Evaluating Agro-Based Waste Materials for Cyanotoxin Sorption for Future Incorporation in Nature-Based Solution Units (NBSUs)

Toxic cyanobacterial blooms are a growing environmental problem, persisting in freshwater bodies globally, and potentially hazardous to populations that rely on surface freshwater supplies. Nature-based solution units (NBSUs) are effective and sustainable approaches for water treatment, with sorption being an important process. The purpose of this study was to evaluate unmodified agro-based waste materials (rice husks, olive pulp pomace pellets (OP), cork granules) and the benchmark NBSU substrates (biochar, light expanded clay aggregate (LECA), and sand) for their microcystin-LR (MC-LR) and cylindrospermopsin (CYN) sorption potential. The kinetics and sorption mechanism of the two best sorbent materials were studied for future incorporation into NBSUs. Pre-screening of the sorbents showed highest sorption with biochar (>86% MC-LR and >98% CYN) and LECA (78% MC-LR and 80% CYN) and lower sorption with rice husk (<10%), cork (<10%), and sand (<26%). Leaching from OP made them unsuitable for further use. The sorption of both the cyanotoxins onto biochar was rapid (8 h), whereas onto LECA it was steadier (requiring 48 h for equilibrium). The pseudo-second-order kinetic model fit the sorption of both cyanotoxins onto biochar and LECA (R2: 0.94–0.99), suggesting that the sorption rate is limited by chemisorption. The sorption of MC-LR and CYN to biochar and LECA fit the Freundlich and D–R models better, suggesting multilayer sorption, high heterogeneity, and porosity in the sorbents (which was also confirmed by SEM/EDS). The sorption capacity was observed to be higher for biochar (Kf: MC-LR = 0.05, CYN = 0.16) than LECA (Kf: MC-LR = 0.02, CYN = 0.01).