Theoccurrencemodesofalkaliandalkaline-earthmetals(AAEMs)incoalrelatetotheirreleasebehaviorandashformationduringcombustion.TobetterunderstandthetransformationofAAEMs,thereleasebehaviorofwater-soluble,HCl-soluble,HCl-insolubleAAEMsduringShenmucoal(SMcoal)oxy-fuelcombustioninthepresenceofSO2andH2Oinadrop-tubereactorwasinvestigatedthroughserialdissolutionusingH2OandHClsolutions.TheresultsshowthatthereleaseratesofAAEMsincreasewithanincreaseintemperatureunderthethreeatmospheresstudied.ThehighreleaseratesofMgandCafromSMcoalaredependentonthehighcontentofsolubleMgandCainSMcoal.SO2inhibitsthereleaseratesofAAEMs,whileH2Opromotesthem.TheeffectsofSO2andH2OontheNaandKspeciesaremoreevidentthanthoseonMgandCaspecies.AllthreetypesofAAEMsincoalcanvolatilizeinthegasphaseduringcoalcombustion.TheW-typeAAEMsreleaseexcessively,whereasthereleaseratesofI-typeAAEMsarerelativelylower.DifferenttypesofAAEMmayinterconvertthroughdifferentpathwaysundercertainconditions.BothSO2andH2Opromotethetransformationreactions.TheeffectofSO2wasrelatedtosulfateformationandthepromotionbyH2OoccursbecauseofadecreaseinthemeltingpointofthesolidaswellasthereactionofH2O.