Interaction between biochar-dissolved organic matter and chlorophenols during biochar adsorption.

Biochar (BC) has been widely applied in the remediation of chlorophenols (CPs) from contaminated sites in which the role and mechanisms of BC dissolved organic matter (BDOM), as a crucial component of BC, with CPs are largely unknown and thus need to be investigated. In this study, DOM was derived from peanut hulls (PDOM) and corn stalks (CDOM) as BC sources, and the interactions between PDOM/CDOM and 2,4,6-trichlorophenol (TCP) were analysed using excitation-emission matrix spectroscopy (EEM) in combination with multiple models. EEM combined with fluorescence region integration (EEM-FRI) indicated that humic-like materials were the major materials of both PDOM and CDOM (percentage fluorescence response R > 60%), and CDOM contained more protein- and fulvic-like materials than PDOM. Based on EEM in combination with parallel factor analysis (EEM-PARAFAC), 4 components were obtained, and the percentage decrease in maximum fluorescence intensities (F) showed that the main components interacting with TCP in PDOM/CDOM were protein- and fulvic-like components (> 25%). Moreover, the modified Stern-Volmer model was used to calculate the stability constants (Log K) of PDOM/CDOM and TCP for the first time, and the mechanism of static quenching was dominant for interacting with TCP in PDOM (Log K: 4.36-4.65) and CDOM (Log K: 3.53-4.73). Furthermore, the sequential TCP binding of fluorescent components in BDOM generally followed the order of protein-like → short-wavelength fulvic-like → long-wavelength fulvic-like → humic-like components. These findings will provide a basis for screening biochar as a functional material for CP remediation applications and for understanding the environmental chemical behaviour of leached DOM during biochar application.