Effects of hydrophyte decomposition on the binding mechanism between fluorescent DOM and copper.

Hydrophyte decomposition caused large amounts of dissolved organic matter (DOM) to enter aquatic environment that influence the migration and transformation of heavy metals (HMs). Six hydrophytes with five dry weight gradients (DWG) were used for the decomposition experiments. The results showed that protein-like materials occupy relatively high content in the hydrophyte-derived DOM. The binding properties of DOM-Cu(II) have been explored by using two-dimensional correlation spectroscopy (2D-COS) in conjunction with synchronous fluorescence spectroscopy (SFS) and log-transformed SFS. The weak signals of binding site can be amplified by the log-transformed 2D-COS analysis. Herein, more binding sites can be identified by the log-transformed 2D-COS analysis. The results reveal that tryptophan-like materials show a preferential sequence of binding Cu(II) in the hydrophyte-derived DOM with a relatively low DWG and sediment DOM, and fulvic-like substances indicate a preferential sequence of binding Cu(II) in the hydrophyte-derived DOM with a relatively high DWG. Meanwhile, the results of binding parameters indicate that the log K is the range of 3.61-4.25, 4.33-4.74, 4.59-4.97, 3.91-4.41, and 4.14-4.78 for D1-D5, respectively, suggesting that hydrophyte decomposition can change the binding affinity between DOM components and Cu(II). The complexes of fluorescent components with Cu(II) showed a high log K value at long wavelength (e.g. humic-like substances), and a relatively low fluorescent ligand proportion (f%) at shorter wavelength in the hydrophyte-derived DOM. However, the log K is the range of 3.08-4.31, 4.09-4.45, 3.93-4.35, 4.39-4.75, and 3.95-4.36 for C1-C5, separately. Protein-like substances with Cu(II) showed a relatively high log K value with the exception of C4. The log-transformed 2D-COS can be an analytical tool to understand the binding heterogeneity of DOM with HMs. The study can provide a guide for managing and controlling the effects of hydrophyte decomposition.