The research focuses on the fate of heavy metals and their emissions from pulp mill recovery boilers. Heavy metals are extremely toxic and cause adverse effects on human health. There is limited information about factors affecting heavy metal vaporization from recovery boilers, in which spent pulping liquors, (also called black liquor) is burnt. The heavy metals are present in trace quantities in black liquor. They are emitted in the air as submicron particles, and their amount of emission depends on the input of metals into the recovery boiler, volatilization of metals in the boiler and the efficiency of the electrostatic precipitator (ESP) to remove the metals. The heavy metals vaporization from different recovery boilers vary widely and the reason is not known. My thesis will focus on determining what conditions affect the volatility of the heavy metals, and whether differences in heavy metal vaporization are due to differences in boiler operating conditions or the composition of the liquor. I will examine black liquor pyrolysis, combustion and gasification in well-controlled laboratory conditions. I will analyze three different black liquors. The liquors will be spray-dried and burnt or gasified in a laminar entrained-flow reactor at high temperatures of 1000-1100C and residence times ranging from 0.5 to 1.5 s. Equilibrium calculations will be performed to determine the distribution of heavy metals and species under set conditions from previous devolatilization experiments. The equilibrium calculations will serve as a useful tool for prior estimation of the distribution of heavy metals. The impact of different liquors on volatilization of heavy metals in the experiments will be determined. The char residue and condensation aerosol (fume) particles from each experiment will be analyzed using ICP-AES. The amount of heavy metals volatilization during combustion and gasification will be determined based on the amount of the metals in the char residues and fume particles. Based on the results of the experimental study combined with data from the equilibrium analysis program the main cause of variability in heavy metal vaporization can be found. Also the boiler operating conditions can be studied to determine its affects on the volatility of the heavy metals.