Complex interplay between formation routes and natural organic matter modification controls capabilities of C60 nanoparticles (nC60) to accumulate organic contaminants

Accumulation of organic contaminants on fullerene nanoparticles (nC₆₀) may significantly affect the risks of C₆₀ in the environment. The objective of this study was to further understand how the interplay of nC₆₀ formation routes and humic acid modification affects contaminant adsorption of nC₆₀. Specifically, adsorption of 1,2,4,5-tetrachlorobenzene (a model nonionic, hydrophobic organic contaminant) on nC₆₀ was greatly affected by nC₆₀ formation route – the formation route significantly affected the aggregation properties of nC₆₀, thus affecting the available surface area and the extent of adsorption via the pore-filling mechanism. Depending on whether nC₆₀ was formed via the “top-down” route (i.e., sonicating C₆₀ powder in aqueous solution) or “bottom-up” route (i.e., phase transfer from an organic solvent) and the type of solvent involved (toluene versus tetrahydrofuran), modification of nC₆₀ with Suwannee River humic acid (SRHA) could either enhance or inhibit the adsorption affinity of nC₆₀. The net effect depended on the specific way in which SRHA interacted with C₆₀ monomers and/or C₆₀ aggregates of different sizes and morphology, which determined the relative importance of enhanced adsorption from SRHA modification via preventing C₆₀ aggregation and inhibited adsorption through blocking available adsorption sites. The findings further demonstrate the complex mechanisms controlling interactions between nC₆₀ and organic contaminants, and may have significant implications for the life-cycle analysis and risk assessment of C₆₀.