Binding interactions of dissolved organic matter with iron and copper: Effects of source and pH

Dissolved organic matter(DOM) fluxes from terrestrial to marine environments have increased as a result of anthropogenic activities and climate change, and DOM is known to facilitate the transport of both metals and trace organics. The nature and composition of DOM may influence its binding properties to metals and thus affect their mobility and fate in aquatic environments. Humic substances make up the majority of DOM in many aquatic ecosystems. Metals such as Fe and Cu are not only important as nutrients in aquatic systems, but also in controlling biogeochemical and ecotoxicological processes respectively. Thus, gaining a better understanding on the interaction of humic substances with Fe or Cu is important in the assessment of the bioavailability of such metals in aquatic systems.

In this study, the binding processes of two different DOM samples (Suwanee River humic acid, SRHA and Nordic Lake fulvic acid, NLFA)with Fe(III) and Cu(II) were examined. With the assistance of excitation-emission matrix fluorescence (EEM) and parallel factor analysis (PARAFAC), three humic-like components (C1, C2 and C4), and one microbial humic-like component (C3), were identified in the characterization of the samples. The quenching rates of C2 and C4 fluorescence in the presence of Cu were similar, which were slightly faster than that forC1. In contrast, the C3 fluorescence was significantly less affected by the addition of metals. In the presence of Fe, the most significant quenching was also observed for C2, and the behavior of C4 fluorescence was dependent on the pH value. Some differences in the fluorescence quenching were also observed between the two humic acid standards (one more higher-plant/terrestrially derived vs. the other more microbial/aquatic derived). In addition, pH had a significant effect on the metal binding with significantly lower quenching at lower pH values. Some variations where observed for the higher pH conditions particularly for Cu(II). A modified version of the Ryan-Weber model was used to calculate conditional stability constants (K_M) and the complex capacity (C_L). Effects of metal type, DOM type and pH on the fluorescence quenching are discussed.