Adsorption of organic contaminants on biochar colloids: effects of pyrolysis temperature and particle size

Biochar (BC) colloids attract increasing interest due to their unique environmental behavior and potential risks. However, the interaction between BC colloids and organic contaminants that may affect their fates in the environment has not been substantially studied. Herein, adsorption and desorption of phenanthrene (PHN), atrazine (ATZ), and oxytetracycline (OTC) by a series of BC colloids derived from bulk rice straw BC samples with 6 pyrolysis temperatures (200-700 degrees C), and 3 particle sizes (250 nm, 500 nm, and 1 mu m) were investigated. Regardless of pyrolysis temperature, BC colloids from a given sized bulk BC had a comparable size, being 30 +/- 6, 70 +/- 18, and 140 +/- 15 nm corresponding to the three sized bulk BCs, respectively. The adsorption kinetics curves were well explained by the pseudo-second-order model, and pore diffusion was the primary rate-determining step. Both Freundlich and Langmuir models well fitted the adsorption isotherms. With increasing pyrolysis temperature or decreasing particle size of bulk BC, the specific surface area and pore volumes of the derived BC colloids increased, the kinetics model fitted adsorption rates (k(2)) of the three organics by the BC colloids all largely decreased, and the Langmuir model fitted adsorption capacities (Q(max)) increased. The highest Q(max) was obtained by BC colloids from the smallest (250 nm) bulk BC with the highest pyrolysis temperature (700 degrees C), being 212 mu mol g(-1) for PHN, 815 mu mol g(-1) for ATZ, and 72.4 mu mol g(-1) for OTC. The adsorption was reversible for PHN and ATZ, while significant desorption hysteresis was observed for OTC on BC colloids with middle pyrolysis temperatures (300-500 degrees C). The underlying mechanisms including hydrophobic interaction, pi-pi electron donor-acceptor interaction, molecular size effect, and irreversible reactions were discussed to explain the difference in the adsorption and desorption behaviors. The findings increased our understanding of the environmental fate and risk of BC.