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This paper presents an experimental investigation of the sulfuration mechanism of concrete. The microstructure, mineral phase composition, substance content, and pH of the concrete were determined using scanning electron microscopy, X-ray diffraction, comprehensive thermal analysis, and pore-solution pH test. It was observed that light-grey spots appeared on the surface of the specimen, and a large amount of powdery precipitated substances appeared. At the initial stage of sulfuration reaction, the formation of ettringite blocked the con