Effective recovery of phosphate from wastewater using biodegradable calcium-rich shell wastes composite macroporous cryogel

Abstract

The recovery of phosphorus from wastewater holds promise as a sustainable source of organic phosphorus for agricultural use while aiding in meeting legislative discharge limits for phosphorus to control and mitigate eutrophication. This study introduces a novel approach in which calcium-rich calcined oyster shell (Ca–COS) is immobilized on a starch-based monolithic cryogel, resulting in a green tablet (Cry–Ca–COS) capable of efficiently recovering phosphate from water through chemisorption on the material surface and precipitation in the liquid phase. The formed tablet prevents sorbent loss post-adsorption, facilitating reusability. Under optimal conditions (i.e., three 0.83 cm thick Cry–Ca–COS tablets, an initial phosphate concentration of 12 mg L−1 in 1 L without pH adjustment (pH 6.3), and a contact time of 60 minutes), a phosphate removal efficiency of 83.11% ± 0.68% and a maximum removal capacity of 9.97 mg g−1 were achieved. Both the Langmuir isotherm model and pseudo-second-order kinetic model exhibited good fits to the experimental data, with an estimated activation energy of 81.9 kJ mol−1 and a positive enthalpy of 9.3 kJ mol−1, indicating an endothermic chemisorption process with a monolayer surface coverage of phosphate on Cry–Ca–COS. In real samples, Cry–Ca–COS demonstrated a high removal efficiency ranging from 98.48% ± 1.87%–99.16% ± 0.72%, with the adsorbed material biodegrading within 24 days under soil burial conditions. A preliminary study was conducted to explore the feasibility of utilizing phosphate-adsorbed Cry–Ca–COS as a fertilizer for cultivating water spinach (Ipomoea aquatica Forsk.), and further in-depth investigation is required for a comprehensive report in the future. Thus, Cry–Ca–COS emerges as an environmentally friendly and effective tool for phosphate removal and recovery.