Understanding the interactions between natural organic matter (NOM) and zero-valent iron nanoparticles (nano-Fe0) and magnetite nanoparticles (nano-Fe3O4) is essential for evaluating their performance in pollutant remediation, as well as determining their fate and transport in the environment. Batch experiments were performed to investigate the sorption/desorption behaviors of humic acid (HA) on commercially available nano-Fe0 and nano-Fe3O4. The sorption/desorption of HA on nano-Fe0 and nano-Fe3O4 were well described by both the Langmuir model and the modified Langmuir model. The adsorption capacities of HA were 8.77 ± 0.31 mg C/g and 10.05 ± 0.95 mg C/g for nano-Fe0 and nano-Fe3O4, respectively. The interactions of HA with nano-Fe0 and nano-Fe3O4 were highly pH-dependent. On one hand, nano-Fe0 had its maximum adsorption of 11.0 mg C/g HA at pH = 3, which decreased to 0.6 mg C/g when pH increased to 11.9; on the other hand, alkaline condition enhanced HA desorption greatly. At pH = 10.1, after 24 h desorption experiments, nearly 80% of initially adsorbed HA desorbed from the nanoparticles. The interactions of HA with nano-Fe0 and nano-Fe3O4 were also influenced by different ion compositions in solution. Divalent cations (e.g. Ca2+, Mg2+) enhanced HA adsorption significantly, while phosphate nearly eliminated HA adsorption and promoted significantly HA desorption.

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