Calcium-Modified Coal-Based Humin Waste Residue: Enhanced Cadmium Remediation in Combined Soil–Plant Systems

Coal-based humic acid waste residue is a solid waste generated during the production of humic acid products. The extraction of coal-based humin (NHM) from such residues presents an effective approach for solid waste resource recovery. In this study, a novel calcium-based humin (Ca-NHM) was synthesized via a low-temperature-assisted method. The material was characterized and its cadmium passivation mechanism was investigated using scanning electron microscopy (SEM), zeta potential analysis (Zeta), carbon nuclear magnetic resonance (¹³C-CPMAS-NMR), and X-ray photoelectron spectroscopy (XPS). Soil incubation experiments were conducted to determine the actual cadmium adsorption capacity of coal-based humin in soils and to evaluate the stability of cadmium passivation. Plant cultivation experiments were carried out to verify the effects of coal-based humin on migration and transformation in soil, as well as on cadmium bioefficiency. The results showed that Ca-NHM passivated soil cadmium through multiple mechanisms such as ion exchange, electrostatic adsorption, complexation reactions, and physical adsorption. Compared with NHM, Ca-NHM exhibited a 69.71% increase in passivation efficiency, and a 2.44% reduction in cadmium leaching concentration. In Ca-NHM treatments, the above- and below-ground biomass of pakchoi increased by 18.06%, and 80.95%, respectively, relative to the control group. Furthermore, Ca-NHM enhanced the cadmium resistance of pakchoi, reduced the enrichment coefficient, activity coefficient, and activity-to-stability ratio in the above-ground portion of pakchoi, and maintained a transfer coefficient below 1, thereby alleviating cadmium toxicity. In summary, this study provides a theoretical foundation for understanding the mechanisms by which coal-based humin mitigates cadmium toxicity in pakchoi.