| Abstract: | A liquid-liquid partition, ligand exchange procedure involving the formation of copper(II) complexes with acetylacetone is presented for the determination of stability constants and concentrations of copper chelators in seawater. Acetylacetone competes with natural ligands for copper, and the equilibrium concentration of the copper acetylacetonate complex is used in speciation calculations. The concentration of the complex is calculated by partitioning a fraction of it into an organic phase and determining the total Cu concentration in that phase by back extracting with acid, and analyzing by flameless atomic absorption spectroscopy. The concentration of Cu acetylacetonate in seawater in equilibrium with the organic phase is calculated from the partition coefficient. The simple, thermodynamically well characterized procedure offers several advantages over previous techniques. Studies using organic free seawater and model ligands show good agreement between experimental and calculated conditional stability constants. Studies from seawater in Biscayne Bay, Florida, indicate two ligand types are present; type 1, K1 = 1.2 × 1012, CL1 = 5.1 × 10−9 M; type 2, K2 = 2.8 × 1010, CL2 = 1.1 × 10−7 M. Speciation is dominated by ligand type 1. Depth profiles of Cu(II)]free/Cu(II)]total measured with the procedure at ambient copper concentrations show an increase from < 5 × 10−5 at 50–60 m to > 1 × 10−3 at the surface at two stations off the Florida coast. |
