Kang, H. G., Krechmer, J. E., Ayres, B. R., Keehan, N. I., Thompson, S. L., Hu, W., Campuzano-Jost, P., Schroder, J. C., Stark, H., DeVault, M. P., Ziemann, P. J., Zarzana, K. J., Wild, R. J., Dubé, W. P., Brown, S. S., and Jimenez, J. L.: Secondary organic aerosol mass yields from NO3 oxidation of α-pinene and Δ-carene: effect of RO2 radical fate, J. Phys. Chem. A, 126, 7309–7330, https://doi.org/10.1021/acs.jpca.2c04419, 2022.
DeVault, M. P., Ziola, A. C., and Ziemann, P. J.: Products and mechanisms of secondary organic aerosol formation from the NO3 radical-initiated oxidation of cyclic and acyclic monoterpenes, ACS Earth Space Chem., 6, 2076–2092, https://doi.org/10.1021/acsearthspacechem.2c00130, 2022.
Doussin, J.-F., Fuchs, H., Kiendler-Scharr, A., Seakins, P., and Wenger, J. (Eds.): A Practical Guide to Atmospheric Simulation Chambers, Springer Nature, https://doi.org/10.1007/978-3-031-22277-1, 2023.
Draper, D. C., Farmer, D. K., Desyaterik, Y., and Fry, J. L.: A qualitative comparison of secondary organic aerosol yields and composition from ozonolysis of monoterpenes at varying concentrations of NO2, Atmos. Chem. Phys., 15, 12267–12281, https://doi.org/10.5194/acp-15-12267-2015, 2015.
Draper, D. C., Myllys, N., Hyttinen, N., Møller, K. H., Kjaergaard, H. G., Fry, J. L., Smith, J. N., and Kurtén, T.: Formation of highly oxidized molecules from NO3 radical initiated oxidation of Δ-3-carene: a mechanistic study, ACS Earth Space Chem., 3, 1460–1470, https://doi.org/10.1021/acsearthspacechem.9b00143, 2019.
Duncianu, M., David, M., Kartigueyane, S., Cirtog, M., Doussin, J.-F., and Picquet-Varrault, B.: Measurement of alkyl and multifunctional organic nitrates by proton-transfer-reaction mass spectrometry, Atmos. Meas. Tech., 10, 1445–1463, https://doi.org/10.5194/amt-10-1445-2017, 2017.
Ehn, M., Thornton, J. A., Kleist, E., Sipilä, M., Junninen, H., Pullinen, I., Springer, M., Rubach, F., Tillmann, R., Lee, B., Lopez-Hilfiker, F., Andres, S., Acir, I.-H., Rissanen, M., Jokinen, T., Schobesberger, S., Kangasluoma, J., Kontkanen, J., Nieminen, T., Kurtén, T., Nielsen, L. B., Jørgensen, S., Kjaergaard, H. G., Canagaratna, M., Maso, M. D., Berndt, T., Petäjä, T., Wahner, A., Kerminen, V.-M., Kulmala, M., Worsnop, D. R., Wildt, J., and Mentel, T. F.: A large source of low-volatility secondary organic aerosol, Nature, 506, 476–479, https://doi.org/10.1038/nature13032, 2014.
EMEP/EEA: EMEP/EEA air pollutant emission inventory guidebook 2023, European Environment Agency, Copenhagen, https://www.eea.europa.eu/en/analysis/publications/emep-eea-guidebook-2023 (last access: 19 January 2025), 2023.
Farmer, D. K., Matsunaga, A., Docherty, K. S., Surratt, J. D., Seinfeld, J. H., Ziemann, P. J., and Jimenez, J. L.: Response of an aerosol mass spectrometer to organonitrates and organosulfates and implications for atmospheric chemistry, P. Natl. Acad. Sci. USA, 107, 6670–6675, https://doi.org/10.1073/pnas.0912340107, 2010.
Faxon, C., Hammes, J., Le Breton, M., Pathak, R. K., and Hallquist, M.: Characterization of organic nitrate constituents of secondary organic aerosol (SOA) from nitrate-radical-initiated oxidation of limonene using high-resolution chemical ionization mass spectrometry, Atmos. Chem. Phys., 18, 5467–5481, https://doi.org/10.5194/acp-18-5467-2018, 2018.
