In the UK there is a longstanding interest in the Cl content of coals because of the adverse effects associated with high-Cl coals during combustion. An average Cl content of a representative suite of coal samples is 0.44 wt.%, but the range is from near zero to over M Several lines of evidence show that in the high-Cl coals the Cl is associated with the coal moisture and that other sources, such as the silicate minerals, are negligible. Although the Cl is moisture associated there is anion exchange with the organic matter, which means that Cl is less than 100% water- soluble unless the Cl is exchanged with other anion species. This occurs if carbonates are present and calcite in particular. The Cl and Br are closely related and the location within the coal is thought to be common to both. These two elements differ from nearly all other trace elements in UK coals in that they are not present in significant concentrations in the mineral matter or bound within the organic matter. Whereas there is a good understanding of the geochemical behaviour of these other elements this is not the case for CI and Br in the coal moisture. Chlorine and Br are thought to be conservative elements in the diagenetic evolution of the porewaters, in which an original marine depositional imprint could have been preserved. In some areas the porewaters may have fully evolved pre-Permian, whereas in other areas the diagenetic evolution could be much longer. (c) 2005 Elsevier B.V All rights reserved.