Unburned carbon (UC) in 21 combustion residues from solid biofuels has been examined using several methods of analysis (including LOI and TOC) as well as micro-Raman spectroscopy. The concentration of unburned carbon in the residues varied over an order of magnitude and in several samples accounted for about 10% of the ash mass. It was observed that TOC had a poor correlation to organic carbon, especially for fly ashes. LOI at all tested temperatures showed a better correlation than TOC to the organic carbon content, whereas the TOC is better correlated to elemental carbon. LOI550 gave a larger variation and a less complete mobilisation of unburned carbon than LOI at 750 or 975 degrees C did, but at the highest temperature metal oxidation was notably affecting the mass balance to the extent that some samples gained mass. For this reason, and of the temperatures tested, LOI750 seem to be the most stable indicator for organic remains in the incineration residuals. Most of the unburned carbon is elemental, and only slowly degradable, so the potential emissions of organic compounds from ashes should not be assessed by using a TOC test. The structure of the detected elemental carbon in UC is similar to that of activated carbon, which indicates a potentially large specific surface. This should be borne in mind when assessing the environmental impact of using ash for different purposes, including use as a construction material. Field studies are needed to verify the actual impact as it may depend on environmental conditions. (C) 2013 Elsevier Ltd. All rights reserved.