Project

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Feedbacks between atmospheric aerosol microphysics and photochemical aging

Applicant Ammann Markus
Number 163074
Funding scheme Project funding (Div. I-III)
Research institution Paul Scherrer Institut
Institution of higher education Paul Scherrer Institute - PSI
Main discipline Physical Chemistry
Start/End 01.01.2016 - 31.12.2019
Approved amount 528'755.00
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All Disciplines (3)

Discipline
Physical Chemistry
Organic Chemistry
Climatology. Atmospherical Chemistry, Aeronomy

Keywords (6)

photosensitizer; viscosity; aerosol; photochemistry; atmospheric chemistry; organic aerosol

Lay Summary (German)

Lead
Atmosphärische Aerosole sind essentieller Bestandteil der natürlichen Wasser- und Stoffkreisläufe und beeinflussen Klima, Oekosysteme und die menschliche Gesundheit. In der Beurteilung der Auswirkungen menschlicher Aktivitäten spielen Aerosole deshalb eine wichtige Rolle. Während der Aufenthaltszeit von Aerosolen in der Atmosphäre von etwa einer Woche, beeinflussen chemische Transformationen die Klimawirksamkeit oder die Toxizität entscheidend. Besonders photochemische Prozesse in der Partikelphase sind noch kaum untersucht worden. Von diesen sind vorallem jene interessant, bei denen Stoffe nicht durch direkte Photolyse durch kurzwelliges UV Licht umgewandelt werden, sondern indirekt durch Energietransfer von Chromophoren, die durch längerwelliges Licht angeregt werden. Dabei spielen die physikalischen Eigenschaften der Partikel wie deren Wassergehalt, Viskosität, optische Absorptionskoeffizienten eine wichtige Rolle beziehungsweise werden von diesen beeinflusst.
Lay summary
Unser übergeordnetes Ziel ist, den Zusammenhang zwischen indirekten photochemischen Prozessen und den mikrophysikalischen Eigenschaften von Aerosolteilchen zu verstehen. Wir wählen eine Herangehensweise über drei verschiedene experimentelle Techniken sowie eine Modellierungsmethode um die experimentellen Resultate einordnen zu können und auf atmosphärische Bedingungen anwenden zu können. Die erste Technik basiert auf einer elektrodynamischen Falle an der ETH Zürich, worin mikrophysikalische Parameter über sehr lange Zeitskalen und über weite Temperatur- und Feuchtebereiche untersucht werden können. Die zweite Technik, Röntgenmikroskopie am Paul Scherrer Institut, erlaubt es, Einzelteilchen in situ während photochemischer Transformationen in ihrer Morphologie und chemischer Zusammensetzung mit hoher Auflösung zu untersuchen. Mit der dritten, dem Strömungsrohr, wird die chemische Kinetik der Produktbildung über ebenfalls einen weiten Temperatur- und Feuchtebereich gemessen. Das kinetische Modell wird dann benutzt, um die experimentellen Beobachtungen zu simulieren und dadurch Informationen über physikalische und chemische Parameter bekommen, die notwendig sind, um die Prozesse unter atmosphärischen Bedingungen zu beschreiben und die Feedbacks zu verstehen, über die sie sich gegenseitig beeinflussen. Mit diesen Methoden werden wir Prozesse mit drei verschiedenen Klassen von Chromophoren untersuchen, Eisenkarboxylatkomplexe, Imidazole und aromatische Ketone, um die Kinetik der Umwandlung von organischen Verbindungen, wie sie in der Atmosphäre vorkommen, zu messen.
Direct link to Lay Summary Last update: 02.12.2015

