Unveiling the Adsorptive Potential of Natural Biopolymers for Olive Mill Wastewater Treatment: A Synergistic Approach Using RSM-BBD, Mixture Design, Kinetics, and Mechanistic Analysis

Abstract

This study evaluates the structural properties and adsorption capacities of four bio-based adsorbents, sawdust (SD), straw (ST), chicken feathers (CFs), and shrimp shells (SSs), for chemical oxygen demand (COD) removal from olive mill wastewater (OMW). Response Surface Methodology (RSM) with a Box-Behnken Design (BBD) was applied to optimize the operational parameters, resulting in maximum COD uptake capacities of 450 mg/g (SD), 575 mg/g (ST), 700 mg/g (CFs), and 750 mg/g (SSs). Among these materials, SSs exhibited the highest COD removal efficiency of 85% under optimal conditions (pH 8, 20 g/L, 30 °C, 5 h, 111 rpm). A mixture design approach was then used to explore the synergistic effects of combining lignocellulosic (SD and ST), chitin-based (SSs), and keratin-based (CFs) adsorbents. The optimized blend (SD 10%, ST 28.9%, SS 38.3%, and CF 22.6%) achieved a COD removal efficiency of 82%, demonstrating the advantage of using mixed biopolymer systems over individual adsorbents. Adsorption mechanisms were investigated through isotherm models (Langmuir, Freundlich, Temkin, and Redlich-Peterson) and kinetic models (pseudo-first-order, pseudo-second-order, Elovich, and intraparticle diffusion). Lignocellulosic adsorbents predominantly followed physisorption mechanisms, while chitin- and keratin-rich materials exhibited a combination of physisorption and chemisorption. Thermodynamic analysis confirmed the spontaneous nature of the adsorption process, with SSs showing the most favorable Gibbs free energy (ΔG = -21.29 kJ/mol). A proposed mechanism for the adsorption of organic compounds onto the bio-adsorbents involves hydrogen bonding, electrostatic interactions, π-π interactions, n-π stacking interactions, hydrophobic interactions, and van der Waals forces. These findings highlight the potential of biopolymer-based adsorbents and their optimized combinations as cost-effective and sustainable solutions for OMW treatment.