Binding characteristics of copper onto biochar-derived DOM using general, heterospectral and moving-window two-dimensional correlation analyses

Dissolved organic matter released from biochar (biochar-derived DOM, BDOM) could dominate the environmental behavior and fate of trace metals by forming BDOM-metal complexes. Here general, heterospectral as well as moving-window (MW) two-dimensional correlation spectroscopy (2DCOS) analyses of synchronous fluorescence and Fourier transform infrared spectra were employed to explore the heterogeneous binding characteristics between sludge BDOM and Cu(II). The results revealed that Cu-BDOM binding first occurred in the fulvic-like (368-380 nm), then humic-like (428 nm) fluorescent fractions, followed by infrared groups of phenolic hydroxyl groups, carboxylate, C-OH of polysaccharide groups, C=C of aromatic carbon, CH of aliphatics and C-O-C of aliphatic ethers. The binding affinity of the hydrophilic groups was stronger than that of hydrophobic groups in BDOM towards Cu(II). Fluorescence components in BDOM played a decisive role in the binding of Cu(II) with trace concentration (1 mu M), while infrared functional groups made a substantial contribution in the complexation of Cu(II) with higher concentration (10-100 mu M). The concentration of final configuration transformation point (11.7 mu mol/mg in this study) by MW2DCOS analysis was suggested as an actual binding threshold that was helpful for evaluating their environmental behaviors.