Temperature-Dependent Molecular Evolution of Biochar-Derived Dissolved Black Carbon and Its Interaction Mechanism with Polyvinyl Chloride Microplastics

Biochar-derived dissolved black carbon (DBC) molecules are dependent on the BC formation temperature and affect the fate of emerging contaminants in waters, such as polyvinyl chloride microplastic (MP_PVC). However, the temperature-dependent evolution and MP_PVC-interaction of DBC molecules remain unclear. Herein, we propose a novel DBC-MP_PVC interaction mechanism by systematically interpreting heterogeneous correlations, sequential responses, and synergistic relationships of thousands of molecules and their linking functional groups. Two-dimensional correlation spectroscopy was proposed to combine Fourier transform-ion cyclotron resonance mass spectrometry and spectroscopic datasets. Increased temperature caused diverse DBC molecules and fluorophores, accompanied by molecular transformation from saturation/reduction to unsaturation/oxidation with high carbon oxidation states, especially for molecules with acidic functional groups. The temperature response of DBC molecules detected via negative-/positive-ion electrospray ionization sequentially occurred in unsaturated hydrocarbons → lignin-like → condensed aromatic → lipid-/aliphatic-/peptide-like → tannin-like → carbohydrate-like molecules. DBC molecular changes induced by temperature and MP_PVC interaction were closely coordinated, with lignin-like molecules contributing the most to the interaction. Functional groups in DBC molecules with m/z < 500 showed a sequential MP_PVC-interaction response of phenol/aromatic ether C-O, alkene C═C/amide C═O → polysaccharides C-O → alcohol/ether/carbohydrate C-O groups. These findings help to elucidate the critical role of DBCs in MP environmental behaviors.