Interactions between carbon-based nanoparticles and steroid hormone micropollutants in water

Highlights: • Hormone adsorption by different carbon-based nanoparticles (CNPs) was evaluated. • CNPs (except C₆₀) shown fast adsorption kinetics and high capacity. • Accessible surface area of CNPs is the most important factor in hormone adsorption. • Accessible surface area greatly depends upon the state of aggregation. • Adsorptive interactions induced in short and long ranges were determined. The occurrence of micropollutants (MPs) including steroid hormones is a global environmental and health challenge. Carbon-based nanoparticles can be incorporated with water treatment processes to allow MP removal by adsorption. The aim was to compare the suitability of such nanoparticles (graphene, graphene oxide, carbon nanotubes and C₆₀) to adsorb steroid hormones for later incorporation in membrane composites. All nanoparticles displayed fast kinetics; carbon nanotubes and graphene showed high adsorption capacities for hormones undeterminable in isotherm studies (over 10 mg/g). External surface adsorption appears to be the most prominent factor impacting adsorption performance. Structure, conformation, geometry and surface charge of nanoparticles can influence the accessibility of surface area through colloidal instability in aqueous solution. Mechanism inspection shows that adsorption initiates at long ranges (up to 10 nm) through hydrophobic and electrostatic interactions. At relatively short ranges (0.2–0.5 nm), adsorption is enhanced by π/π stacking, XH / π (X = C, O) interactions, van der Waals forces and hydrogen bonding. Both long- and short-range forces transporting hormones from the liquid bulk into the adsorbed phase could control the rate. With relatively short residence time required and high adsorption capacity, carbon nanotubes and graphene are promising for incorporation in a membrane composite.