Understanding the Behavior of Radioactive Cesium during the Incineration of Contaminated Municipal Solid Waste and Sewage Sludge by Thermodynamic Equilibrium Calculation.

Abstract

Following the nuclear accident at the Fukushima Daiichi Nuclear Power Plant in 2011, even the municipal solid waste (MSW) and sewage sludge (SS) in northeastern Japan became contaminated by radioactive nuclides such as 137Cs and 134Cs. To understand the state of radioactive cesium (r-Cs) in the incineration residues of the municipal wastes, research groups studied the concentration and the chemical form of r-Cs in the residues, as well as its water-leaching behavior. In the present study, we conducted thermodynamic equilibrium calculations to estimate the possible chemical forms of r-Cs in the incineration residues. Thermodynamic data for cesium oxides and aluminosilicates were collected and compiled into a new database to perform equilibrium calculations for systems that include Cs. The calculation results suggested that Cs (radiocesium and stable cesium) in municipal solid waste was transformed into gaseous CsCl or crystalline aluminosilicate at incineration temperatures and, when a molten aluminosilicate phase (i.e., slag phase) was generated, a proportion of the Cs species was dissolved into the slag phase. In the case of sewage sludge, Cs was calculated to be transformed mostly into crystalline aluminosilicate at incineration temperatures, whereas by analogy with the behaviors of Na and K, Ca,Cs-phosphate double salts were also potential incineration products. These results could account for the high leaching rates of r-Cs from the MSW incineration fly ash and the low leaching rates from the MSW incineration bottom ash and SS incineration fly ash reported in earlier studies. In the case of dewatered SS that included a large amount of slaked lime as a flocculant, it was exceptionally difficult for the calculation to represent the fate of Cs, and we needed to include the contribution of silica sand in a fluidized-bed combustor in the equilibrium calculation to represent the low leaching rates of alkali species from the dewatered SS fly ash. From the results of the thermodynamic equilibrium calculations and also from the calculated standard Gibbs energy of cesium aluminosilicate formation/decomposition reactions, the effects of waste composition and incineration temperature on the fate of Cs were examined: High incineration temperature and large amounts of Ca and Cl in the waste composition increased the fraction of gaseous CsCl in the furnace and thus resulted in the high distribution ratios of Cs in the fly ash of MSW and the high leaching rates of Cs from the fly ash.