Fisher, J. A., Jacob, D. J., Travis, K. R., Kim, P. S., Marais, E. A., Chan Miller, C., Yu, K., Zhu, L., Yantosca, R. M., Sulprizio, M. P., Mao, J., Wennberg, P. O., Crounse, J. D., Teng, A. P., Nguyen, T. B., St. Clair, J. M., Cohen, R. C., Romer, P., Nault, B. A., Wooldridge, P. J., Jimenez, J. L., Campuzano-Jost, P., Day, D. A., Hu, W., Shepson, P. B., Xiong, F., Blake, D. R., Goldstein, A. H., Misztal, P. K., Hanisco, T. F., Wolfe, G. M., Ryerson, T. B., Wisthaler, A., and Mikoviny, T.: Organic nitrate chemistry and its implications for nitrogen budgets in an isoprene- and monoterpene-rich atmosphere: constraints from aircraft (SEAC4RS) and ground-based (SOAS) observations in the Southeast US, Atmos. Chem. Phys., 16, 5969–5991, https://doi.org/10.5194/acp-16-5969-2016, 2016.
Fouqueau, A., Cirtog, M., Cazaunau, M., Pangui, E., Doussin, J.-F., and Picquet-Varrault, B.: A comparative and experimental study of the reactivity with nitrate radical of two terpenes: α-terpinene and γ-terpinene, Atmos. Chem. Phys., 20, 15167–15189, https://doi.org/10.5194/acp-20-15167-2020, 2020.
Fouqueau, A., Cirtog, M., Cazaunau, M., Pangui, E., Doussin, J.-F., and Picquet-Varrault, B.: An experimental study of the reactivity of terpinolene and β-caryophyllene with the nitrate radical, Atmos. Chem. Phys., 22, 6411–6434, https://doi.org/10.5194/acp-22-6411-2022, 2022.
Fry, J. L., Kiendler-Scharr, A., Rollins, A. W., Brauers, T., Brown, S. S., Dorn, H.-P., Dubé, W. P., Fuchs, H., Mensah, A., Rohrer, F., Tillmann, R., Wahner, A., Wooldridge, P. J., and Cohen, R. C.: SOA from limonene: role of NO3 in its generation and degradation, Atmos. Chem. Phys., 11, 3879–3894, https://doi.org/10.5194/acp-11-3879-2011, 2011.
Fry, J. L., Draper, D. C., Barsanti, K. C., Smith, J. N., Ortega, J., Winkler, P. M., Lawler, M. J., Brown, S. S., Edwards, P. M., Cohen, R. C., and Lee, L.: Secondary organic aerosol formation and organic nitrate yield from NO3 oxidation of biogenic hydrocarbons, Environ. Sci. Technol., 48, 11944–11953, https://doi.org/10.1021/es502204x, 2014.
Geyer, A., Alicke, B., Konrad, S., Schmitz, T., Stutz, J., and Platt, U.: Chemistry and oxidation capacity of the nitrate radical in the continental boundary layer near Berlin, J. Geophys. Res.-Atmos., 106, 8013–8025, https://doi.org/10.1029/2000JD900681, 2001.
Goldstein, A. H. and Galbally, I. E.: Known and unknown organic constituents in the Earth's atmosphere, Environ. Sci. Technol., 41, 1514–1521, https://doi.org/10.1021/es072476p, 2007.
Guenther, A., Karl, T., Harley, P., Wiedinmyer, C., Palmer, P. I., and Geron, C.: Estimates of global terrestrial isoprene emissions using MEGAN (Model of Emissions of Gases and Aerosols from Nature), Atmos. Chem. Phys., 6, 3181–3210, https://doi.org/10.5194/acp-6-3181-2006, 2006.
Guenther, A. B., Jiang, X., Heald, C. L., Sakulyanontvittaya, T., Duhl, T., Emmons, L. K., and Wang, X.: The Model of Emissions of Gases and Aerosols from Nature version 2.1 (MEGAN2.1): an extended and updated framework for modeling biogenic emissions, Geosci. Model Dev., 5, 1471–1492, https://doi.org/10.5194/gmd-5-1471-2012, 2012.
