Joint influence of surfactants and humic matter on PAH solubility. Are mixed micelles formed?

Mobilization of polycyclic aromatic hydrocarbons (PAH) by surfactants, present at contaminated sites or deliberately introduced for remediation purposes, is inevitably associated with the influence of humic substances, which are ubiquitous in natural systems. Therefore, the solubilizing effects of anthropogenic and natural amphiphiles must be considered in their combined action since synergistic or antagonistic effects may be expected, for instance, as a consequence of mixed micellization. In this paper, solubilization of (14)C-labeled pyrene in single-component and mixed solutions of surfactants and humic acid (coal-derived) was investigated up to the micellar concentration range. At low concentrations, antagonistic effects were observed for systems with cationic as well as anionic surfactants. Solubility enhancements in the presence of humic acid were canceled on addition of a cationic surfactant (DTAB) since charge compensation at humic colloids entailed precipitation. Solubility was also found to be decreased in the presence of an anionic surfactant (SDS), which was attributed to a competitive effect in respect of pyrene-humic interaction. This explanation is based on octanol-water partitioning experiments with radiolabeled humic acid, yielding evidence of different interaction modes between humic colloids and cationic/anionic surfactants. At higher concentrations, the effects of humic acid and SDS were found to be additive. Thus, a formation of mixed micelles is very unlikely, which was confirmed by size exclusion chromatography of mixed systems. It can be concluded that remediation measures on the basis of micellar solubilization are not significantly affected by the presence of natural amphiphilic compounds.