Adsorption of hydroxamate siderophores and EDTA on goethite in the presence of the surfactant sodium dodecyl sulfate

Siderophore-promoted iron acquisition by microorganisms usually occurs in the presence of other organic molecules, including biosurfactants. We have investigated the influence of the anionic surfactant sodium dodecyl sulfate (SDS) on the adsorption of the siderophores DFOB (cationic) and DFOD (neutral) and the ligand EDTA (anionic) onto goethite (α-FeOOH) at pH 6. We also studied the adsorption of the corresponding 1:1 Fe(III)-ligand complexes, which are products of the dissolution process. Adsorption of the two free siderophores increased in a similar fashion with increasing SDS concentration, despite their difference in molecule charge. In contrast, SDS had little effect on the adsorption of EDTA. Adsorption of the Fe-DFOB and Fe-DFOD complexes also increased with increasing SDS concentrations, while adsorption of Fe-EDTA decreased. Our results suggest that hydrophobic interactions between adsorbed surfactants and siderophores are more important than electrostatic interactions. However, for strongly hydrophilic molecules, such as EDTA and its iron complex, the influence of SDS on their adsorption seems to depend on their tendency to form inner-sphere or outer-sphere surface complexes. Our results demonstrate that surfactants have a strong influence on the adsorption of siderophores to Fe oxides, which has important implications for siderophore-promoted dissolution of iron oxides and biological iron acquisition

The role of the surfactant head group in the emulsification process: Binary (nonionic-ionic) surfactant mixtures

Dilute emulsions of dodecane in water were prepared under constant flow rate conditions with binary surfactant systems. The droplet size distribution was measured as a function of the mixed surfactant composition in solution. The systems studied were: (a) SDS-C12E6 and (b) DPC-C12E6. At a constant concentration of SDS or DPC surfactant in solution (below the CMC) the mean emulsion droplet size decreases with the increase in the amount of C12E6 added to the solution. However, a sharp break of this droplet size occurs at a critical concentration and beyond this point the mean droplet size did not significantly change upon further increase of the C12E6. This point was found to corresponded to the CMC of the mixed surfactant systems (as previously determined from microcalorimetry measurements) and this result suggested the mixed adsorption layer on the emulsion droplet was similar to the surfactant composition on the mixed micelles. The emulsion droplet size as a function of composition at the interface was also studied. The mean emulsion droplet size in SDS-C12E6 solution was found to be lower than that in DPC-C12E6 system at the equivalent mole fraction of ionic surfactant at interface. This was explained by the stronger interactions between sulphate and polyoxyethylene head groups at the interface, which facilitate the droplet breakup. Counterion binding parameter (b) was also determined from zeta-potential of dodecane droplets under the same conditions and it was found that (b) was independent of the type of the head group and the mole fraction of ionic surfactant at interface.</p

The role of surfactant head group in the dynamic emulsification process. Single surfactant systems

To clarify the effect of the surfactant head group on the emulsification process, dilute dodecane in water emulsions were prepared in a small flow-through cell with three surfactants which had the same hydrocarbon tail length but different head groups. The different surfactants types were (a) a nonionic, hexa(ethyleneglycol) mono n-dodecyl ether (C12E6), (b) an anionic, sodium dodecyl sulfate (SDS), and (c) a cationic, n-dodecyl pyridinium chloride (DPC), and the emulsions were prepared under the same conditions. From dynamic light scattering measurements, it was shown that the mean steady state droplet size of the emulsions (obtained after 20 min dispersion) could be related to the interfacial tension at concentrations in the region of the cmc. This result was in agreement with laminar and turbulent viscous flow theory. However, the particle size versus surface tension data for the different surfactant systems did not fall on a single line. This behavior suggested that the surfactant played a secondary role in defining the droplet size (in addition to reducing the interfacial tension) possibly through diffusion and relaxation, during deformation of the interface. In addition, it was found that the values of the equilibrium "surfactant packing densities" of the different surfactants at the oil/water interface were almost equal near the cmc, but the mean droplet size and the interfacial tension at the cmc decreased following the order DPC>SDS>C12E6</p