Guo, Y., Shen, H., Pullinen, I., Luo, H., Kang, S., Vereecken, L., Fuchs, H., Hallquist, M., Acir, I.-H., Tillmann, R., Rohrer, F., Wildt, J., Kiendler-Scharr, A., Wahner, A., Zhao, D., and Mentel, T. F.: Identification of highly oxygenated organic molecules and their role in aerosol formation in the reaction of limonene with nitrate radical, Atmos. Chem. Phys., 22, 11323–11346, https://doi.org/10.5194/acp-22-11323-2022, 2022.
Hallquist, M., Ljungström, E., Wängberg, I., Barnes, I., and Becker, K. H.: Aerosol and product yields from NO3 radical-initiated oxidation of selected monoterpenes, Environ. Sci. Technol., 33, 553–559, https://doi.org/10.1021/es980292s, 1999.
Hao, L. Q., Yli-Pirilä, P., Tiitta, P., Romakkaniemi, S., Vaattovaara, P., Kajos, M. K., Rinne, J., Heijari, J., Kortelainen, A., Miettinen, P., Kroll, J. H., Holopainen, J. K., Smith, J. N., Joutsensaari, J., Kulmala, M., Worsnop, D. R., and Laaksonen, A.: New particle formation from the oxidation of direct emissions of pine seedlings, Atmos. Chem. Phys., 9, 8121–8137, https://doi.org/10.5194/acp-9-8121-2009, 2009.
Harb, S., Cirtog, M., Cazaunau, M., Pangui, E., Bergé, A., and Picquet-Varrault, B.: Experimental kinetic study of the reactions between NO3 radicals and α- and β-phellandrenes, Int. J. Chem. Kinet., 57, 364–371, https://doi.org/10.1002/kin.21782, 2025.
Harb, S., Picquet-Varrault, B., Cirtog, M., Cazaunau, M., Pangui, E., Berge, A., Giorio, C., Battaglia, F., Michoud, V., Alage, S., and Cantrell, C.: Datasets – α-phellandrene + NO3 and β-phellandrene [data], https://doi.org/10.25326/1QJ4-Z433, 2025.
He, C., Murray, F., and Lyons, T.: Monoterpene and isoprene emissions from 15 Eucalyptus species in Australia, Atmos. Environ., 34, 645–655, https://doi.org/10.1016/S1352-2310(99)00219-8, 2000.
Hjorth, J., Ottobrini, G., Cappellani, F., and Restelli, G.: A Fourier transform infrared study of the rate constant of the homogeneous gas-phase reaction nitrogen oxide (N2O5) + water and determination of absolute infrared band intensities of N2O5 and nitric acid, J. Phys. Chem., 91, 1565–1568, https://doi.org/10.1021/j100290a055, 1987.
Huang, W., Saathoff, H., Shen, X., Ramisetty, R., Leisner, T., and Mohr, C.: Chemical characterization of highly functionalized organonitrates contributing to night-time organic aerosol mass loadings and particle growth, Environ. Sci. Technol., 53, 1165–1174, https://doi.org/10.1021/acs.est.8b05826, 2019.
Ito, A., Sillman, S., and Penner, J. E.: Effects of additional nonmethane volatile organic compounds, organic nitrates, and direct emissions of oxygenated organic species on global tropospheric chemistry, J. Geophys. Res.-Atmos., 112, D06309, https://doi.org/10.1029/2005JD006556, 2007.
Janson, R.: Monoterpene concentrations in and above a forest of Scots pine, J. Atmos. Chem., 14, 385–394, https://doi.org/10.1007/BF00115246, 1992.
Jokinen, T., Berndt, T., Makkonen, R., Kerminen, V.-M., Junninen, H., Paasonen, P., Stratmann, F., Herrmann, H., Guenther, A. B., Worsnop, D. R., Kulmala, M., Ehn, M., and Sipilä, M.: Production of extremely low volatile organic compounds from biogenic emissions: measured yields and atmospheric implications, P. Natl. Acad. Sci. USA, 112, 7123–7128, https://doi.org/10.1073/pnas.1423977112, 2015.
