Two recyclable and complementary adsorbents of coal-based and bio-based humic acids: High efficient adsorption and immobilization remediation for Pb(II) contaminated water and soil

Humic acid can effectively bind heavy metals and is a promising remediation agent for heavy metals-contaminated water and soil. Many successful applications of humic acid have been reported, but rarely studied the specific process and mechanism of heavy metal removal by humic acids from water and soil, especially the simultaneous application of coal-based and bio-based humic acids. In this work, two kinds of coal-based and bio-based humic acid materials (CHA and BHA) from weathered coal and rice husk were industrially produced and studied their Pb(II) adsorption and immobilization characteristics and mechanisms in water and soil. The batch adsorption experiments obtained the Pb(II) adsorption by CHA and BHA both were spontaneous and endothermic monolayer chemisorption and controlled by three rate-limiting steps (bulk, film, and pore) in the adsorption process. CHA and BHA had highly efficient Pb(II) adsorption capacities, obtained their maximum adsorption capacity was 201 and 188 mg g-1, respectively. In addition to the two main adsorption mechanisms of ion exchange and surface complexation, electrostatic interaction, precipitation reaction, and π-π interaction were also involved. Soil culture experiments showed that CHA and BHA both exhibited a highly efficient immobilization effect on Pb(II)-contaminated soil, and CHA and BHA had a better synergistic promotion effect. Compared with the CK soil, the content of DTPA-Pb(II) decreased by 10.2-13.2% and the content of RES-Pb(II) increased by 14-22% in soils treated with different humic acids. Ion exchange, complexation, precipitation, and electrostatic attraction promote the transformation of unstable Pb(II) to stable Pb(II), which was of great significance for the immobilization of Pb(II) in soil. Overall, CHA and BHA have the potential to be used as green, efficient, and promising adsorbents to remove and immobilize Pb(II) from wastewater and soil.