Hydrophobicity and octanol-water partitioning of trace metals in natural waters

The hydrophobicities of dissolved Al, Cu, Mn, and Pb have been determined in various contaminated natural water samples by 1-octanol extraction and C18 column retention. Octanol extraction varied among the metals studied and between the environments sampled but, in general, was greatest for Pb, whose conditional octanol-water partition coefficient, Dow, exceeded unit value in some samples. In most cases, metal partition into octanol either increased with increasing pH or exhibited a maximum under near-neutral conditions. Although the order and pH-dependence of metal retention by the C18 columns was consistent with these observations, the extent of retention was generally greater than the extent of metal extraction by octanol, possibly because of interferences effected by the C18 column matrix. Speciation calculations and results of controlled experiments employing metals in the presence of model ligands suggest that metals may become hydrophobic either by neutralizing relatively hydrophilic ligands or by combining with ligands that are intrinsically hydrophobic themselves. Given that octanol solubility affords an upper estimate of lipophilicity, the results of this investigation may have important implications regarding our understanding of metal bioavailability and toxicity in natural waters.