Transformations of Phosphorus Speciation during (Hydro)thermal Treatments of Animal Manures

Phosphorus (P) in animal manures is an important P pool for P recycling and reclamation. In recent years, thermochemical techniques have gained much interests for effective waste treatment and P recycling. This study comparatively characterized the transformation of P during two representative thermochemical treatments (pyrolysis and hydrothermal carbonization, HTC) of four animal manures (swine, chicken, beef, and dairy manures) by combining nuclear magnetic resonance spectroscopy, X-ray absorption spectroscopy, and sequential extraction. For both pyrolysis and HTC treatments, degradation of organic phosphate and crystallization of Ca phosphate minerals were observed and were highly dependent on treatment temperature. Extensive crystallization of Ca phosphate minerals occurred at temperatures above 450 °C during pyrolysis, compared to the lower temperature (175 and 225 °C) requirements during HTC. As a result, P was immobilized in the hydrochars and high temperature pyrochars, and was extracted primarily by HCl. Because Ca is the dominating P-complexing cation in all four manures, all manures showed similar P speciation and transformation behaviors during the treatments. Results from this work provided deeper insights into the thermochemical processes occurred during the pyrolysis and HTC treatments of biological wastes, as well as guidance for P reclamation and recycling from these wastes.