Enhanced adsorption of aqueous perfluorooctanoic acid on iron-functionalized biochar: elucidating the roles of inner-sphere complexation

Abstract

Perfluorooctanoic acid (PFOA) is ubiquitously detected in various water bodies, which raises the urgent need for developing effective and economic remediation methods in response to its health risks. The adsorptive removal of PFOA by biochar (BC) is regarded as a simple, effective, and economical technique. However, engineered BCs, including FeCl3-activated BC, for PFOA removal and adsorption mechanisms have been ill-studied. In this study, a FeCl3-activated dairy manure-derived biochar (Fe@MBC) was prepared via one-step pyrolysis/activation, and its properties and adsorption characteristics were compared with a pristine manure-derived biochar (P-MBC). The FeCl3 activation largely increased the surface area of Fe@MBC and the deposition of FexOy minerals on surface of Fe@MBC while significantly elevating the surface roughness of Fe@MBC. The maximum adsorption capacity of Fe@MBC for PFOA (233 mg·g−1) was five times higher than that of P-MBC (46 mg·g−1). PFOA adsorption was favorable at low solution pH and was independent on ionic strength, which supported the major contribution by inner-sphere complexation rather than out-sphere complexation. This mechanism was further confirmed by the disappearance of FeO peak on Fourier transform infrared spectrum and the blue-shift of Fe binding energies on X-ray photoelectron Fe 2p spectrum of Fe@MBC after PFOA adsorption. Fe@MBC maintained a near 100% adsorption capacity for PFOA after 4 cycles of chemical regeneration. Fe@MBC also exhibited efficient removal for PFOA and other PFAS compounds at trace levels in the lake water and wastewater treatment plant effluent. Thus, this study highlights a promising insight for selectively eliminating PFASs from water.