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The technology of packed bed dielectric barrier discharge (DBD) plasma followed by a chemical absorption has been developed and was found to be an efficient way for decomposition treatment of sulfuryl fluoride (SO2F2) in simulated residual fumigant. The effects of energy density, initial SO2F2 concentration, and residence time on the removal efficiency of SO2F2 for the DBD plasma treatment alone were investigated. It was found that the SO2F2 could be removed completely when initial volume concentration, energy density, and residence time were 0.5%, 33.9 kJ/L, and 5.1 s, respectively. The removal mechanism of SO2F2 in the packed bed DBD reactor was discussed. Based on the detailed analysis of SO2F2 molecular stability and its exhaust products in the DBD plasma reactor, it was concluded that the energetic electrons generated in the packed bed DBD reactor played a key role on the removal of SO2F2, and the major decomposition products of SO2F2 detected were SO2, SiF4, and S (Sulfur). Among these products, SiF4 was formed by the F atom reacted with the filler-quartz glass beads (SiO2) in the packed bed DBD reactor. Aqueous NaOH solution was used as the chemical absorbent for the gaseous products of SO2F2 after plasma pretreatment. It was found that the gaseous products in the plasma exhaust could be absorbed and fixed by the subsequent aqueous NaOH solution.