Project

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Heterogeneous chemistry of tropospheric aerosol particles with nitrogen oxides from trace gas kinetics, surface chemical and bulk structural perspectives

Applicant Ammann Markus
Number 130175
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 01.09.2010 - 30.11.2013
Approved amount 522'618.00
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All Disciplines (2)

Discipline
Physical Chemistry
Climatology. Atmospherical Chemistry, Aeronomy

Keywords (2)

ozone; climate

Lay Summary (English)

Lead
Lay summary
Chemical processing of aerosol particles in the atmosphere is a major aspect in determining their environmental impact, such as on climate, the atmosphere's oxidation capacity, human health or sensitive ecosystems. Nitrogen oxides are key players in the gas phase atmospheric chemistry as they largely control the ozone budget over the globe. This project provides kinetic information about the interaction of nitrogen oxides with aerosol particles as well as the associated changes of particle chemical and structural properties. Interactions between gas phase nitrogen oxides and aerosol particles play an important role in the ozone budget and the climate effect of the particles. Among these, the hydrolysis of dinitrogen pentoxide (N2O5) plays a particularly significant role in the nocturnal atmosphere as it represents a removal pathway of nitrogen oxides. Understanding the kinetics of these processes is still limited. On the other hand, such processes significantly alter the particle properties, especially in relation to their climate impact. This includes changes to the surface chemical composition, their phase state (solid/liquid), morphology and their ability to act as cloud condensation nuclei. We will specifically focus on kinetic aspects of N2O5 hydrolysis as well as the so-called nitrate effect, where using a radioactive tracer technique offers a unique opportunity to make use of isotopic dilution to separate the initial uptake from follow up processes. The results will allow improving current atmospheric chemistry models to correctly implement N2O5 chemistry. We will separately use novel tools, namely ambient pressure X-ray photoelectron spectroscopy (HP-XPS) as well as Scanning Transmission X-Ray Microscopy (STXM) to address interfacial chemistry and internal particle structure and morphology, respectively. The aim is to elucidate the role of exposure of deposited particles to various nitrogen oxides, including N2O5, to the surface chemical composition as well as internal particle structure. This part of the project will support assessing chemistry - climate links in a changing environment. Overall, this project extends our basis for understanding chemical processes in the atmosphere as well as their link to climate relevant parameters of aerosol particles.
Direct link to Lay Summary Last update: 21.02.2013

