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Multiphase kinetics and chemistry at aqueous solution and mineral oxide - air interfaces

Applicant Ammann Markus
Number 169176
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 01.01.2017 - 31.07.2020
Approved amount 417'392.00
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All Disciplines (3)

Discipline
Physical Chemistry
Climatology. Atmospherical Chemistry, Aeronomy
Other disciplines of Environmental Sciences

Keywords (11)

heterogeneous chemistry; atmospheric chemistry; aerosol; uptake coefficient; halogens; sea spray aerosol; photochemistry; nitrogen oxides; ice nucleation; mineral dust; X-ray photoelectron spectroscopy

Lay Summary (German)

Lead
Die Grenzflächen zwischen festen oder flüssigen Materialien und Luft in der Umwelt - sei es an der Oberfläche der Kontinente, der Ozeane oder von luftgetragenen Stoffen wie Feinstaub oder Wolkentröpfchen spielen eine wichtige Rolle in Prozessen in der Atmosphäre. Die für diese Prozesse involvierten Grenzflächen oder chemischen Reaktionen daran sind noch zuwenig untersucht worden, und es ist nicht klar, welchen Anteil sie an den genannten Stoffkreisläufen haben, und inwieweit sie die Zusammensetzung der Atmosphäre oder das Klima beeinflussen.
Lay summary

Wir interessieren uns für drei verschiedene Beispiele von Grenzflächenprozessen: I) Oxidationsprozesse an der Oberfläche von Meerwasser führen zur Freisetzung von Halogenverbindungen, die in der Troposphäre einen grossen Einfluss auf das Ozonbudget haben. II) Nitrat kann an der Oberfläche von Mineraloxiden (zum Beispiel Saharastaub) zu Stickoxiden reduziert werden. Dies hat einen Einfluss auf  die Oxidationskapazität der Atmosphäre. III) Die Bildung von Eispartikeln in der Atmosphäre läuft oft an den Grenzflächen zwischen den sogenannten Eiskeimen und flüssigem Wasser oder Luft ab. Die erwähnten Prozesse sind im Detail bisher nicht genügend verstanden und es ist nicht klar, inwieweit sie die Zusammensetzung der Atmosphäre oder das Klima beeinflussen. 

Unser Ziel ist, die obengenannten Prozesse in Laborexperimenten nachzustellen, chemische Reaktionsraten direkt zu messen, sowie einen detaillierten Einblick auf molekularem Niveau zu bekommen. Wir haben in den letzten Jahren Methoden entwickelt, um Grenzflächenprozesse direkt spektroskopisch zu verfolgen. Wir verwenden dazu Elektronenspektroskopie, die wir so weiterentwickelt haben, dass wir sie auch für Proben mit hohen Dampfdrücken, wie Wasser, oder in Anwesenheit von Spurengasen, einsetzen können. Dies eröffnet komplett neue Möglichkeiten in der Atmosphärenchemie. Dies wird uns erlauben, einen vertieften Einblick in die Photolyse von Nitrat an der Oberfläche von Mineralstaub, in die Oxidationsprozesse von Halogeniden an der Oberfläche von wässrigen Lösungen und in die Organisation von Wasser an der Oberfläche von Eiskeimen liefern.

Unsere Arbeit wird wichtige neue Erkenntnisse über die chemischen Details von Grenzflächenprozessen in der Atmosphäre liefern. Die Ergebnisse werden in Modelle eingebunden, die verwendet werden, um Stoffkreisläufe zu verstehen, um die Luftqualität zu beurteilen, oder um den Einfluss von menschgemachten Emissionen auf Klima und Umwelt einzuschätzen.
Direct link to Lay Summary Last update: 06.10.2016

