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Transformation of As in the post-combustion zone has a significant effect on its emission characteristics. In this study, redistribution of As that occurs during the interaction between flue gas and ash has been elucidated using a double-layer fixed-bed reactor at 800–1000 °C. Herein, flue gas and ash samples with different As contents and inorganic components were produced by two varieties of coals. The As content in the ash with high Ca and Al contents increased after interacting with the flue gas with a high As content, indicating gaseous As adsorption. However, the As content in the ash decreased by up to 67% for other cases. The blank experiments showed that the As occurrences in ash were thermally stable, suggesting that the decrease was caused by the action of flue gas. Accordingly, the effect of flue gas components on the release of As from the ash was investigated. It was found that a significant amount of As release was primarily caused by the reaction of gaseous Na in the flue gas with the residual As in ash. A bi-directional interaction was observed between the high-temperature flue gas and ash, which led to the redistribution of As. Unlabelled Image • Interaction between high-temperature flue gas and ash caused As transformation. • Ash with high Ca and Al contents obviously adsorbed gaseous As in the flue gas. • Gaseous Na promoted the residual As release via reaction with aluminosilicate. [ABSTRACT FROM AUTHOR]