Eco-Friendly Starch Composite Supramolecular Alginate-Ca²⁺ Hydrogel as Controlled-Release P Fertilizer with Low Responsiveness to Multiple Environmental Stimuli

Environmentally friendly fertilizers (EFFs) have been developed to improve fertilizer efficiency and minimize adverse environmental impacts, but their release behavior under various environmental conditions has been less explored. Using phosphorus (P) in the form of phosphate as a model nutrient, we present a simple method for preparing EFFs based on incorporating the nutrient into polysaccharide supramolecular hydrogels using Cassava starch in the Ca²⁺-induced cross-link gelation of alginate. The optimal conditions for creating these starch-regulated phosphate hydrogel beads (s-PHBs) were determined, and their release characteristics were initially evaluated in deionized water and then under various environmental stimuli, including pH, temperature, ionic strength, and water hardness. We found that incorporating a starch composite in s-PHBs at pH = 5 resulted in a rough but rigid surface and improved their physical and thermal stability, compared with phosphate hydrogel beads without starch (PHBs), due to the dense hydrogen bonding-supramolecular networks. Additionally, the s-PHBs showed controlled phosphate-release kinetics, following a parabolic diffusion with reduced initial burst effects. Importantly, the developed s-PHBs exhibited a promising low responsiveness to environmental stimuli for phosphate release even under extreme conditions and when tested in rice field water samples, suggesting their potential as a universally effective option for large-scale agricultural activities and potential value for commercial production.