The technique of competitive ligand-exchange/anodic stripping voltammetry (CLE-SV) was used to investigate effects of pH and Ca concentration on cadmium complexation by fulvic acid (FA), as well as Cd speciation in two different freshwaters, a hardwater Lake Greifen and a softwater River Wyre. Binding of Cd to Suwannee river FA (10 mg/l) was determined at different pH (7–8.5) and in the presence of various concentration of Ca2+ (0–2 mmol/l). The results from one-ligand discrete models were compared to simulations by the WHAM VI model. In Lake Greifen, the determined dissolved [Cd2+] ranged from 10−13 to 10−12 mol/l, and the conditional stability constant with natural ligands was log K CdL about 9.5–10.5 (pH 8.6–8.8) with ligand concentrations of 1.2–7.8 × 10−6 mol/g C. In the softwater River Wyre, dissolved [Cd2+] ranged from 4 × 10−12 to 1 × 10−11 mol/l, and the ligands were weaker (log K CdL 8.9–9.8, pH 8.0) with lower ligand concentrations (0.9–2.3 × 10−6 mol/g C). The titration curves of FA samples were close to the simulated curves by the WHAM VI model at pH 8.0–8.5, but deviated more from the model at lower pH, indicating that the results determined with CLE-SV for Cd-FA complexation are relevant to the data base in the model. Calculation of the Ca competition for Cd binding by FA showed a competition effect of similar strength as the measured one, but indicated a systematic difference between measured and modeled data at pH 7.5. Using the WHAM model for comparison with FA, the complexation of Cd by the River Wyre ligands was close to that of FA, whereas stronger complexation was observed in the Lake Greifen water. These differences may originate from different ligand composition in the lake and the river.
Keywords: FA complexation - pH - Calcium - Cd speciation