Humic Acid-Stabilized Biogenic FeS Nanoparticles for Cr(VI) Removal Under Simulated Acidic Mine Drainage Conditions: Optimization and Interfacial Transformation Pathways

Acidic mine drainage (AMD) poses a severe global environmental threat due to its high acidity and elevated levels of toxic hexavalent chromium (Cr(VI)), for which biogenic iron sulfide (FeS) nanoparticles have emerged as a promising remediation agent; however, their practical application is hindered by aggregation and oxidative deactivation. This research synthesized biogenic FeS nanoparticles via sulfate-reducing bacteria (SRB) and employed humic acid (HA) as a stabilizing agent to enhance Cr(VI) removal performance in simulated AMD conditions. Single-factor experiments combined with response surface methodology identified the optimal biosynthetic conditions for FeS: yeast extract powder dosage of 2.2 g/L, Fe/S molar ratio of 0.8, and NH₄Cl dosage of 3.1 g/L. Under these conditions, the material achieved 84.25% Cr(VI) removal, with the Fe/S molar ratio identified as the most influential parameter governing synthesis and performance. Introducing HA at an optimal dosage of 2 mg/L drove marked improvements in both nanoparticle yield and reactivity: FeS yield increased to 1096.26 mg/L, Cr(VI) removal efficiency reached 99.62%, and residual Cr(VI) dropped from 15.75 mg/L to just 0.38 mg/L. Kinetic and isotherm analyses, paired with SEM/TEM imaging and zeta potential measurements, revealed that HA stabilization improved particle dispersion and reduced lamellar stacking, resulting in a surface-controlled Cr(VI) removal process. FTIR and 2D-COS analyses demonstrated that HA-derived oxygen-containing functional groups, including O-H/N-H, C=O, and C-O moieties, played a central role in interfacial interactions during Cr(VI) sequestration. XRD results confirmed that Cr(VI) was reduced to Cr(III) and primarily immobilized as low-solubility CrOOH and Cr₂S₃, while the formation of Fe-Cr spinel-like phases remains tentative without X-ray Photoelectron Spectroscopy (XPS) validation. Further investigation via surface-sensitive spectroscopy and dynamic leaching tests is needed to fully assess the long-term stability of the reaction products.