The interaction of different chlorine-based additives with swine manure during pyrolysis: Effects on biochar properties and heavy metal volatilization

Poor properties and high concentrations of heavy metals are still major concerns of successful application of animal manure-derived biochar into the environment. This work thus proposed to add chlorine-based additives (Cl-additives, i.e., CaCl2, MgCl2, KCl, NaCl, and PVC, 50 g Cl/ kg) to improve biochar properties and enhance heavy metal volatilization during swine manure pyrolysis. The results showed that the addition of CaCl2 could improve the retention of carbon (C) by up to 13.1% during pyrolysis, whereas other Cl-additives had little effect on it. Moreover, CaCl2 could enhance the aromaticity of biochar, as indicated by lower H/C ratio than raw biochar. Pretreatment with CaCl2, MgCl2 and PVC reduced phosphorus (P) solubility but increased its bioavailability via the formation of chlorapatite (Ca5(PO4)3Cl). The CaCl2 was more effective for enhancing the volatilization efficiency of heavy metals than other Cl-additives, except for Pb that tended to react with the generated Ca5(PO4)3Cl to form more stable and less volatile Pb5(PO4)3Cl. However, high pyrolysis temperature (900℃) was essential for CaCl2 to simultaneously decrease the bioavailability of heavy metals. Our results indicated that co-pyrolysis of swine manure with CaCl2 is a promising strategy to increase C retention, P bioavailability, and volatilization of heavy metals, and, at higher temperature, reduce the bioavailability of biochar-born heavy metals.