Enhanced Biosorption of Cr(III) from Aqueous Solutions Using Tamarind Shell (Tamarindus indica L.): Effect of Pretreatments, Thermodynamic Analysis and Surface Characterization

The discharge of metal-containing effluents into aquatic systems remains a major environmental concern because metal ions can persist in water bodies and accumulate in biological systems, potentially affecting ecosystem and human health. Among these contaminants, Cr(III) is frequently encountered in waste streams generated by industrial activities, making its removal an important objective in water quality management. This study investigated the adsorption behavior of Cr(III) using lignocellulosic biosorbents obtained from tamarind shell (Tamarindus indica) after water, H2O2, and HCl pretreatments, with particular emphasis on equilibrium behavior, thermodynamic characteristics, and pretreatment-induced physicochemical modifications. Batch adsorption experiments were conducted to evaluate equilibrium behavior. The highest adsorption capacity (41.6 mg g−1) was obtained with the water-treated biosorbent at 60 °C. The equilibrium data were best represented by the Sips model, suggesting that Cr(III) adsorption occurred on surfaces containing adsorption sites with different energetic characteristics. Thermodynamic analysis revealed that the adsorption process was spontaneous, while the enthalpy changes indicated predominantly endothermic behavior for the pretreated biosorbents. ATR-FTIR, SEM, EDS, and XRD analyses were performed to characterize the biosorbents before and after adsorption. The characterization results indicated that oxygen-containing functional groups, particularly hydroxyl and carbonyl functionalities, were associated with the adsorption process. SEM images showed morphological changes associated with pore occupation, while EDS confirmed chromium adsorption and suggested possible ion-exchange mechanisms. XRD patterns indicated a mainly amorphous structure. The results demonstrated that pretreatment-induced modifications strongly influenced the adsorption performance of tamarind shell. Water pretreatment produced the most favorable adsorption behavior, yielding the highest adsorption capacity among the evaluated biosorbents. The combined interpretation of equilibrium, thermodynamic, and characterization results revealed a close relationship between surface properties and Cr(III) uptake.