Combined effects of humic matter and surfactants on PAH solubility: Is there a mixed micellization?

1. Introduction
It has been recognized that solid-liquid distribution and transport of hydrophobic contaminants such as PAH (polycyclic aromatic hydrocarbons) are governed by their interaction with mineral-bound and dissolved humic matter, acting as a sink or a mobilizing agent, respectively. As surface-active compounds, humic substances are often compared to surfactants. Emerging environmental technologies involve a deliberate application of surfactants to enhance the sorption capacity of soils and aquifer materials, or to increase the efficiency of soil washing procedures and pump-and-treat operations for groundwater decontamination. Whereas contaminant binding to humics as well as to surfactants has been extensively studied, there is a notable lack of literature on their combined action in mixed systems. This topic is, however, important because environmental influences of surfactants are inevitably associated with the effects of the ubiquitous natural organics. Since both are amphiphilic, it seems conceivable that mixed micelles can be formed, involving synergistic or antagonistic effects in the solubilization of organic compounds.
In this study, we have examined the joint influence of humic acid and surfactants (cationic, anionic) on the water solubility of pyrene as a representative of PAH, at surfactant concentrations below and above the critical micelle concentration (CMC). In order to detect and characterize interaction processes, we have investigated the octanol-water partitioning of humic acid in the presence of various surfactants, using radiolabelled humic material. In particular, the hypothesis of a micellar nature of dissolved humic substances has been addressed.

2. Materials and Methods: omitted here

3. Results and Discussion
The water solubility of pyrene is increased in the presence of humic acid, which acts as a carrier due to hydrophobic interaction of both components. When adding the cationic surfactant dodecyltrimethylammonium bromide (DTAB), this solubility enhancement was found to be cancelled; the humic colloids were precipitated as a consequence of charge compensation by the organo-cations.
Interestingly, an antagonistic effect was also observed on addition of an anionic surfactant, sodium dodecylsulfate (SDS). While no precipitation was induced in this case, the solubility of pyrene was reduced by half and remained constant on further addition. Only at surfactant concentrations above the CMC, the solubility increased sharply owing to micellar incorporation. The presence of HA did not cause any change in the CMC of SDS, as is normally observed on addition of a second amphiphilic compound. Furthermore, the effects of HA and micellar SDS on pyrene solubility turned out to be strictly additive. Consequently, they are based on distinct processes, occurring independently of each other, i.e., there is no mixed micellization with humic molecules acting as a co-surfactant.
The octanol-water partition ratios of HA changed significantly in the presence surfactants. The partitioning equilibrium was shifted towards the organic phase on addition of cationic surfactants, and towards the aqueous phase on addition of anionic surfactants. Based on these findings, different modes of interaction could be identified, providing an explanation for the decline in pyrene solubilization in systems of HA and SDS. Obviously, a competitive situation arises in the hydrophobic binding of the PAH and the surfactant tail groups. The fact that the pyrene molecules cannot be displaced completely supports the proposition that different binding sites exist in humic colloids: weak near-surface sites and strong inner sites.
The size distribution of the colloids was found to be unaffected by the association with anionic as well as with cationic surfactants. A general micellar character is thus unlikely since a co-aggregation should then entail substantial disruptions and rearrangement processes.

4. Conclusions: omitted here