Joutsensaari, J., Yli-Pirilä, P., Korhonen, H., Arola, A., Blande, J. D., Heijari, J., Kivimäenpää, M., Mikkonen, S., Hao, L., Miettinen, P., Lyytikäinen-Saarenmaa, P., Faiola, C. L., Laaksonen, A., and Holopainen, J. K.: Biotic stress accelerates formation of climate-relevant aerosols in boreal forests, Atmos. Chem. Phys., 15, 12139–12157, https://doi.org/10.5194/acp-15-12139-2015, 2015.
Junninen, H., Ehn, M., Petäjä, T., Luosujärvi, L., Kotiaho, T., Kostiainen, R., Rohner, U., Gonin, M., Fuhrer, K., Kulmala, M., and Worsnop, D. R.: A high-resolution mass spectrometer to measure atmospheric ion composition, Atmos. Meas. Tech., 3, 1039–1053, https://doi.org/10.5194/amt-3-1039-2010, 2010.
Kenagy, H. S., Romer Present, P. S., Wooldridge, P. J., Nault, B. A., Campuzano-Jost, P., Day, D. A., Jimenez, J. L., Zare, A., Pye, H. O. T., Yu, J., Song, C. H., Blake, D. R., Woo, J.-H., Kim, Y., and Cohen, R. C.: Contribution of organic nitrates to organic aerosol over South Korea during KORUS-AQ, Environ. Sci. Technol., 55, 16326–16338, https://doi.org/10.1021/acs.est.1c05521, 2021.
Kerdouci, J., Picquet-Varrault, B., and Doussin, J.-F.: Prediction of rate constants for gas-phase reactions of nitrate radical with organic compounds: a new structure–activity relationship, Chem. Phys. Chem., 11, 3909–3920, https://doi.org/10.1002/cphc.201000673, 2010.
Kiendler-Scharr, A., Mensah, A. A., Friese, E., Topping, D., Nemitz, E., Prevot, A. S. H., Äijälä, M., Allan, J., Canonaco, F., Canagaratna, M., Carbone, S., Crippa, M., Dall Osto, M., Day, D. A., De Carlo, P., Di Marco, C. F., Elbern, H., Eriksson, A., Freney, E., Hao, L., Herrmann, H., Hildebrandt, L., Hillamo, R., Jimenez, J. L., Laaksonen, A., McFiggans, G., Mohr, C., O'Dowd, C., Otjes, R., Ovadnevaite, J., Pandis, S. N., Poulain, L., Schlag, P., Sellegri, K., Swietlicki, E., Tiitta, P., Vermeulen, A., Wahner, A., Worsnop, D., and Wu, H.-C.: Ubiquity of organic nitrates from nighttime chemistry in the European submicron aerosol, Geophys. Res. Lett., 43, 7735–7744, https://doi.org/10.1002/2016GL069239, 2016.
Kourtchev, I., Fuller, S. J., Giorio, C., Healy, R. M., Wilson, E., O'Connor, I., Wenger, J. C., McLeod, M., Aalto, J., Ruuskanen, T. M., Maenhaut, W., Jones, R., Venables, D. S., Sodeau, J. R., Kulmala, M., and Kalberer, M.: Molecular composition of biogenic secondary organic aerosols using ultrahigh-resolution mass spectrometry: comparing laboratory and field studies, Atmos. Chem. Phys., 14, 2155–2167, https://doi.org/10.5194/acp-14-2155-2014, 2014.
Kroll, J. H. and Seinfeld, J. H.: Chemistry of secondary organic aerosol: Formation and evolution of low-volatility organics in the atmosphere, Atmos. Environ., 42, 3593–3624, https://doi.org/10.1016/j.atmosenv.2008.01.003, 2008.
Lai, K. and Nazaroff, W. W.: Modeling indoor particle deposition from turbulent flow onto smooth surfaces, J. Aerosol Sci., 31, 463–476, https://doi.org/10.1016/S0021-8502(99)00536-4, 2000.
