The natural oxidation/weathering of coal continues to be a subject of interest both scientifically and industrially, in part due to the complexity of the molecular processes at hand as well as to the commercial implications involved. It is widely recognized that coking can be adversely affected by weathering whereas, combustion processes appear to be enhanced as result of oxidation. Combustion techniques are commonly used in the analysis of coal, and organic compounds in general, for the determination of elemental hydrogen, carbon and nitrogen. For oxygen, the method in common practice involves the determination by difference from directly determined values for moisture, ash, sulphur, hydrogen, carbon and nitrogen. This has led us to consider the use of thermogravimetry coupled to gas analysis by infrared spectroscopy (TG-FTIR) to measure organic oxygen in coal directly. Although this technique, developed by Solomon and coworkers, has been extensively used by our group and others, it appears not to have been considered for this particular purpose. Recently, we have shown that TG-FTIR is capable of measuring all the organic oxygen in both fresh and oxidized coal by simultaneous measurement of the three main oxygen-containing gases H2O, CO and CO2 evolved during rapid pyrolysis. This gives us a way of measuring quantitatively the oxygen introduced into the coal matrix during oxidation and at least a partial capability of establishing oxygen speciation. We have found, using TG-FTIR, that the early stages of coal oxidation results in the appearance of O-containing functional groups not present in the original coal. The nature of these functional groups is directly related to the oxidation reaction mechanism. These results will be presented and discussed in detail. Crown Copyright (C) 2004 Published by Elsevier Ltd. All rights reserved.