1Laboratory of Radiochemistry and Environmental Chemistry, Paul Scherrer Institut, 5232 Villigen PSI, Switzerland
2EMPA, Swiss Federal Laboratories for Materials Research and Testing, Electronics/Metrology Laboratory, Ueberlandstrasse 129, 8600 Dübendorf, Switzerland
3Laboratory of Atmospheric Chemistry, Paul Scherrer Institut, 5232 Villigen PSI, Switzerland
4Swiss Light Source, Paul Scherrer Institut, 5232 Villigen PSI, Switzerland
*now at: swissQuant Group AG, Kuttelgasse 7, 8001 Zurich, Switzerland
**now at: Italian National Agency for New Technologies, Energy and Sustainable Economic Development (ENEA), UTAPRAD-DIM, Via E. Fermi 45, 00044 Frascati, Italy
Received: 13 Apr 2011 – Published in Atmos. Chem. Phys. Discuss.: 11 May 2011
Abstract. Soot particles can significantly influence the Earth's climate by absorbing and scattering solar radiation as well as by acting as cloud condensation nuclei. However, despite their environmental (as well as economic and political) importance, the way these properties are affected by atmospheric processing of the combustion exhaust gases is still a subject of discussion. In this work, individual soot particles emitted from two different vehicles, a EURO 2 transporter, a EURO 3 passenger car, and a wood stove were investigated on a single-particle basis. The emitted exhaust, including the particulate and the gas phase, was processed in a smog chamber with artificial solar radiation. Single particle specimens of both unprocessed and aged soot were characterized using near edge X-ray absorption fine structure spectroscopy (NEXAFS) and scanning electron microscopy. Comparison of NEXAFS spectra from the unprocessed particles and those resulting from exhaust photooxidation in the chamber revealed changes in the carbon functional group content. For the wood stove emissions, these changes were minor, related to the relatively mild oxidation conditions. For the EURO 2 transporter emissions, the most apparent change was that of carboxylic carbon from oxidized organic compounds condensing on the primary soot particles. For the EURO 3 car emissions oxidation of primary soot particles upon photochemical aging has likely contributed as well. Overall, the changes in the NEXAFS fingerprints were in qualitative agreement with data from an aerosol mass spectrometer. Furthermore, by taking full advantage of our in situ microreactor concept, we show that the soot particles from all three combustion sources changed their ability to take up water under humid conditions upon photochemical aging of the exhaust. Due to the selectivity and sensitivity of the NEXAFS technique for the water mass, also small amounts of water taken up into the internal voids of agglomerated particles could be detected. Because such small amounts of water uptake do not lead to measurable changes in particle diameter, it may remain beyond the limits of volume growth measurements, especially for larger agglomerated particles.
Revised: 20 Oct 2011 – Accepted: 14 Nov 2011 – Published: 24 Nov 2011
Citation: Zelenay, V., Mooser, R., Tritscher, T., Křepelová, A., Heringa, M. F., Chirico, R., Prévôt, A. S. H., Weingartner, E., Baltensperger, U., Dommen, J., Watts, B., Raabe, J., Huthwelker, T., and Ammann, M.: Aging induced changes on NEXAFS fingerprints in individual combustion particles, Atmos. Chem. Phys., 11, 11777-11791, doi:10.5194/acp-11-11777-2011, 2011.