Lamkaddam, H., Gratien, A., Pangui, E., Cazaunau, M., Picquet-Varrault, B., and Doussin, J.-F.: High-NOx photooxidation of n-dodecane: Temperature dependence of SOA formation, Environ. Sci. Technol., 51, 192–201, https://doi.org/10.1021/acs.est.6b03821, 2017.
Lee, B. H., Mohr, C., Lopez-Hilfiker, F. D., Lutz, A., Hallquist, M., Lee, L., Romer, P., Cohen, R. C., Iyer, S., Kurtén, T., Hu, W., Day, D. A., Campuzano-Jost, P., Jimenez, J. L., Xu, L., Ng, N. L., Guo, H., Weber, R. J., Wild, R. J., Brown, S. S., Koss, A., de Gouw, J., Olson, K., Goldstein, A. H., Seco, R., Kim, S., McAvey, K., Shepson, P. B., Starn, T., Baumann, K., Edgerton, E. S., Liu, J., Shilling, J. E., Miller, D. O., Brune, W., Schobesberger, S., D'Ambro, E. L., and Thornton, J. A.: Highly functionalized organic nitrates in the southeast United States: Contribution to secondary organic aerosol and reactive nitrogen budgets, P. Natl. Acad. Sci. USA, 113, 1516–1521, https://doi.org/10.1073/pnas.1508108113, 2016.
Li, H., Madden, J. L., and Potts, B. M.: Variation in volatile leaf oils of the Tasmanian Eucalyptus species – 1. Subgenus Monocalyptus, Biochem. Syst. Ecol., 23, 299–318, https://doi.org/10.1016/0305-1978(95)97455-6, 1995.
Liebmann, J., Sobanski, N., Schuladen, J., Karu, E., Hellén, H., Hakola, H., Zha, Q., Ehn, M., Riva, M., Heikkinen, L., Williams, J., Fischer, H., Lelieveld, J., and Crowley, J. N.: Alkyl nitrates in the boreal forest: formation via the NO
Maghsoodlou, M. T., Kazemipoor, N., Valizadeh, J., Falak Nezhad Seifi, M., and Rahneshan, N.: Essential oil composition of Eucalyptus microtheca and Eucalyptus viminalis, Avicenna J. Phytomed., 5, 540–552, https://doi.org/10.22038/ajp.2015.4470, 2015.
Maleknia, S. D., Bell, T. L., and Adams, M. A.: Eucalypt smoke and wildfires: Temperature dependent emissions of biogenic volatile organic compounds, Int. J. Mass Spectrom., 279, 126–133, https://doi.org/10.1016/j.ijms.2008.10.027, 2009.
Mayorga, R., Xia, Y., Zhao, Z., Long, B., and Zhang, H.: Peroxy radical autoxidation and sequential oxidation in organic nitrate formation during limonene nighttime oxidation, Environ. Sci. Technol., 56, 15337–15346, https://doi.org/10.1021/acs.est.2c04030, 2022.
Mentel, T. F., Springer, M., Ehn, M., Kleist, E., Pullinen, I., Kurtén, T., Rissanen, M., Wahner, A., and Wildt, J.: Formation of highly oxidized multifunctional compounds: autoxidation of peroxy radicals formed in the ozonolysis of alkenes – deduced from structure–product relationships, Atmos. Chem. Phys., 15, 6745–6765, https://doi.org/10.5194/acp-15-6745-2015, 2015.
Messina, P., Lathière, J., Sindelarova, K., Vuichard, N., Granier, C., Ghattas, J., Cozic, A., and Hauglustaine, D. A.: Global biogenic volatile organic compound emissions in the ORCHIDEE and MEGAN models and sensitivity to key parameters, Atmos. Chem. Phys., 16, 14169–14202, https://doi.org/10.5194/acp-16-14169-2016, 2016.
Mogensen, D., Gierens, R., Crowley, J. N., Keronen, P., Smolander, S., Sogachev, A., Nölscher, A. C., Zhou, L., Kulmala, M., Tang, M. J., Williams, J., and Boy, M.: Simulations of atmospheric OH, O3 and NO3 reactivities within and above the boreal forest, Atmos. Chem. Phys., 15, 3909–3932, https://doi.org/10.5194/acp-15-3909-2015, 2015.
