Lignin–Sustainable Polymer for Mn(II) Biosorption from Aqueous Media
Elena Ungureanu, Bogdan M. Tofanică, Maria E. Fortună, Ovidiu C. Ungureanu, Răzvan Rotaru, Valentin I. PopaIn the context of the circular bioeconomy and environmental protection trends, the efficient use of renewable resources has become a driving force for industry, and lignin represents precisely a renewable carbon resource, abundant in terrestrial biomass that could become a sustainable substitute for fossil resources, under conditions of full exploitation. This study systematically evaluates the biosorption of Manganese (Mn(II)) from aqueous media using unmodified Tripidium bengalense (Sarkanda grass) lignin. Under optimal operating conditions (adsorbent dosage of 5 g/L, pH 6.5, and 20 °C), a highly competitive experimental adsorption capacity of 12.52 mg/g was achieved. Kinetic studies revealed exceptionally rapid uptake rates, with thermodynamic equilibrium established within the first 30 min, fitting perfectly with the pseudo-second-order (Ho-McKay) model (R2 ≥ 0.9998). Equilibrium data were best described by the Freundlich isotherm (R2 ≥ 0.9886), confirming chemisorption via preferential inner-sphere complexation on a heterogeneous surface. Thermodynamic analysis verified that the process is spontaneous (ΔG ranging from −13.24 to −26.19 kJ/mol) and endothermic (ΔH from 11.21 to 14.83 kJ/mol). FTIR, SEM-EDX, and TG/DTG analyses confirmed successful Mn–O coordination involving phenolic hydroxyl and carboxylic groups. Furthermore, the lignin showed excellent recyclability, maintaining a retention efficiency over 70% (70.7–85.8%) after three desorption-resorption cycles using 1N HCl. Ecotoxicological validation via Sorghum bicolor L. germination tests confirmed the complete detoxification of the post-adsorption filtrates (up to 100% germination capacity), while the Mn(II)-loaded lignin completely suppressed seed germination (0%), proving secure metal immobilization. These findings establish raw Sarkanda grass lignin as an efficient, scalable, and ecologically sustainable biosorbent for heavy metal remediation.