Chlorella vulgaris-Derived Biochars for Metribuzin Removal: Influence of Thermal Processing Pathways on Sorption...

Carbonaceous sorbents were prepared from Chlorella vulgaris via hydrothermal carbonization (200 °C and 250 °C) and slow pyrolysis (300-500 °C) to assess their effectiveness in removing the herbicide metribuzin from water. The biomass was cultivated under controlled laboratory conditions, allowing for consistent feedstock quality and traceability throughout processing. Using a single microalgal feedstock for both thermal methods enabled a direct comparison of hydrochar and pyrochar properties and performance, eliminating variability associated with different feedstocks and allowing for a clearer assessment of the influence of thermal conversion pathways. While previous studies have examined algae-derived biochars for heavy metal adsorption, comprehensive comparisons targeting organic micropollutants, such as metribuzin, remain scarce. Moreover, few works have combined kinetic and isotherm modeling to evaluate the underlying adsorption mechanisms of both hydrochars and pyrochars produced from the same algal biomass. Therefore, the materials investigated in the present work were characterized using a combination of standard physicochemical and structural techniques (FTIR, SEM, BET, pH, ash content, and TOC). The kinetics of sorption were also studied. The results show better agreement with the pseudo-second-order model, consistent with chemisorption, except for the hydrochar produced at 250 °C, where physisorption provided a more accurate fit. Freundlich isotherms better described the equilibrium data, indicating heterogeneous adsorption. The hydrochar obtained at 200 °C reached the highest adsorption capacity, attributed to its intact cell structure and abundance of surface functional groups. The pyrochar produced at 500 °C exhibited the highest surface area (44.3 m²/g) but a lower affinity for metribuzin due to the loss of polar functionalities during pyrolysis. This study presents a novel use of Chlorella vulgaris-derived carbon materials for metribuzin removal without chemical activation, which offers practical benefits, including simplified production, lower costs, and reduced chemical waste. The findings contribute to expanding the applicability of algae-based sorbents in water treatments, particularly where low-cost, energy-efficient materials are needed. This approach also supports the integration of carbon sequestration and wastewater remediation within a circular resource framework.