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Volume 8, issue 11 | Copyright
Atmos. Meas. Tech., 8, 4803-4815, 2015
© Author(s) 2015. This work is distributed under
the Creative Commons Attribution 3.0 License.

Research article 18 Nov 2015

Research article | 18 Nov 2015

Characterization of trace metals on soot aerosol particles with the SP-AMS: detection and quantification

S. Carbone1,a, T. Onasch2, S. Saarikoski1, H. Timonen1, K. Saarnio1, D. Sueper2,3, T. Rönkkö4, L. Pirjola5,6, A. Häyrinen7, D. Worsnop1,2,5, and R. Hillamo1 S. Carbone et al.
  • 1Atmospheric Composition Research, Finnish Meteorological Institute, P.O. Box 503, 00101 Helsinki, Finland
  • 2Aerodyne Research, Inc. 45 Manning Road, 01821-3976, Billerica, MA, USA
  • 3Cooperative Institute for Research In Environmental Sciences, University of Colorado, Boulder, CO 80303, USA
  • 4Tampere University of Technology, Department of Physics, Tampere, Finland
  • 5Department of Physics, University of Helsinki, P.O. Box 64, 00014 Helsinki, Finland
  • 6Metropolia University of Applied Sciences, P.O. Box 4021, Helsinki, Finland
  • 7Helen Ltd., 00090 Helen, Helsinki, Finland
  • anow at: Department of Applied Physics, University of São Paulo, São Paulo, Brazil

Abstract. A method to detect and quantify mass concentrations of trace metals on soot particles by the Aerodyne soot-particle aerosol mass spectrometer (SP-AMS) was developed and evaluated in this study. The generation of monodisperse Regal black (RB) test particles with trace amounts of 13 different metals (Na, Al, Ca, V, Cr, Mn, Fe, Ni, Cu, Zn, Rb, Sr and Ba) allowed for the determination of the relative ionization efficiency of each metal relative to black carbon (RIEmeas). The observed RIEmeas / RIEtheory values were larger than unity for Na, Rb, Ca, Sr and Ba due to thermal surface ionization (TSI) on the surface of the laser-heated RB particles. Values closer to unity were obtained for the transition metals Zn, Cu, V and Cr. Mn, Fe, and Ni presented the lowest RIEmeas / RIEtheory ratios and highest deviation from unity. The latter discrepancy is unexplained; however it may be related to problems with our calibration method and/or the formation of metal complexes that were not successfully quantified. The response of the metals to the laser power was investigated and the results indicated that a minimum pump laser current of 0.6 A was needed in order to vaporize the metals and the refractory black carbon (rBC). Isotopic patterns of metals were resolved from high-resolution mass spectra, and the mass-weighted size distributions for each individual metal ion were obtained using the high-resolution particle time-of-flight (HR-PToF) method. The RIEmeas values obtained in this study were applied to the data of emission measurements in a heavy-fuel-oil-fired heating station. Emission measurements revealed a large number of trace metals, including evidence for metal oxides and metallic salts, such as vanadium sulfate, calcium sulfate, iron sulfate and barium sulfate, which were identified in the SP-AMS high-resolution mass spectra. SP-AMS measurements of Ba, Fe, and V agreed with ICP-MS analyzed filter samples within a factor of 2 when emitted rBC mass loadings were elevated.

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Short summary
The purpose of this study was to develop a method for the quantification of trace metal content in black carbon aerosol in real time, such as combustion-related emissions, by using the SP-AMS. The properties of 13 different trace metals (Na, Al, Ca, V, Cr, Fe, Mn, Ni, Cu, Zn, Rb, Sr and Ba) were investigated in a controlled laboratory experiment. The results from the laboratory tests were applied to study fine particles in emissions of a heavy-fuel-oil-fired heating station.
The purpose of this study was to develop a method for the quantification of trace metal content...