Boron and its compounds are environmentally hazardous substance and are well-known condensed products that appear in coal fly ash during combustion of coal in coal-fired electric power stations. In a previous study, we suggested that boron in coal fly ash obtained from Nantun coal in China, identified as Ash-N, may exist on the surface of relatively large coal fly ash particles or as very fine particles generated by homogeneous nucleation. Although the characterization of boron in coal fly ash is important for its effective stabilization or removal, its detection is quite difficult because of its low concentration in coal fly ash and its light atomic weight. In the present work, solid-state magic angle spinning nuclear magnetic resonance (MAS-NMR) technique has been applied to reveal the local chemical structures of boron in Ash-N. In the B-11 MAS-NMR spectrum of Ash-N, two peaks which are attributed to a three-oxygen coordinated boron unit (BO3) and a four-oxygen coordinated boron unit (BO4) were observed with high resolution. We have estimated quadrupole parameters of the BO3 unit in Ash-N using computer simulation, and we have fingerprinted these moieties with the parameters of borates. The result of the present analysis shows that calcium-or magnesium-bearing orthoborate or pyroborate are the most likely forms of boron in Ash-N. (C) 2009 Elsevier Ltd. All rights reserved.