Chemical studies of copper-organic complexes isolated from estuarine waters using C18 reverse-phase liquid chromatography

Dissolved organic matter (DOM) and dissolved copper-organic complexes were isolated from the estuarine waters of Narragansett Bay, RI, using reverse-phase liquid chromatography employing C₁₈ Sep-Pak cartridges (Waters Associates). The cartridges were found to have a constant retention efficiency for processing ? 1-l volumes of seawater. Fractionation of the isolated material, by sequential elution of the Sep-Pak with water: methanol mixtures of increasing organic solvent concentration, yielded a fraction of the organic matter with a specific copper activity six times greater than the overall activity for the isolated DOM. Analysis of this fraction by high performance liquid chromatography suggested that the organic components are of intermediate polarity and have appreciable aromatic character.An investigation of the protonation characteristics of the isolated complexes indicated that most of the copper is associated with a broad range of acidic sites on the DOM. Analysis by electron paramagnetic resonance spectroscopy confirmed the organic association of the isolated copper and also suggested the presence of several types of binding sites which probably involve oxygen donor ligands.Studies of the exchange of ⁶⁴Cu with these binding sites on the isolated DOM indicated that 70% of the sites undergo rapid exchange with copper in seawater while 20% of these sites did not exchange in a 24-h time period.