Responsible applicant and co-applicants

Employees

Publications

Publication
Photolytic radical persistence due to anoxia in viscous aerosol particles
Alpert Peter A., Dou Jing, Corral Arroyo Pablo, Schneider Frederic, Xto Jacinta, Luo Beiping, Peter Thomas, Huthwelker Thomas, Borca Camelia N., Henzler Katja D., Schaefer Thomas, Herrmann Hartmut, Raabe Jörg, Watts Benjamin, Krieger Ulrich K., Ammann Markus (2021), Photolytic radical persistence due to anoxia in viscous aerosol particles, in Nature Communications, 12(1), 1769-1769.
Photochemical degradation of iron(III) citrate/citric acid aerosol quantified with the combination of three complementary experimental techniques and a kinetic process model
Dou Jing, Alpert Peter A., Corral Arroyo Pablo, Luo Beiping, Schneider Frederic, Xto Jacinta, Huthwelker Thomas, Borca Camelia N., Henzler Katja D., Raabe Jörg, Watts Benjamin, Herrmann Hartmut, Peter Thomas, Ammann Markus, Krieger Ulrich K. (2021), Photochemical degradation of iron(III) citrate/citric acid aerosol quantified with the combination of three complementary experimental techniques and a kinetic process model, in Atmospheric Chemistry and Physics, 21(1), 315-338.
Visualizing reaction and diffusion in xanthan gum aerosol particles exposed to ozone
Alpert Peter A., Corral Arroyo Pablo, Dou Jing, Krieger Ulrich K., Steimer Sarah S., Förster Jan-David, Ditas Florian, Pöhlker Christopher, Rossignol Stéphanie, Passananti Monica, Perrier Sebastien, George Christian, Shiraiwa Manabu, Berkemeier Thomas, Watts Benjamin, Ammann Markus (2019), Visualizing reaction and diffusion in xanthan gum aerosol particles exposed to ozone, in Physical Chemistry Chemical Physics, 21(37), 20613-20627.
Carbon Dioxide Diffusivity in Single, Levitated Organic Aerosol Particles
Dou Jing, Luo Beiping, Peter Thomas, Alpert Peter A., Corral Arroyo Pablo, Ammann Markus, Krieger Ulrich K. (2019), Carbon Dioxide Diffusivity in Single, Levitated Organic Aerosol Particles, in The Journal of Physical Chemistry Letters, 10(15), 4484-4489.
Aircraft soot from conventional fuels and biofuels during ground idle and climb-out conditions: Electron microscopy and X-ray micro-spectroscopy
Liati A., Schreiber D., Alpert P.A., Liao Y., Brem B.T., Corral Arroyo P., Hu J., Jonsdottir H.R., Ammann M., Dimopoulos Eggenschwiler P. (2019), Aircraft soot from conventional fuels and biofuels during ground idle and climb-out conditions: Electron microscopy and X-ray micro-spectroscopy, in Environmental Pollution, 247, 658-667.
Halogen activation and radical cycling initiated by imidazole-2-carboxaldehyde photochemistry
Corral Arroyo Pablo, Aellig Raffael, Alpert Peter A., Volkamer Rainer, Ammann Markus (2019), Halogen activation and radical cycling initiated by imidazole-2-carboxaldehyde photochemistry, in Atmospheric Chemistry and Physics Discussions, in press, 1-18.
Time evolution of steep diffusion fronts in highly viscous aerosol particles measured with Mie resonance spectroscopy
Bastelberger S., Krieger U. K., Luo B. P., Peter Th. (2018), Time evolution of steep diffusion fronts in highly viscous aerosol particles measured with Mie resonance spectroscopy, in The Journal of Chemical Physics, 149(24), 244506-244506.
Influence of humidity and iron( iii ) on photodegradation of atmospheric secondary organic aerosol particles
Arroyo Pablo Corral, Malecha Kurtis T., Ammann Markus, Nizkorodov Sergey A. (2018), Influence of humidity and iron( iii ) on photodegradation of atmospheric secondary organic aerosol particles, in Physical Chemistry Chemical Physics, 20(47), 30021-30031.
Particle-Phase Photosensitized Radical Production and Aerosol Aging
Corral Arroyo Pablo, Bartels-Rausch Thorsten, Alpert Peter A., Dumas Stéphane, Perrier Sébastien, George Christian, Ammann Markus (2018), Particle-Phase Photosensitized Radical Production and Aerosol Aging, in Environmental Science & Technology, 52(14), 7680-7688.
Technical note: Monte Carlo genetic algorithm (MCGA) for model analysis of multiphase chemical kinetics to determine transport and reaction rate coefficients using multiple experimental data sets
Berkemeier Thomas, Ammann Markus, Krieger Ulrich K., Peter Thomas, Spichtinger Peter, Pöschl Ulrich, Shiraiwa Manabu, Huisman Andrew J. (2017), Technical note: Monte Carlo genetic algorithm (MCGA) for model analysis of multiphase chemical kinetics to determine transport and reaction rate coefficients using multiple experimental data sets, in Atmospheric Chemistry and Physics, 17(12), 8021-8029.
Heterogeneous photochemistry of imidazole-2-carboxaldehyde: HO<sub>2</sub> radical formation and aerosol growth
González Palacios Laura, Corral Arroyo Pablo, Aregahegn Kifle Z., Steimer Sarah S., Bartels-Rausch Thorsten, Nozière Barbara, George Christian, Ammann Markus, Volkamer Rainer (2016), Heterogeneous photochemistry of imidazole-2-carboxaldehyde: HO<sub>2</sub> radical formation and aerosol growth, in Atmospheric Chemistry and Physics, 16(18), 11823-11836.
Ozone uptake on glassy, semi-solid and liquid organic matter and the role of reactive oxygen intermediates in atmospheric aerosol chemistry
Berkemeier Thomas, Steimer Sarah S., Krieger Ulrich K., Peter Thomas, Pöschl Ulrich, Ammann Markus, Shiraiwa Manabu (2016), Ozone uptake on glassy, semi-solid and liquid organic matter and the role of reactive oxygen intermediates in atmospheric aerosol chemistry, in Physical Chemistry Chemical Physics, 18(18), 12662-12674.

