Development and Modelling of Cellulose Nano-Crystal from Agricultural Wastes for Adsorptive Removal of Pharmaceuticals in Wastewater

Authors: Abubakar Muhammad Hammari, Usman Dadum Hamza, Maryam Ibrahim, Kabir Garba, Idris Muhammad Misau, .

Abstract:

Pharmaceuticals are increasingly present in water systems, posing threats to ecosystems and human health. The effective treatment of pharmaceutical wastewater presents a significant challenge due to the complex and diverse organic and inorganic contaminants it contains. Conventional treatment methods often struggle to completely remove these pollutants due to their stability and water solubility, leading to environmental concerns and potential health risks. This research proposes the use of cellulose nanocrystals (CNCs) derived from agricultural waste as efficient and sustainable adsorbents for pharmaceutical wastewater treatment. CNCs offer high surface area, biodegradability, and low cost compared to existing options. This study evaluates the production, characterization, adsorption properties, and reusability of cellulose nanocrystals (CNCs) derived from waste paper (CNC-WP), rice husk (CNC-RH), and groundnut shell (CNC-GS). The percentage yield of CNCs was highest from wastepaper at 50.67%, followed by groundnut shell at 33.40% and rice husk at 26.46%. X-ray diffraction (XRD) confirmed the cellulose crystalline structure across all samples while scanning electron microscopy (SEM) revealed a needle-like morphology with size distribution variations. Energy-dispersive X-ray spectroscopy (EDX) identified carbon and oxygen as the primary elements, with minor residual inorganic materials varying by source. BET analysis indicated high surface areas for all CNCs, with CNC-RH exhibiting the highest value (464.592 m²/g), suggesting a more porous structure. The pore sizes of all samples fell within the meso-pore range (2.108 nm to 2.153 nm). Adsorption studies focused on metronidazole (MNZ) removal using CNC-WP. Isotherm models, including Langmuir and Sips, described the equilibrium between MNZ concentration and adsorption onto CNC-WP, showing the best fit with R² values exceeding 0.95. The adsorption process was favourable, with monolayer coverage and potential binding energy heterogeneity. Kinetic modelling identified the pseudo-second-order model as the best fit (R² = 1, SSE = 5.00 x 10-₇), indicating chemisorption as the predominant mechanism. Thermodynamic analysis revealed negative ΔG values at all temperatures, indicating spontaneous adsorption, with more favourable adsorption at higher temperatures. The adsorption process was exothermic, as indicated by negative ΔH values. Reusability studies demonstrated that CNC-WP retained high MNZ removal efficiency, with a modest decrease from 99.59% to 89.11% over ten regeneration cycles. This study highlights the efficiency of wastepaper as a raw material for CNC production and its potential for effective and reusable MNZ adsorption.

Keywords: cellulose nanocrystals (CNCs), adsorption efficiency, metronidazole removal, reusability