The No. 6 coal from the Haerwusu Surface Mine, Inner Mongolia, China, is enriched in Al and Ga, which are valuable metal resources that could be extracted from fly ash. However, fluorine in the coal is unusually high (mean 286 mu g/g) and potentially toxic to the environment in the extraction process. In this paper, a sequential extraction/density separation procedure (SE/DS) was designed to examine the modes of occurrence of fluorine in the coal. The results show that fluorine extracted in distilled water, NH(4)Ac (1 mol/l), and HCl (0.5%) leachates is low, and that in sulfide fraction is below the detection limit. The organic and silicate associations are inferred to account for more than 90% of the total fluorine in the coal. Boehmite and kaolinite are prime carriers of fluorine (the fluorine content in silicate fraction of the boehmite-enriched sample H-14 is up to 1906 mu g/g, and that of the kaolinite-enriched sample H-29 is 384 mu g/g). In bench samples H-2 and H-3, a minor amount of fluorine is related to goyazite. The relationship between fluorine and boehmite indicates that they were probably derived from the sediment source region, the weathered bauxite of the uplifted Benxi Formation situated to the northeastern Jungar coalfield. (C) 2010 Elsevier Ltd. All rights reserved.