This paper is based on results obtained during co-combustion of wood pellets and straw in a 12 MW circulating fluidised bed (CFB) boiler. Elemental sulphur (S) and ammonium sulphate ((NH4)(2)SO4) were used as additives to convert the alkali chlorides (mainly KCl) to less corrosive alkali sulphates. Their performance was then evaluated using several measurement tools including, IACM (on-line measurements of gaseous alkali chlorides), a low-pressure impactor (particle size distribution and chemical composition of extracted fly ash particles), and deposit probes (chemical composition in deposits collected). The importance of the presence of either SO2 or SO3 for gas phase sulphation of KCl is also discussed. Ammonium sulphate performed significantly better than elemental sulphur. A more efficient sulphation of gaseous KCl was achieved with (NH4)(2)SO4 even when the S/Cl molar ratio was less than half compared to sulphur. Thus the presence of gaseous SO3 is of greater importance than that of SO2 for the sulphation of gaseous KCl. (C) 2010 The Combustion Institute. Published by Elsevier Inc. All rights reserved.