Responsible applicant and co-applicants

Employees

Publications

Publication
Ordered Hydrogen Bonding Structure of Water Molecules Adsorbed on Silver Iodide Particles under Subsaturated Conditions
Yang Huanyu, Boucly Anthony, Gabathuler Jérôme Philippe, Bartels-Rausch Thorsten, Artiglia Luca, Ammann Markus (2021), Ordered Hydrogen Bonding Structure of Water Molecules Adsorbed on Silver Iodide Particles under Subsaturated Conditions, in The Journal of Physical Chemistry C, 125(21), 11628-11635.
Surface Propensity of Aqueous Atmospheric Bromine at the Liquid–Gas Interface
Gladich Ivan, Chen Shuzhen, Vazdar Mario, Boucly Anthony, Yang Huanyu, Ammann Markus, Artiglia Luca (2020), Surface Propensity of Aqueous Atmospheric Bromine at the Liquid–Gas Interface, in The Journal of Physical Chemistry Letters, 11(9), 3422-3429.
Disordered Adsorbed Water Layers on TiO2 Nanoparticles under Subsaturated Humidity Conditions at 235 K
Orlando Fabrizio, Artiglia Luca, Yang Huanyu, Kong Xiangrui, Roy Kanak, Waldner Astrid, Chen Shuzhen, Bartels-Rausch Thorsten, Ammann Markus (2019), Disordered Adsorbed Water Layers on TiO2 Nanoparticles under Subsaturated Humidity Conditions at 235 K, in The Journal of Physical Chemistry Letters, 10(23), 7433-7438.
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, 19(16), 10817-10828.
The opposing effect of butanol and butyric acid on the abundance of bromide and iodide at the aqueous solution–air interface
Lee Ming-Tao, Orlando Fabrizio, Khabiri Morteza, Roeselová Martina, Brown Matthew A., Ammann Markus (2019), The opposing effect of butanol and butyric acid on the abundance of bromide and iodide at the aqueous solution–air interface, in Physical Chemistry Chemical Physics, 21(16), 8418-8427.
Physicochemical uptake and release of volatile organic compounds by soil in coated-wall flow tube experiments with ambient air
Li Guo, Cheng Yafang, Kuhn Uwe, Xu Rongjuan, Yang Yudong, Meusel Hannah, Wang Zhibin, Ma Nan, Wu Yusheng, Li Meng, Williams Jonathan, Hoffmann Thorsten, Ammann Markus, Pöschl Ulrich, Shao Min, Su Hang (2019), Physicochemical uptake and release of volatile organic compounds by soil in coated-wall flow tube experiments with ambient air, in Atmospheric Chemistry and Physics, 19(4), 2209-2232.
Microphysics of the aqueous bulk counters the water activity driven rate acceleration of bromide oxidation by ozone from 289–245 K
Edebeli Jacinta, Ammann Markus, Bartels-Rausch Thorsten (2019), Microphysics of the aqueous bulk counters the water activity driven rate acceleration of bromide oxidation by ozone from 289–245 K, in Environmental Science: Processes & Impacts, 21(1), 63-73.
X-Ray Excited Electron Spectroscopy to Study Gas–Liquid Interfaces of Atmospheric Relevance
Ammann Markus, Bartels-RauschThorsten, ArtigliaLuca (2018), X-Ray Excited Electron Spectroscopy to Study Gas–Liquid Interfaces of Atmospheric Relevance, in Faust Jennifer A. (ed.), Elsevier, Amsterdam, 135-166.
Technical note: Influence of surface roughness and local turbulence on coated-wall flow tube experiments for gas uptake and kinetic studies
Li Guo, Su Hang, Kuhn Uwe, Meusel Hannah, Ammann Markus, Shao Min, Pöschl Ulrich, Cheng Yafang (2018), Technical note: Influence of surface roughness and local turbulence on coated-wall flow tube experiments for gas uptake and kinetic studies, in Atmospheric Chemistry and Physics, 18(4), 2669-2686.
A surface-stabilized ozonide triggers bromide oxidation at the aqueous solution-vapour interface
Artiglia Luca, Edebeli Jacinta, Orlando Fabrizio, Chen Shuzhen, Lee Ming-Tao, Corral Arroyo Pablo, Gilgen Anina, Bartels-Rausch Thorsten, Kleibert Armin, Vazdar Mario, Andres Carignano Marcelo, Francisco Joseph S., Shepson Paul B., Gladich Ivan, Ammann Markus (2017), A surface-stabilized ozonide triggers bromide oxidation at the aqueous solution-vapour interface, in Nature Communications, 8(1), 700-700.
Efficient bulk mass accommodation and dissociation of N<sub>2</sub>O<sub>5</sub> in neutral aqueous aerosol
Gržinić Goran, Bartels-Rausch Thorsten, Türler Andreas, Ammann Markus (2017), Efficient bulk mass accommodation and dissociation of N<sub>2</sub>O<sub>5</sub> in neutral aqueous aerosol, in Atmospheric Chemistry and Physics, 17(10), 6493-6502.