Collaboration

Group / person Country
Types of collaboration
Ch. George / IRCELYON France (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Research Infrastructure
- Exchange of personnel
R. Volkamer, University of Colorado United States of America (North America)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Research Infrastructure
- Exchange of personnel
H. Herrmann, IFT Leipzig Germany (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
M. Shiraiwa and U. Pöschl, Max Planck Institute for Chemistry Germany (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Research Infrastructure
- Exchange of personnel

Scientific events

Active participation

Title Type of contribution Title of article or contribution Date Place Persons involved
American Geophysical Union 2019 Fall Meeting Talk given at a conference Watching Multi-Phase Chemistry Inside Single Aerosol Particles 09.12.2019 San Francisco, United States of America Alpert Peter;
American Geophysical Union Fall Meeting 2019 Talk given at a conference Carbon dioxide diffusivity in single, levitated organic aerosol particles 09.12.2019 San Francisco, United States of America Dou Jing;
International Aerosol Modeling Algorithms Conference 2019 Talk given at a conference Photochemical reaction and diffusion (PRAD) model: The influence of viscosity on photochemistry in single aerosol particles. 05.12.2019 Davis, CA, United States of America Dou Jing;
17th Swiss Geoscience Meeting 2019 Talk given at a conference Chemically Mapping Ice Forming Particles 22.11.2019 Fribourg, Switzerland Alpert Peter; Krieger Ulrich;
Swiss Geoscience Meeting 2019 Talk given at a conference Photochemical aging processes in iron containing aerosols 22.11.2019 Fribourg, Switzerland Dou Jing;
Max Planck Institute of Chemistry Department of Multiphase Chemistry Retreat Talk given at a conference Overview Surface Chemistry group at PSI 09.11.2019 Bingen, Germany Ammann Markus;
ACS 2019: Fundamental Chemical Processes Common to Dissolved Organic Matter & Atmospheric Organic Aerosols Talk given at a conference Feedbacks between aerosol microphysics and photochemical aging in an iron containing secondary organic aerosol (SOA) proxy 27.08.2019 San Diego, United States of America Krieger Ulrich;
European Aerosol Conference 2019 Talk given at a conference Photochemical aging processes in iron containing aerosols 05.08.2019 Gothenburg, Sweden Dou Jing;
Atmospheric Chemistry Gordon Research Conference: : New Science in Air Quality and Climate from Charney to AR6 Talk given at a conference Molecular Diffusion Limitations During Photochemical Aging of Organic Aerosol 28.07.2019 Newry ME, United States of America Alpert Peter;
European Geophysical Union General Assembly Talk given at a conference Diffusion and reaction impeded iron carboxylate complex photochemistry 03.05.2019 Wien, Austria Ammann Markus; Dou Jing; Alpert Peter; Corral Arroyo Pablo; Krieger Ulrich;
European Geophysical Union General Assembly Talk given at a conference Iodine activation photosensitized by imidazole carboxaldehyde 03.05.2019 Wien, Austria Alpert Peter; Corral Arroyo Pablo; Ammann Markus;
CECAM Workshop: Microscopic simulations: forecasting the next two decades Talk given at a conference Interfacing atmospheric multiphase chemistry experiments with theory of electronic structure and molecular dynamics and with simulations of transport and chemical kinetics 24.04.2019 Toulouse, France Ammann Markus;
NOSA(Nordic Society for Aerosol Research)-FAAR(Finnish Association for Aerosol Research) Aerosol Symposium 2018 Poster Photochemical aging processes in iron containing aerosols 04.03.2019 Helsinki, Finland Dou Jing;
Xiamen Symposium on Marine Environmental Sciences Talk given at a conference Photochemical aging processes in iron containing aerosols. 01.01.2019 Xiamen, China Dou Jing;
15 th IGAC Science Conference 2018 Poster Photocatalytic degradation of single, levitated organic aerosol particles containing iron nanoparticles or Arizona test dust 25.09.2018 Takamatsu, Japan Krieger Ulrich;
Towards a moclecular understanding of atmospheric aerosol (MUAA 2018) Poster Iron reoxidation in photochemical cycling 26.08.2018 Bad Honnef, Germany Dou Jing;
Seminar at Peking University, College of Environmental Sciences and Engineering Talk given at a conference Atmospheric aging of viscous organic aerosol particles: a laboratory perspective 30.11.2017 Beijing, China Ammann Markus;
