Aluminum (Al) is a concentration-dependent toxic metal found in the crust of earth that has no recognized biological use. Nonetheless, the mechanism of Al toxicity to submerged plants remains obscure, especially from a cell/subcellular structure and functional group perspective. Therefore, multiple dosages of Al³⁺ (0, 0.3, 0.6, 1.2, and 1.5 mg/L) were applied hydroponically to the submerged plant Vallisneria natans in order to determine the accumulation potential of Al at the subcellular level and their ultrastructural toxicity. More severe structural and ultrastructural damage was determined when V. natans exposed to ≥ 0.6 mg/L Al³⁺. In 1.2 and 1.5 mg/L Al³⁺ treatment groups, the total chlorophyll content of leaves significantly reduced 3.342, 3.838 mg/g FW, some leaves even exhibited chlorosis and fragility. Under 0.3 mg/L Al³⁺ exposure, the middle-age and young leaves were potent phytoexcluders, whereas at 1.5 mg/L Al³⁺, a large amount of Al could be transferred from the roots to other parts, among which the aged leaves were the most receptive tissues (7.306 mg/g). Scanning/Transmission electron microscopy analysis displayed the Al-mediated disruption of vascular bundle structure in leaf cells, intercellular space and several vegetative tissues, and demonstrated that Al in vacuole and chloroplast subcellular segregation into electron dense deposition. Al and P accumulation in the roots, stolons and leaves varied significantly among treatments and different tissues (P < 0.05). Fourier transform infrared spectroscopy of plant biomass also indicated possible metabolites (amine, unsaturated hydrocarbon, etc.) of V. natans that may bind Al³⁺. Conclusively, results revealed that Al³⁺ disrupts the cellular structure of leaves and roots or binds to functional groups of biological tissues, thereby affecting plant nutrient uptake and photosynthesis. Findings might have scientific and practical significance for the restoration of submerged vegetation in Al-contaminated lakes.

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