Novel Insights into the Molecular-Level Mechanism Linking the Chemical Diversity and Copper Binding Heterogeneity of Biochar-Derived Dissolved Black Carbon and Dissolved Organic Matter

Biochar-derived dissolved black carbon (DBC) varies in chemical composition and significantly affects the environmental fate of metal ions. However, the intrinsic molecular composition of DBC fractions and their molecular interaction mechanisms with metal ions remain unclear. We propose a novel, molecular-level covariant binding mechanism to comparatively interpret the heterogeneities, active sites, and sequential responses of copper binding with molecular compounds in DBC and natural dissolved organic matter (DOM). Relatively large proportions of lipid/aliphatic/peptide-like compounds with low mass distributions and lignin-like compounds with oxidized/unsaturated groups existed in acidic- and alkaline-extracted DBC, respectively. A larger percentage of tannin-like/condensed aromatic compounds and higher average conditional stability constants (logK̅ Cu) of visible fluorescent components were found for DOM than for DBC. Overall, 200–320 Da and 320–480 Da molecular components contributed significantly to the logK̅ Cu values of UVA and visible fluorescent components, respectively, in DBC/DOM. Nitrogenous groups likely exhibited stronger binding affinities than phenolic/carboxylic groups. The sequential copper-binding responses of molecular compounds in DBC/DOM generally followed the order lipid/aliphatic/peptide-like compounds → tannin-like compounds → condensed aromatic compounds. These insights will improve the prediction of the potential effects of DBC on various contaminants and the risks of biochar application to ecosystems.