Moldanova, J. and Ljungström, E.: Modelling of particle formation from NO3 oxidation of selected monoterpenes, J. Aerosol Sci., 31, 1317–1333, https://doi.org/10.1016/S0021-8502(00)00041-0, 2000.
Møller, K. H., Bates, K. H., and Kjaergaard, H. G.: The importance of peroxy radical hydrogen-shift reactions in atmospheric isoprene oxidation, J. Phys. Chem. A, 123, 920–932, https://doi.org/10.1021/acs.jpca.8b10432, 2019.
Møller, K. H., Otkjær, R. V., Chen, J., and Kjaergaard, H. G.: Double bonds are key to fast unimolecular reactivity in first-generation monoterpene hydroxy peroxy radicals, J. Phys. Chem. A, 124, 2885–2896, https://doi.org/10.1021/acs.jpca.0c01079, 2020.
Mutzel, A., Zhang, Y., Böge, O., Rodigast, M., Kolodziejczyk, A., Wang, X., and Herrmann, H.: Importance of secondary organic aerosol formation of α-pinene, limonene, and m-cresol comparing day- and nighttime radical chemistry, Atmos. Chem. Phys., 21, 8479–8498, https://doi.org/10.5194/acp-21-8479-2021, 2021.
Nah, T., Sanchez, J., and Boyd, C. M.: Photochemical aging of α-pinene and β-pinene secondary organic aerosol formed from nitrate radical oxidation, Environ. Sci. Technol., 50, 222–231, https://doi.org/10.1021/acs.est.5b04594, 2016.
Ng, N. L., Brown, S. S., Archibald, A. T., Atlas, E., Cohen, R. C., Crowley, J. N., Day, D. A., Donahue, N. M., Fry, J. L., Fuchs, H., Griffin, R. J., Guzman, M. I., Herrmann, H., Hodzic, A., Iinuma, Y., Jimenez, J. L., Kiendler-Scharr, A., Lee, B. H., Luecken, D. J., Mao, J., McLaren, R., Mutzel, A., Osthoff, H. D., Ouyang, B., Picquet-Varrault, B., Platt, U., Pye, H. O. T., Rudich, Y., Schwantes, R. H., Shiraiwa, M., Stutz, J., Thornton, J. A., Tilgner, A., Williams, B. J., and Zaveri, R. A.: Nitrate radicals and biogenic volatile organic compounds: oxidation, mechanisms, and organic aerosol, Atmos. Chem. Phys., 17, 2103–2162, https://doi.org/10.5194/acp-17-2103-2017, 2017.
Odum, J. R., Hoffmann, T., Bowman, F., Collins, D., Flagan, R. C., and Seinfeld, J. H.: Gas/particle partitioning and secondary organic aerosol yields, Environ. Sci. Technol., 30, 2580–2585, https://doi.org/10.1021/es950943+, 1996.
Pavlova, L. V., Platonov, I. A., Nikitchenko, N. V., and Novikova, E. A.: Evaluation of the efficiency of volatile organic compounds extraction from Eucalyptus viminalis (Eucalypti viminalis Labill) using subcritical extractants, Russ. J. Phys. Chem. B, 9, 1109–1115, https://doi.org/10.1134/S1990793115080084, 2015.
Picquet-Varrault, B., Scarfogliero, M., Helal, W. A., and Doussin, J.-F.: Reevaluation of the rate constant for the reaction propene + NO3 by absolute rate determination, Int. J. Chem. Kinet., 41, 73–81, https://doi.org/10.1002/kin.20371, 2009.
Picquet-Varrault, B., Suarez-Bertoa, R., Duncianu, M., Cazaunau, M., Pangui, E., David, M., and Doussin, J.-F.: Photolysis and oxidation by OH radicals of two carbonyl nitrates: 4-nitrooxy-2-butanone and 5-nitrooxy-2-pentanone, Atmos. Chem. Phys., 20, 487–498, https://doi.org/10.5194/acp-20-487-2020, 2020.
