Influence of water chemistry and dissolved organic matter (DOM) molecular size on copper and mercury binding...

The effects of water chemistry (i.e. pH and Ca(2+) concentration) dissolved organic carbon (DOC) concentration) and DOM quality (i.e. composition and molecular weight) on metal complexation were successfully investigated by a combination of tangential flow filtration, excitation-emission matrix fluorescence, parallel factor analysis (PARAFAC), and fluorescence quenching on four freshwater samples and one extracted Suwannee River fulvic acid (SRFA). Two terrestrial and one microbial humic-like components were found in this study. Despite strong correlation between the Ryan-Weber model and the multiresponse model, the latter is more appropriate for the calculation of binding parameters in multiple-ligand DOM system. Decreasing pH from 6 to 4 significantly reduced logK-Cu(2+) from 5.22±0.24 to 4.60±0.30 at pH 6 and 4, respectively (p<0.001), while the impacts of Ca(2+) and DOC were not discernible at concentrations<100ppm and<2.06ppm, respectively. For natural freshwater DOM binding, the three humic-like components had similar logK values for both metals. High molecular weight (>1kDa) DOM generally had higher logK and binding fluorophore abundance than bulk (unfractionated) and low molecular weight (<1kDa) DOM for both metals. This trend however was not always true for Hg(2+) where the binding parameters were quite variable. Overall the combined results provide evidence that binding parameters are not only affected by water chemistry, but also depend on DOM molecular weight.