Collaboration

Group / person Country
Types of collaboration
Dr. C. George, IRCELYON France (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Exchange of personnel
Prof. J. Osterwalder, University of Zürich Switzerland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Research Infrastructure
Prof. A. Michaelides Great Britain and Northern Ireland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
Prof. J. van Bokhoven, ETH Zürich and PSI Switzerland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Research Infrastructure
- Exchange of personnel
M. Shiraiwa and U. Pöschl, Max Planck Institute for Chemistry Germany (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Exchange of personnel
Prof. C. Dutcher United States of America (North America)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
Prof. H. Grothe, Vienna University of Technology Austria (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
Dr. M.A. Brown, ETH Zürich Switzerland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Research Infrastructure
Prof. R. Volkamer, University of Colorado United States of America (North America)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
Dr. I. Gladich, Qatar Environment and Energy Research Institute (QEERI) Qatar (Asia)
- in-depth/constructive exchanges on approaches, methods or results
- Publication

Scientific events

Active participation

Title Type of contribution Title of article or contribution Date Place Persons involved
European Geophysical Union General Assembly Talk given at a conference Iodine activation by imidazole carboxaldehyde 03.05.2020 Wien, Austria Ammann Markus;
Max Planck Institute for Chemistry, Department of Multiphase Chemistry Individual talk Introduction to X-ray photoelectron spectroscopy and X-ray absorption spectroscopy of environmental interfaces 11.11.2019 Bingen, Germany Ammann Markus;
European Geophysical Union General Assembly Talk given at a conference Hydrogen bonding structure of adsorbed water on silicate solid substrates monitored by in-situ spectroscopy 03.05.2019 Wien, Austria Ammann Markus; Yang Huanyu;
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;
Ambient pressure X-ray photoelectronspectroscopy workshop Poster The hydrogen bonding structure of adsorbed water on ice nucleation active solid substrates 11.12.2018 Berlin, Germany Yang Huanyu;
256th ACS Meeting Talk given at a conference Surface properties of hypobromite at the liquid-vapor interface from Liquid jet XPS method 19.08.2018 Boston, United States of America Chen Shuzhen;
Science of Surfaces, Interfaces and Nanostructures (SAOG) Talk given at a conference Surface properties of hypobromite at the liquid-vapor interface studied by Liquid jet XPS 01.02.2018 Fribourg, Switzerland Chen Shuzhen;
Seminar at Chinese Academy of Science, Institute of Chemistry Talk given at a conference A surface science approach to heterogeneous atmospheric chemistry 30.11.2017 Beijing, China Ammann Markus;
Sino-European School on Atmospheric Chemistry (SASAC-3) Talk given at a conference Heterogeneous chemistry with liquid substrates - a journey from interface to bulk 27.11.2017 Shanghai, China Ammann Markus;
Sino-European School on Atmospheric Chemistry (SESAC-3) Poster [Br•OOO−] intermediate species in the ozonolysis of bromide at the liquid/vapor interface from liquid jet XPS 21.11.2017 Shanghai, China Chen Shuzhen;
Seminar at University of Pierre et Marie Curie, Department of Chemistry Talk given at a conference The surface science of atmospheric processes 16.10.2017 Paris, France Ammann Markus;
European Geosciences Union Poster Identification of a [Br•OOO−] intermediate species in the ozonolysis of bromide at the liquid/vapor interface from liquid jet XPS 22.04.2017 Vienna, Austria Chen Shuzhen;