Responsible applicant and co-applicants

Employees

Publications

Publication
Emerging Areas in Atmospheric Photochemistry
George Christian, D'Anna Barbara, Herrmann Hartmut, Weller Christian, Vaida Veronica, Donaldson D. J., Bartels-Rausch Thorsten, Ammann Markus Emerging Areas in Atmospheric Photochemistry, (2014), Emerging Areas in Atmospheric Photochemistry, Springer-Verlag, Berlin Heidelberg1-54.
Evaluated kinetic and photochemical data for atmospheric chemistry: Volume VI – heterogeneous reactions with liquid substrates
Ammann M, Cox R.A., Crowley J.N., Jenkin M.E., Mellouki A., Rossi M.J., Troe J., Wallington T.J. (2013), Evaluated kinetic and photochemical data for atmospheric chemistry: Volume VI – heterogeneous reactions with liquid substrates, in Atmospheric Chemistry and Physics, 13, 8045-8228.
Kinetic regimes and limiting cases of gas uptake and heterogeneous reactions in atmospheric aerosols and clouds: a general classification scheme
Berkemeier T., Huisman A. J., Ammann M., Shiraiwa M., Koop T., Pöschl U. (2013), Kinetic regimes and limiting cases of gas uptake and heterogeneous reactions in atmospheric aerosols and clouds: a general classification scheme, in Atmos. Chem. Phys., 13, 6663-6686.
Ozone-Induced Band Bending on Metal-Oxide Surfaces Studied under Environmental Conditions
Lampimäki Markus, Zelenay Veronika, Křepelová Adéla, Liu Zhi, Chang Rui, Bluhm Hendrik, Ammann Markus (2013), Ozone-Induced Band Bending on Metal-Oxide Surfaces Studied under Environmental Conditions, in ChemPhysChem, 14, 2419-2425.
Multiphase Chemical Kinetics of the Nitration of Aerosolized Protein by Ozone and Nitrogen Dioxide
Shiraiwa M, Selzle K, Yang H, Sosedova Y, Ammann M, Poschl U (2012), Multiphase Chemical Kinetics of the Nitration of Aerosolized Protein by Ozone and Nitrogen Dioxide, in ENVIRONMENTAL SCIENCE & TECHNOLOGY, 46(12), 6672-6680.
Standard States and Thermochemical Kinetics in Heterogeneous Atmospheric Chemistry
Donaldson DJ, Ammann M, Bartels-Rausch T, Poschl U (2012), Standard States and Thermochemical Kinetics in Heterogeneous Atmospheric Chemistry, in JOURNAL OF PHYSICAL CHEMISTRY A, 116(24), 6312-6316.
Gas uptake and chemical aging of semisolid organic aerosol particles
Shiraiwa M, Ammann M, Koop T, Poschl U (2011), Gas uptake and chemical aging of semisolid organic aerosol particles, in PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AME, 108(27), 11003-11008.
The role of long-lived reactive oxygen intermediates in the reaction of ozone with aerosol particles
Shiraiwa M, Sosedova Y, Rouvière A, Yang H, Zhang Y, Abbatt JPD, Ammann M, Pöschl U (2011), The role of long-lived reactive oxygen intermediates in the reaction of ozone with aerosol particles, in Nature Chemistry, 3(4), 291-295.
UVA/Vis-induced nitrous acid formation on polyphenolic films exposed to gaseous NO2
Sosedova Y, Rouviere A, Bartels-Rausch T, Ammann M (2011), UVA/Vis-induced nitrous acid formation on polyphenolic films exposed to gaseous NO2, in PHOTOCHEMICAL & PHOTOBIOLOGICAL SCIENCES, 10(10), 1680-1690.

Scientific events

Active participation

Title Type of contribution Title of article or contribution Date Place Persons involved
American Geophysical Union Poster The humidity dependence of N2O5 uptake to citric acid aerosol particles 08.12.2013 San Francisco, United States of America Ammann Markus;
26th Annual MAX IV Laboratory Users Meeting Talk given at a conference Observing atmospheric processes in aerosol particles and ice – a STXM and XPS perspective 23.09.2013 Lund, Sweden Ammann Markus;
International Meeting on Atomic and Molecular Physics and Chemistry Talk given at a conference Influence of nitrogen oxides and UV-radiation on metal oxide surfaces: XPS investigation 02.07.2013 Lille, France Lampimäki Markus;
European Geophysical Union General Assembly Poster Uptake of 13N-labeled N2O5 to citric acid aerosol particles 07.04.2013 Wien, Austria Ammann Markus; Grzinic Goran;
29th European Conference on Surface Science (ECOSS) Talk given at a conference Ozone decomposition and nitrate formation on Fe- and Ti-oxide surfaces studied by 03.09.2012 Edinburgh, Great Britain and Northern Ireland Lampimäki Markus; Ammann Markus;
4th EuCheMS Chemistry Congress Talk given at a conference Chemistry on Aerosol Particles and Ice 26.08.2012 Prag, Czech Republic Ammann Markus;
22nd International Symposium on Gas Kinetics Talk given at a conference Constraining kinetic parameters of gas particle interactions in the transition from liquid to solid 18.06.2012 Boulder, CO, United States of America Ammann Markus;
Photocatalysis : Science and Application for Urban Air Quality The LIFE+ PhotoPaq conference 2012 Talk given at a conference Electron spectroscopic studies on metal oxide surfaces: Effect of ozone, nitrogen 14.05.2012 Corsica, France Lampimäki Markus;
European Geophysical Union General Assembly Poster Towards an experiment to investigate N2O5 uptake to aerosol particles at conditions using the radioactive tracer 13N 22.04.2012 Wien, Austria Ammann Markus; Grzinic Goran;
13th EuCheMS Internl Conf on Chemistry & the Environment (ICCE) Poster Chemical and photochemical reactions of organic aerosol particles with atmospheric oxidants 11.09.2011 Zürich, Switzerland, Switzerland Ammann Markus; Grzinic Goran;
European Conference on Applications of Surface and Interface Analysis (ECASIA) Poster Nanostructure and hygroscopicity of tannic acid particles: Influence of O3 and UV-radiation 04.09.2011 Cardiff, Great Britain and Northern Ireland Lampimäki Markus;
American Chemical Society National Meeting Talk given at a conference Reactivity at the sea salt - air interface: Spectroscopy and kinetics 28.08.2011 Denver, CO, United States of America Ammann Markus;


