Mechanisms of calcium-mediated As(V) immobilization by undissolved and dissolved biochar in saline-alkali environments.

The environmental impact of arsenic (As) pollution has been a focal point within environmental science. In arsenic-polluted saline-alkali environment, the addition of exogenous biochar can affect the morphological transformation of As both through direct and indirect mechanisms, with calcium ions (Ca(II)) playing a crucial role. This study investigates the immobilization mechanisms of undissolved biochar (UOB) and dissolved biochar (DOB) on As(V) in the absence and presence of Ca(II) under alkaline conditions and aerobic atmosphere. While UOB and DOB alone are insufficient for As(V) immobilization, their combined action in the presence of Ca(II) achieves remarkable immobilization rates of 91.9% and 98.1%, respectively. Precipitation of calcium arsenate is identified as the primary immobilization pathway in both the UOB-Ca(II)-As(V) and DOB-Ca(II)-As(V) systems. Furthermore, Ca(II) acts as a mediator for As(V) immobilization through the formation of ternary UOB/DOB-Ca-As complexes, which are corroborated by Density Functional Theory (DFT) analysis from a microscopic perspective. Notably, the synergistic immobilization of As by DOB and newly generated CaCO in DOB-Ca(II)-As(V) system is highlighted. Additionally, the increase in Ca(II) concentration (0-100 mM) and solution pH (9.0-12.0) both significantly enhance the immobilization of As(V). An increase in the dosage of UOB (0.4-4 g/L) reduces the immobilization of As(V), while effect of the DOB concentration is insignificant. This study provides new insights into how the release of two biochar fractions into a typical Ca(II)-rich saline-alkali environment may alter the fate and transport of As species.