14Sodium emissions during pulverized-coal combustion (PCC) are known to result in severe 15 ash-related operating issues of coal furnaces, e.g., fouling, slagging and corrosion. To relieve these 16 issues and advance the clean utilization technologies of coal, a better understanding of the 17 fundamental mechanisms driving the formation and transformation of the sodium species is required. 18In the present study, sodium emissions have been simulated in both one-dimensional (1D) 19 premixed/diffusion flames of the coal volatile and an early-stage two-dimensional (2D) 20 pulverized-coal flame. The properties of Loy Yang brown coal are used. The DRM22 skeletal 21 mechanism is employed for volatile-gas combustion, and the reaction of sodium species is modeled 22 by a detailed mechanism encompassing the elements Na, C, H, O, S and Cl. The compositions of the 23 volatile fuels are obtained from the chemical percolation devolatilization (CPD) model, including 24 CH4, C2H2, CO, H2, CO2 and H2O. The initial species of Na, Cl and S in the volatile gas is set to be 25NaOH, HCl and SO2, respectively. The transformation characteristics of 12 sodium species are 26 investigated in both the 1D volatile flames and the 2D pulverized-coal flame. The response of the 27 sodium chemistry to volatile-gas combustion is analyzed under fuel-lean, stoichiometric and 28 2 fuel-rich conditions. Na, NaOH and NaCl are found to be the major sodium species during the 29 combustion. Parametric studies with HCl, SO2 or both species removed from the volatile are then 30 performed to investigate their effects on the sodium transformation characteristics in both the 1D and 31 2D flames. The results show that HCl has a much stronger ability to react with sodium species than 32 SO2. 33