Citrate-modified biochar for simultaneous and efficient plant-available silicon release and copper adsorption: Performance and mechanisms

Silicon (Si) deficiency and heavy metals (HMs) pollution are common for farmland soil because of long-term intensive farming. In this study, a novel citrate-modified biochar (C-BC) was introduced as a soil conditioner to simultaneously increase the amount of plant-available Si (PASi) and immobilize HMs. The maximum amount of PASi released was 33.00 mg⋅g-1 from C-BC pre-treated with 0.1 mol⋅L-1 citrate (C-BC0.1). A formation-transport coupling mechanism for increasing the amount of PASi released was developed. Stable Si in the biomass was pyrolyzed to give silicate that was relatively mobile via nucleophilic attack of citrate and hydrolysis of amorphous Si. Silicate species were then released through the porous surface and widening cracks caused by pyrolysis. At citrate concentrations >0.1 mol⋅L-1, the surface and cracks were easily blocked by precipitates formed during pyrolysis. The ability of C-BC to remove HMs was assessed using Cu as an example. C-BC0.1 was optimal for adsorbing Cu, and the maximum adsorption capacity was 271.73 mg⋅g-1. The Cu adsorption mechanism mainly involved surface precipitation, surface complexation, electrostatic attraction and hydrogen bonding. Our research provides important implications for simultaneously addressing Si deficiency and HMs contaminant problems by these materials for soil amendment in agro-ecosystem.