Communication with the public

Communication Title Media Place Year
Media relations: print media, online media Atmosphäre im Röntgenlicht Medienmitteilung German-speaking Switzerland International 2017
Media relations: print media, online media Atmosphäre im Röntgenlicht: Das Paul-Scherrer-Institut hat eine neue Experimentierkammer Aargauer Zeitung German-speaking Switzerland 2017

Associated projects

Number Title Start Funding scheme
170747 Ambient pressure XPS for operando studies of (photoelectro)chemical reactions at the solid-liquid interface 01.01.2017 R'EQUIP
178962 Interfacial Chemistry of Ice: Photolysis and Acid-Base Equilibria in the QLL and Brine 01.08.2018 Project funding (Div. I-III)
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)
149492 The surface chemistry of tropospheric gas - particle interactions 01.12.2013 Project funding (Div. I-III)
149629 Surface Sensitive Investigations of the Interaction of Atmospheric Acidic Trace Gases with Ice Surfaces 01.03.2014 Project funding (Div. I-III)
163074 Feedbacks between atmospheric aerosol microphysics and photochemical aging 01.01.2016 Project funding (Div. I-III)
155999 The impact of the physical micro-environment of impurities in snow on their re-distribution during metamorphism, chemical reactivity, and transfer to ice core archives. 01.05.2015 Project funding (Div. I-III)

Abstract

Interfacial chemistry at the surface of airborne and ground based environmental materials such as solid or liquid aerosol particles, cloud droplets, ocean and terrestrial ground surfaces is playing a crucial role in atmospheric sciences, e.g., in the chemistry of halogen compounds, in the cycling of nitrogen oxides, in cloud droplet activation, and in ice nucleation. In this project we continue our previous laboratory based activities towards understanding important aspects of halogen activation at ocean or sea spray aerosol surfaces and of indirect photochemical nitrate reduction on mineral oxides. We will use a combination of kinetic experiments and in situ spectroscopy methods to unravel molecular level details of the processes at the corresponding interfaces. Indirect nitrate photochemistry initiated by a photosensitizer will be studied on titania and hematite as a proxy for photocatalytic materials in atmospheric mineral dust or in depolluting nanomaterial applications by means of in situ X-ray photoelectron spectroscopy (XPS) under atmospherically relevant conditions, a technique that we have built up over the past years at PSI that allows experiments to be performed at ambient relative humidity. Since these processes occur on hydroxylated oxide interfaces interacting with water vapor, the characterization of adsorbed water on mineral oxide and other solid polyfunctional organic materials is important for understanding the chemical processes. In addition, it is also relevant for heterogeneous ice nucleation, since substrates active as ice nuclei tend to structure the hydrogen bonding environment in their vicinity. We will therefore address the hydrogen bonding network of adsorbed water by measuring electron yield X-absorption spectra. Flow tube experiments will be used to study the impact of surface active organic compounds on halide oxidation by ozone at the aqueous solution - air interface. This is one of the halide oxidation reactions for which several studies have suggested surface specific reaction pathways, which are still not clarified. The hypohalides evolving from this reaction are thought to mainly react with abundant chloride or bromide to form molecular halogen compounds; potential recycling reactions, e.g., with hydrogen peroxide potentially interfering and reforming the halides will be studied in this project to assess their relevance. Furthermore, oxidation of halides initiated by photosensitizers will be studied as an important halogen activation pathway under conditions of low ozone or in absence of other radical sources. The formation of reactive intermediates in halide oxidation at the same halide solution - air interfaces will be addressed by liquid jet XPS. XPS on a liquid jet and on a droplet train will be used to characterize the surface of complex ternary solutions relevant for halogen chemistry and the activation of aerosol particles into cloud droplets, which will also serve to benchmark thermodynamic models of surface tension. Electron yield oxygen K-edge X-ray absorption spectroscopy will be used to study the hydrogen bonding environment in concentrated aqueous solutions/suspensions of ice nucleating biogenic organic macromolecules or proxies thereof to provide insight into their activity.
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