Impact of catalytic hydrothermal treatment and Ca/Al-modified hydrochar on lability, sorption, and speciation of phosphorus in swine manure: Microscopic and spectroscopic investigations

The effects of catalytic hydrothermal (HT) pretreatment on animal manure followed by the addition of hydrochar on the nutrients recovery have not yet been investigated using a combination of chemical, microscopic, and spectroscopic techniques. Therefore, a catalytic HT process was employed to pretreat swine manure without additives (manure-HT) and with H₂O₂ addition (manure-HT- H₂O₂) to improve the conversion efficiency of labile or organic phosphorus (P) to inorganic phase. Then, a Ca–Al layered double hydroxide hydrochar (Ca/Al LDH@HC) derived from corn cob biomass was synthesized and applied to enhance P sorption. Scanning electron microscopy (SEM), and three-dimensional excitation emission matrix (3D-EEM), X-ray photoelectron spectroscopy (XPS), P k-edge X-ray absorption near edge structure (XANES), were used to elucidate the mechanisms of P release and capture. The H₂O₂ assisted HT treatment significantly enhanced the release of inorganic P (251.4 mg/L) as compared to the untreated manure (57.2 mg/L). The 3D-EEM analysis indicated that the labile or organic P was transformed and solubilized efficiently along with the deconstruction of manure components after the H₂O₂ assisted HT pretreatment. Application of Ca/Al LDH@HC improved the removal efficiency of P from the derived P-rich HT liquid. This sorption process was conformed to the pseudo-second-order model, suggesting that chemisorption was the primary mechanism. The results of SEM and P k-edge XANES exhibited that Ca, as the dominated metal component, could act as a reaction site for the formation of phosphate precipitation. These results provide critical findings about recovering P from manure waste, which is useful for biowastes management and nutrients utilization, and mitigating unintended P loss and potential environmental risks.