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Silicon has been found to enhance the plants' tolerance to heavy metal stress. In a field study, the effect of different types of Si-rich soil amendments (slag, ground slag, and diatomaceous earth) and fertilizers (activated slag, ground activated slag, and commercial Si fertilizer) on the distribution of soluble and insoluble forms of Cd in the rice plant organs grown on long-term cultivated paddy soil contaminated with Cd (central part of Hunan Province, China) was investigated. The soluble Si and Cd were tested in the apoplast and symplast of the roots, stems, and leaves of rice at a tillering stage. The Si-rich materials increased rice biomass by up to 15.5% and reduced the total leaf Cd by 8.5 to 21.9%. Commercial Si fertilizer was the most effective. Three main locations of the most active Si-Cd interactions were distinguished in the soil-plant system: soil, where monosilicic acid affords adsorption and fixation of the bioavailable Cd and root apoplast and apoplast above roots, where monosilicic acid can precipitate Cd. The transport of Cd to stems and leaves and the mobility of Cd in the soil depend on the content of monosilicic acid in the system.