Communication with the public

Communication Title Media Place Year
Media relations: print media, online media Auch Feinstaub altert PSI Press release German-speaking Switzerland 2011

Associated projects

Number Title Start Funding scheme
139139 Near ambient pressure photoelectron spectroscopy for environmental and catalysis research 01.12.2011 R'EQUIP
142687 Environmental STXM as a tool for in situ observations of cooking aerosol aging 01.05.2012 International short research visits
163074 Feedbacks between atmospheric aerosol microphysics and photochemical aging 01.01.2016 Project funding (Div. I-III)
109341 Phasentransfer-Eigenschaften und heterogene Photochemie von atmosphärischen Spurengasen mit organischen Aerosolen 01.11.2005 Project funding (Div. I-III)
149492 The surface chemistry of tropospheric gas - particle interactions 01.12.2013 Project funding (Div. I-III)

Abstract

Chemical processing of aerosol particles in the atmosphere is a major aspect in determining their environmental impact, such as on climate, the atmosphere’s oxidation capacity, human health or sensitive ecosystems. Nitrogen oxides are key players in the gas phase atmospheric chemistry as they largely control the ozone budget over the globe. Nitrogen oxides are involved in a rich heterogeneous chemistry with aerosol particles. Among these, the hydrolysis of dinitrogen pentoxide (N2O5) plays a particularly significant role in the nocturnal atmosphere as it represents a removal pathway of nitrogen oxides. As part of this removal pathway, also reactive intermediates are formed that feed back into the oxidative chemistry. Understanding the kinetics of these processes is still limited. Based on our background in heterogeneous kinetics of especially nitrogen oxides, in particular using the short-lived radioactive tracer 13N, we propose to extend our suite of trace gas species to N2O5 and specifically focus on the temperature dependence of N2O5 hydrolysis as well as the so-called nitrate effect, where using the tracer offers a unique opportunity to make use of isotopic dilution to separate the initial uptake from follow up processes. Condensed phase processing by nitrogen oxides contributes to the continuous transformation of aerosol particles. While our trace gas kinetics experiments performed earlier and proposed above cover short time chemical processes, the longterm effects on the surface properties as well as on particle bulk structure are very important for their environmental impact. We have recently explored novel tools, namely ambient pressure X-ray photoelectron spectroscopy (HP-XPS) as well as Scanning Transmission X-Ray Microscopy (STXM) to address interfacial chemistry and internal particle structure, respectively. We propose to extend these investigations by exploring the condensed phase chemistry and photochemistry of NO2 and HNO3 with mineral oxides and organic substrates. HP-XPS will provide us with shallow depth resolved surface chemical composition and electronic structure. On the other hand, STXM, combined with X-ray absorption spectroscopy (XAS) allows monitoring the chemical transformation of the interior of particles.
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