Mechanisms of Cd immobilization in contaminated calcareous soils with different textural classes treated by acid- and base-modified biochars

Acid or base modification of biochars has shown promise for enhancing the immobilization of potentially toxic elements (PTEs) such as cadmium (Cd) in contaminated soils. However, limited information is available on the interaction between soil textural classes and modified biochar application for Cd stabilization in contaminated calcareous soils. Therefore, the objective of the study was to examine the extent of Cd immobilization in contaminated calcareous soils with diverse textural classes, utilizing both acid (HNO₃) and alkali (NaOH) modified and unmodified biochars derived from sheep manure and rice husk residues. The modified or unmodified biochars were applied at a rate of 2% (w/w) to Cd-contaminated silty clay loam, loam, and sandy loam soils, followed by a 90-day incubation at field water capacity. Sequential extraction and EDTA-release kinetics studies were used to assess the effect of the treatments on the extent and mechanisms of Cd immobilization. Among the treatments, acid-modified manure biochar was most effective at reducing water soluble and exchangeable Cd fractions (-20.5%), by converting them into metal oxide and organic matter bound fractions. This effectiveness was primarily attributed to the significant increase in surface oxygen functional groups in the acid-modified biochar which could promote Cd complexation. However, the acid-modified manure biochar released more immobilized Cd during EDTA extraction than the base-modified manure biochar, suggesting that EDTA extraction of R-O-Cd complexes was easier than extracting Cd associated with insoluble compounds. This difference was likely due to the acidic pH and lower ash content of the acid-modified biochars compared to the base-modified manure biochars. Additionally, the extent of Cd immobilization was lower in sandy loam soil, highlighting the importance of immobilizing Cd in light-textured soils to prevent its transfer to organisms.