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Characterization and adsorption performance of New Zealand biochar for the removal of paracetamol and ibuprofen from synthetic solutions in batch and column systems

Abstract
Pharmaceuticals are a significant class of emerging organic contaminants that have been increasingly detected in aquatic environments. Their persistence and limited removal by conventional treatment methods poses considerable risks to both flora and fauna. The study investigates the adsorption performance of New Zealand-sourced biochar both raw and surface-modified for the removal of two widely used pharmaceuticals, paracetamol and ibuprofen, from aqueous solutions. With its local availability and carbon-rich structure, biochar was evaluated as an innovative solution to address the growing challenge of emerging pharmaceutical pollutants in aquatic environments. The research aimed to characterize the physicochemical properties of biochar and evaluate its adsorption capacity under batch and column configurations, addressing removal efficiency, equilibrium behaviour, kinetic mechanisms, and dynamic breakthrough performance. The biochar was instrumentally analysed by BET surface area analysis, Fourier-transform infrared spectroscopy (FTIR) and scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM–EDX) to examine the biochar’s surface structure and functional groups. Premium Biochar demonstrated the highest BET surface area (308.3 m²/g), which further increased to 354 m²/g after 30% KOH activation, indicating enhanced porosity and improved availability of adsorption sites. Batch adsorption experiments revealed that paracetamol achieved higher removal efficiencies and adsorption capacities (up to 8.5 mg/g) compared to ibuprofen (maximum of 2.8 mg/g), largely due to its smaller molecular size and greater polarity. The non-linear technique using isotherm and kinetic model was used to validate the process efficiency of pharmaceuticals removal. Kinetic modelling indicated pseudo-second order and Elovich models best described the adsorption mechanisms (R² > 0.997), confirming chemisorption on heterogeneous surfaces as the dominant process. Isotherm analysis showed multilayer Freundlich adsorption for paracetamol and monolayer Langmuir adsorption for ibuprofen reflecting differences in multilayer versus monolayer adsorption behaviour. Column experiments were conducted under single-pass, closed-loop recirculation, and semi-continuous dosing modes. Single-pass continuous flow showed in rapid breakthrough at short empty bed contact times (1.6–4.5 minutes) due to hydraulic limitations. In contrast, closed-loop recirculation columns achieved up to 90% paracetamol removal and 58% ibuprofen removal under extended operation, specifically, the optimal condition when using 1 mm particle size KOH-activated biochar (1 mm KOH-modified biochar, 15 L/min flow, 500 min runtime). Semi-continuous dosing experiments demonstrated gradual adsorbent saturation with final adsorption capacities of approximately 0.43–0.57 mg/g, supporting the need for regeneration strategies in long-term applications.
Type
Thesis
Type of thesis
Series
Citation
Date
2025-07-06
Publisher
The University of Waikato
Supervisors
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