Seminar at Chinese Academy of Science Talk given at a conference Oxidation and photooxidation in viscous organic aerosol particles 24.11.2017 Guangzhou, China Ammann Markus;
School of Energy and Environment, City University of Hong Kong Talk given at a conference Indirect photochemical oxidation in aqueous aerosol particles 23.11.2017 Hongkong, Hongkong Ammann Markus;
Seminar for the Laboratory of Environmental Chemistry Talk given at a conference Adressing atmospheric aerosol microphysics and chemistry with X-ray microspectroscopy 03.11.2017 Berne, Switzerland Alpert Peter;
American Association for Aerosol Research 2017 Poster Feedbacks between atmospheric aerosol microphysics and photochemistry of iron citrates 16.10.2017 Raleigh, United States of America Ammann Markus; Alpert Peter; Dou Jing; Krieger Ulrich; Corral Arroyo Pablo;
European Aerosol Conference 2017 Poster Feedbacks between microphysics and photochemical aging in viscous aerosol 27.08.2017 Zürich, Switzerland Alpert Peter; Ammann Markus; Corral Arroyo Pablo; Dou Jing; Krieger Ulrich;
European Aerosol Conference 2017 Poster Molecular diffusion limitations during photochemical aging of iron citrate aerosols 27.08.2017 Zurich, Switzerland Corral Arroyo Pablo; Alpert Peter; Ammann Markus; Dou Jing; Krieger Ulrich;
American Geophysical Union Fall Meeting Poster Reaction Gradients Viewed Inside Single Photoactive Particles 30.07.2017 New Orleans, United States of America Corral Arroyo Pablo; Dou Jing; Alpert Peter; Krieger Ulrich; Ammann Markus;
Seminar for the State Key Laboratory of Marine Environmental Science Talk given at a conference X-ray Microspectroscopy Applications to Field Studies and Fundamental Research 11.07.2017 Xiamen, China Alpert Peter;
Atmospheric Chemical and Biological processes: interactions and impacts (ATMOCHEMBIO) Talk given at a conference Indirect photochemical oxidation in aqueous sea spray and secondary organic aerosol particles 20.06.2017 Clermont-Ferrand, France Ammann Markus;
Atmospheric chemistry in the anthropocene: Faraday Discussion Poster Feedbacks between microphysics and photochemical aging in viscous aerosol 22.05.2017 York, Great Britain and Northern Ireland Dou Jing;
European Geophysical Union General Assembly 2017 Poster Photochemistry of iron citrates initiated by UV-VUS light 23.04.2017 Vienna, Austria Ammann Markus; Alpert Peter; Corral Arroyo Pablo; Krieger Ulrich; Dou Jing;
European Geosciences Union General Assembly 2017 Talk given at a conference Feedbacks between microphysics and photochemical aging in viscous aerosol 23.04.2017 Vienna, Austria Dou Jing;
International Conference on Aerosol Cycle 2017 Poster Radical production and aerosol aging sustained by photosensitizers within atmospheric particles 21.03.2017 Lille, France Corral Arroyo Pablo; Ammann Markus; Alpert Peter;
European Aerosol Conference 2016 Talk given at a conference Radical production from photosensitization of imidazoles, benzophenone and 4-BBA 05.09.2016 Tours, France Corral Arroyo Pablo;
Towards a molecular level understand of atmospheric aerosols Talk given at a conference Ozone Penetration and Reaction in Organic Aerosol Particles 28.08.2016 Santa Cruz, United States of America Alpert Peter;
CECAM 2016 Workshop: Computational Methods for Modelling Multiply-Charged Droplets Talk given at a conference An Atmospheric Chemistry and Physics Perspective of Aqueous Aerosol Particles 06.07.2016 Lausanne, Switzerland Alpert Peter;
European Geophysical Union General Assembly 2016 Talk given at a conference Radical production from photosensitization of imidazoles, benzophenone and 4-BBA 17.04.2016 Vienna, Austria Corral Arroyo Pablo;


Communication with the public

Communication Title Media Place Year
New media (web, blogs, podcasts, news feeds etc.) Doubts about reaction induced radial chemical composition gradients in viscous aerosol particles? twitter International 2019
New media (web, blogs, podcasts, news feeds etc.) Links between brown carbon photochemistry, peroxy radicals and halogens twitter International 2019
New media (web, blogs, podcasts, news feeds etc.) Brown Carbon #aerosol in the #environment not only absorbs sun light but also transforms energy... twitter International 2018

