Selenium-phosphorus modified biochar reduces mercury methylation and bioavailability in agricultural soil

Abstract

Biochar is a frequently employed for solidifying and stabilizing mercury (Hg) contamination in soil. However, it often results in an elevated presence of soil methylmercury (MeHg), which introduces new environmental risks. Consequently, there is a necessity for developing a safer modified biochar for use in Hg-contaminated soil. This study employed sodium selenite (at a safe dosage for soil) and hydroxyapatite to modify straw biochar (BC) based on the interaction between selenium (Se) and phosphorus (P). This process led to the formation of Se-modified biochar (Se-BC), P-modified biochar (P-BC), and Se and P co-modified biochar (Se-P-BC). Additionally, solvent adsorption experiments and pot experiments (BC/soil mass ratio: 0.5 %) were conducted to investigate the impacts of these soil amendments on soil Hg methylation and bioavailability. Se and P co-modification substantially increased the surface area, pore volume, and Hg adsorption capacity of BC. BC treatment increased the simulated gastric acid-soluble Hg, organo-chelated Hg, and MeHg in the soil. Conversely, Se-P-BC significantly reduced these forms of Hg in the soil, indicating that Se-P-BC can transform soil Hg into less bioavailable states. Among the different biochar treatments, Se-P-BC exhibited the most pronounced reductions in soil MeHg, total Hg, and MeHg in water spinach, achieving reductions of 63 %, 71 %, and 70 %, respectively. The co-modification of Se and P displayed a synergistic reduction effect in managing soil Hg pollution, which is associated with the increase of available Se in the soil due to phosphorus addition. The significantly reduced dissolved organic carbon and the abnormally high SO₄^2- concentration in the soil of Se-P-BC treatment also inhibited Hg methylation and bioavailability in the soil. In summary, Se-P-BC substantially increased reduction percentage in plant Hg content while mitigating the risk of secondary pollution arising from elevated soil MeHg.

Keywords: Biochar; Hg; Hydroxyapatite; MeHg; Se; Soil.