Passivation mechanism of Cu and Zn with the introduction of composite passivators during anaerobic digestion of pig manure

•Degradation rate of composite passivator added to organic matter reached 30.01%.•Composite passivator promoted the formation of humus.•Binding characteristics of Cu and Zn with humus were changed after digestion.•Passivators and humus played different roles in passivation of Cu and Zn. Heavy metals in livestock manure pose a threat to the environment after biogas fertilizer being utilized, while its bioavailability is reduced substantially by passivator during the anaerobic digestion. In this study, an optimal composite passivator of humic acid, fly ash and biochar with proportion of 7.5%:7.5%:7.5% and 5.0%:7.5%:7.5% is obtained and the passivation mechanism on Cu and Zn during anaerobic digestion of pig manure is explored. The content of humic acid (HA) in biogas residue increased by 15.66–27.82%, which promoted the transformation from FA-Cu/Zn to HA-Cu/Zn and was beneficial to the passivation of Cu and Zn. The bioavailability of Cu and Zn was reduced by the adsorption and complexation at the early and middle stages of anaerobic digestion. Humic substances play a major role in the passivation of heavy metals at the late stage. The composite passivator can improve the humification degree of biogas residue and reduce heavy metal biotoxicity.