Adsorption of Caffeine and Demethylated Metabolites on Na+-Exchanged Bentonite

Clay minerals are promising candidates for caffeine removal due to their environmental friendliness and natural abundance. In this study, a commercially available bentonite was modified by Na+ exchange and characterized using Fourier transform infrared spectroscopy, X-ray diffractometry, scanning electron microscopy, zeta potential measurements, and specific surface area analysis. Caffeine adsorption was rapid, reaching equilibrium within 15 min. Adsorption isotherms for caffeine and its metabolites (theobromine, paraxanthine, and theophylline) in pure water were analyzed at 25.0 ± 0.5 °C using Langmuir and Freundlich models, both individually and in mixtures. Only caffeine exhibited favorable adsorption behavior, fitting the Langmuir equation, which allowed for the determination of a maximum adsorption capacity of 20 ± 3 mg/g, regardless of metabolite presence. The removal exceeded 85% of the caffeine from a 5.0 mg/L solution. The adsorption affinity of the studied compounds toward Na+-exchanged bentonite followed the order: caffeine >>> theobromine > paraxanthine ~ theophylline. The modified bentonite was then tested for caffeine removal from beverages and synthetic urine, achieving removal efficiencies exceeding 87%. To our knowledge, this is the first study investigating the effect of major caffeine metabolites on adsorption rates across different sample matrices, such as artificial urine, cola soda, soluble coffee, energy drinks, green tea, and yerba mate.