Rindelaub, J. D., McAvey, K. M., and Shepson, P. B.: The photochemical production of organic nitrates from α-pinene and loss via acid-dependent particle phase hydrolysis, Atmos. Environ., 100, 193–201, https://doi.org/10.1016/j.atmosenv.2014.11.010, 2015.
Rothman, L. S., Barbe, A., Benner, D. C., Brown, L. R., Camy-Peyret, C., Carleer, M. R., Chance, K., Clerbaux, C., Dana, V., Devi, V. M., Fayt, A., Flaud, J.-M., Gamache, R. R., Goldman, A., Jacquemart, D., Jucks, K. W., Lafferty, W. J., Mandin, J.-Y., Massie, S. T., Nemtchinov, V., Newnham, D. A., Perrin, A., Rinsland, C. P., Schroeder, J., Smith, K. M., Smith, M. A. H., Tang, K., Toth, R. A., Vander Auwera, J., Varanasi, P., and Yoshino, K.: The HITRAN molecular spectroscopic database: edition of 2000 including updates through 2001, J. Quant. Spectrosc. Ra., 82, 5–44, https://doi.org/10.1016/S0022-4073(03)00146-8, 2003.
Saunders, S. M., Jenkin, M. E., Derwent, R. G., and Pilling, M. J.: Protocol for the development of the Master Chemical Mechanism, MCM v3 (Part A): tropospheric degradation of non-aromatic volatile organic compounds, Atmos. Chem. Phys., 3, 161–180, https://doi.org/10.5194/acp-3-161-2003, 2003.
Shen, H., Zhao, D., Pullinen, I., Kang, S., Vereecken, L., Fuchs, H., Acir, I.-H., Tillmann, R., Rohrer, F., Wildt, J., Kiendler-Scharr, A., Wahner, A., and Mentel, T. F.: Highly oxygenated organic nitrates formed from NO3 radical-initiated oxidation of β-pinene, Environ. Sci. Technol., 55, 15658–15671, https://doi.org/10.1021/acs.est.1c03978, 2021.
Shen, H., Vereecken, L., Kang, S., Pullinen, I., Fuchs, H., and Zhao, D.: Unexpected significance of a minor reaction pathway in daytime formation of biogenic highly oxygenated organic compounds, Sci. Adv., 8, eabp8702, https://doi.org/10.1126/sciadv.abp8702, 2022.
Sindelarova, K., Granier, C., Bouarar, I., Guenther, A., Tilmes, S., Stavrakou, T., Müller, J.-F., Kuhn, U., Stefani, P., and Knorr, W.: Global data set of biogenic VOC emissions calculated by the MEGAN model over the last 30 years, Atmos. Chem. Phys., 14, 9317–9341, https://doi.org/10.5194/acp-14-9317-2014, 2014.
Slade, J. H., de Perre, C., Lee, L., and Shepson, P. B.: Nitrate radical oxidation of γ-terpinene: hydroxy nitrate, total organic nitrate, and secondary organic aerosol yields, Atmos. Chem. Phys., 17, 8635–8650, https://doi.org/10.5194/acp-17-8635-2017, 2017.
Spittler, M., Barnes, I., Bejan, I., Brockmann, K. J., Benter, Th., and Wirtz, K.: Reactions of NO3 radicals with limonene and α-pinene: product and SOA formation, Atmos. Environ., 40, 116–127, https://doi.org/10.1016/j.atmosenv.2005.09.093, 2006.
Suarez-Bertoa, R., Picquet-Varrault, B., Tamas, W., Pangui, E., and Doussin, J.-F.: Atmospheric fate of a series of carbonyl nitrates: photolysis frequencies and OH-oxidation rate constants, Environ. Sci. Technol., 46, 12502–12509, https://doi.org/10.1021/es302613x, 2012.
Takeuchi, M. and Ng, N. L.: Chemical composition and hydrolysis of organic nitrate aerosol formed from hydroxyl and nitrate radical oxidation of α-pinene and β-pinene, Atmos. Chem. Phys., 19, 12749–12766, https://doi.org/10.5194/acp-19-12749-2019, 2019.
