Structural changes of CAST soot during a thermal-optical measurement protocol

Abstract. Thermal-optical measurement techniques are widely used to classify carbonaceous material. The results of different methods for total carbon are comparable, but can vary by > 44 % for elemental carbon. One major cause of variation is the formation of pyrolyzed carbon during the heating process which occurs mainly in samples with a high amount of brown carbon (BrC). In this study the structural changes of two different CAST aerosol samples caused by the heating procedure in a thermal-optical instrument were investigated with UV-VIS and Raman spectroscopy, the Integrating Sphere technique and transmission electron microscopy. All analysis techniques showed significant structural changes for BrC rich samples at the highest temperature level (870 °C) in helium. The structure of the heated BrC-rich sample resembles the structure of an unheated BrC-poor sample. Heating the BrC rich sample to 870 °C increases the graphitic domain size within the material from 1.6 nm to 2 nm. Although the Raman spectra unambiguously show this increase of ordering only at the highest temperature step, UV-VIS and IS analyses show a continuous change of the optical properties also at lower temperatures. The sample with a negligible amount of BrC, however, did not show any significant structural changes during the whole heating procedure.