Awards

Title Year
Top Poster Contest Winner 10th International Aerosol Conference, September 2-7, 2018, St. Louis 2018
Poster prize at the Atmospheric Chemistry in the Anthropocene: Faraday Discussion. 2017
Chemistry Travel Award by The «Platform Chemistry» of the Swiss Academy of Sciences (SCNAT), together with the Swiss Chemical Society (SCS). 2017

Associated projects

Number Title Start Funding scheme
188662 The interplay between reactive oxygen species and the multiphase chemistry of nitrogen, halogen and secondary organic species in aerosol particles 01.03.2020 Project funding (Div. I-III)
189939 Infectivity of influenza viruses in expiratory aerosols under ambient temperatures and humidities (IVEA) 01.06.2020 Sinergia
130175 Heterogeneous chemistry of tropospheric aerosol particles with nitrogen oxides from trace gas kinetics, surface chemical and bulk structural perspectives 01.09.2010 Project funding (Div. I-III)
169176 Multiphase kinetics and chemistry at aqueous solution and mineral oxide - air interfaces 01.01.2017 Project funding (Div. I-III)
146760 Physical states of mixed organic-inorganic aerosols 01.09.2013 Project funding (Div. I-III)
149492 The surface chemistry of tropospheric gas - particle interactions 01.12.2013 Project funding (Div. I-III)

Abstract

Aerosol aging refers to the multitude of physical and chemical transformation atmospheric particles undergo, which play an important role in the impact of aerosols on climate, air quality and health. In this project, we consider indirect photochemical processes, which catalyze redox processes of non-absorbing molecules. Indirect photochemistry is especially relevant in the lower troposphere where UV light intensity with sufficiently low wavelengths to directly photolyze the major organic or inorganic aerosol components is low. Important indirect photochemical processes are transition metal complex photochemistry and photosensitized processes. Iron (Fe(III)) carboxylate complexes absorb light below about 500 nm, which leads to reduction of iron to Fe(II) and oxidation of the carboxylate ligands, a process that represents an important sink of organic acids in the troposphere. Photosensitizers, such as aromatic ketones or imidazoles, form triplet excited states which initiate redox processes with other compounds. Photosensitized processes provide an important contribution to condensed phase radical production, to fragmentation of organics and also to buildup of secondary organic matter. The radical induced oxidation processes in turn also affect the microphysical properties through building up products exhibiting different hydration properties. Furthermore, some of the products of condensed phase oxidation may themselves be chromophores, which may induce an increase in the absorbance of aerosol particles (cf brown carbon) but which may also be active as photosensitizers. It has recently been recognized that aqueous aerosol particles may attain highly viscous, semi-solid or even glassy physical states under a wide range of conditions in the atmosphere. While the impact of reduced mobility of aerosol constituents in high viscosity particles on dark chemical reactions has received substantial attention over the past five years, systematic studies on the effect of high viscosity on photochemical processes are scarce. The reduced mobility and low water content in highly viscous particles impacts on the indirect photochemical processes through affecting the initial absorption process, charge and energy transfer, and by preventing diffusion of intermediates. In turn, the formation of higher molecular weight and more oxygenated products mix may lead to an increase in viscosity of the particles. Thus, a multitude of feedbacks exist that link microphysics and photochemistry in aerosol particles. The approach in this joint project between the ‘Ammann group’ at PSI and the ‘Krieger group’ at ETH follows directly on our previous work, where we have established a link between microphysics and dark oxidation processes. We plan to work with three model systems: Fe(III)-citrate induced citric acid degradation, imidazole carboxaldehyde sensitized citric acid degradation, and imidazole carboxaldehyde sensitized oxidation of phenolic biomass burning proxy compounds. Mass, size, water diffusivity, and optical properties of single levitated particles will be measured in an electrodynamic balance at ETH. Spatially resolved O:C ratios, carbon functional group composition, and Fe oxidation state will be measured by in situ scanning transmission X-ray microscopy (STXM). Measurements of product formation rates and assessment of radical budgets and redox activity will be performed in an irradiated coated wall flow tube (CWFT) experiment. In each of these techniques, the model systems will be followed over time as a function of irradiation, RH and temperature. The integration of the results will be assisted by kinetic model tools. It will provide a sound basis to understand the bidirectional feedbacks between indirect photochemical aerosol aging, optical properties and viscosity for the selected particle system.
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