Vereecken, L. and Nozière, B.: H migration in peroxy radicals under atmospheric conditions, Atmos. Chem. Phys., 20, 7429–7458, https://doi.org/10.5194/acp-20-7429-2020, 2020.
Vereecken, L., Carlsson, P. T. M., Novelli, A., Bernard, F., Brown, S. S., Cho, C., Crowley, J. N., Fuchs, H., Mellouki, A., Reimer, D., Shenolikar, J., Tillmann, R., Zhou, L., Kiendler-Scharr, A., and Wahner, A.: Theoretical and experimental study of peroxy and alkoxy radicals in the NO3-initiated oxidation of isoprene, Phys. Chem. Chem. Phys., 23, 5496–5515, https://doi.org/10.1039/D0CP06267G, 2021.
Wang, J., Doussin, J. F., Perrier, S., Perraudin, E., Katrib, Y., Pangui, E., and Picquet-Varrault, B.: Design of a new multi-phase experimental simulation chamber for atmospheric photosmog, aerosol and cloud chemistry research, Atmos. Meas. Tech., 4, 2465–2494, https://doi.org/10.5194/amt-4-2465-2011, 2011.
Wang, L., Wu, R., and Xu, C.: Atmospheric oxidation mechanism of benzene: fates of alkoxy radical intermediates and revised mechanism, J. Phys. Chem. A, 117, 14163–14168, https://doi.org/10.1021/jp4101762, 2013.
Xu, L., Suresh, S., Guo, H., Weber, R. J., and Ng, N. L.: Aerosol characterization over the southeastern United States using high-resolution aerosol mass spectrometry: spatial and seasonal variation of aerosol composition and sources with a focus on organic nitrates, Atmos. Chem. Phys., 15, 7307–7336, https://doi.org/10.5194/acp-15-7307-2015, 2015.
Yassaa, N., Song, W., Lelieveld, J., Vanhatalo, A., Bäck, J., and Williams, J.: Diel cycles of isoprenoids in the emissions of Norway spruce, four Scots pine chemotypes, and in Boreal forest ambient air during HUMPPA-COPEC-2010, Atmos. Chem. Phys., 12, 7215–7229, https://doi.org/10.5194/acp-12-7215-2012, 2012.
Ylisirniö, A., Buchholz, A., Mohr, C., Li, Z., Barreira, L., Lambe, A., Faiola, C., Kari, E., Yli-Juuti, T., Nizkorodov, S. A., Worsnop, D. R., Virtanen, A., and Schobesberger, S.: Composition and volatility of secondary organic aerosol (SOA) formed from oxidation of real tree emissions compared to simplified volatile organic compound (VOC) systems, Atmos. Chem. Phys., 20, 5629–5644, https://doi.org/10.5194/acp-20-5629-2020, 2020.
Zhao, Y., Thornton, J. A., and Pye, H. O. T.: Quantitative constraints on autoxidation and dimer formation from direct probing of monoterpene-derived peroxy radical chemistry, P. Natl. Acad. Sci. USA, 115, 12142–12147, https://doi.org/10.1073/pnas.1812147115, 2018.
Zielinski, A. T., Kourtchev, I., Bortolini, C., Fuller, S. J., Giorio, C., Popoola, O. A. M., Bogialli, S., Tapparo, A., Jones, R. L., and Kalberer, M.: A new processing scheme for ultra-high resolution direct infusion mass spectrometry data, Atmos. Environ., 178, 129–139, https://doi.org/10.1016/j.atmosenv.2018.01.034, 2018.
Short summary
We investigated the reactions of α- and β-phellandrenes (from vegetation emissions) with NO3 radicals, a major nighttime oxidant from human activities. Using lab-based simulations, we examined these reactions and measured particle formation and by-products. Our findings reveal that α- and β-phellandrenes are efficient particle sources and enhance our understanding of biogenic–anthropogenic interactions and their contributions to atmospheric changes affecting climate and health.
We investigated the reactions of α- and β-phellandrenes (from vegetation emissions) with NO3...
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