Micellar interactions in nonionic/ionic mixed surfactant systems

To study the influence of the chemical nature of headgroups and the type of counterion on the process of micellization in mixed surfactant systems, the cmc's of several binary mixtures of surfactants with the same length of hydrocarbon tail but with different headgroups have been determined as a function of the monomer composition using surface tension measurements. Based on these results, the interaction parameter between the surfactant species in mixed micelles has been determined using the pseudophase separation model. Experiments were carried out with (a) the nonionic/anionic C12E6/SDS ((hexa(ethyleneglycol) mono-n-dodecyl ether)/(sodium dodecyl sulfate)), (b) amphoteric/anionic DDAO/SDS ((dodecyldimethylamine oxide)/(sodium dodecyl sulfate)), and (c) amphoteric/nonionic C12E6/DDAO mixed surfactant systems. In the case of the mixed surfactant systems containing DDAO, experiments were carried out at pH 2 and pH 8 where the surfactant was in the cationic and nonionic form, respectively. It was shown that the mixtures of the nonionic surfactants with different kinds of headgroups exhibit almost ideal behavior, whereas for the nonionic/ionic surfactant mixtures, significant deviations from ideal behavior (attractive interactions) have been found, suggesting binding between the head groups. Molecular orbital calculations confirmed the existence of the strong specific interaction between (1) SDS and nonionic and cationic forms of DDAO and between (2) C12E6 and the cationic form of DDAO. In the case for the C12E6/SDS system, an alternative mechanism for the stabilization of mixed micelles was suggested, which involved the lowering in the free energy of the hydration layer</p

The Interaction Parameter in Binary Surfactant Mixtures of a Chelating Surfactant and a Foaming Agent

The micellisation in binary mixed surfactant systems of a chelating surfactant and a foaming agent has been studied by surface tension measurements in order to calculate the interaction parameter (beta). 2-dodecyldiethylenetriamine pentaacetic acid, 4-C(12)-DTPA, is an amphoteric chelating surfactant applicable for removing disturbing metal ions from industrial processes, or for heavy metal decontamination of soil or leachate. 4-C(12)-DTPA contains multiple donor atoms and forms very stable coordination complexes with metal ions. The metal complexes can easily be recovered from water by flotation, if the foaming is enhanced by a foaming agent with strong interactions to the chelating surfactant. Two foaming agents were examined, one cationic and one anionic. As expected, strong interactions were found between the negatively charged 4-C(12)-DTPA and the cationic dodecyltrimethylammonium chloride, DTAC. The influence of metal ion chelation, as well as pH, on the interaction parameter was also investigated.</p

Performance and Efficiency of Anionic Dishwashing Liquids with Amphoteric and Nonionic Surfactants

Performance and efficiency of anionic [sodium lauryl ether sulfate (SLES) and sodium alpha-olefin sulfonate (AOS)] and amphoteric [cocamidopropyl betaine (CAB)] as well as nonionic [cocodiethanol amide (DEA), various ethoxylated alcohols (C-12-C-15-7EO, C-10-7EO and C-9-C-11-7EO) and lauramine oxide (AO)] surfactants in various dishwashing liquid mixed micelle systems have been studied at different temperatures (17.0, 23.0 and 42.0 degrees C). The investigated parameters were critical micelle concentration (CMC), surface tension (gamma), cleaning performance and, foaming, biodegradability and irritability of anionic (SLES/AOS) and anionic/amphoteric/nonionic (SLES/AOS/CAB/AO) as well as anionic/nonionic (SLES/AOS/DEA/AO, SLES/AOS/C-12-C-15-7EO/AO, SLES/AOS/C-10-7EO/AO and SLES/AOS/C-9-C-11-7EO/AO) dishwashing surfactant mixtures. In comparison to the starting binary SLES/AOS surfactant mixture, addition of various nonionic surfactants promoted CMC and gamma lowering, enhanced cleaning performance and foaming, but did not significantly affect biodegradability and irritability of dishwashing formulations. The anionic/nonionic formulation SLES/AOS/C-9-C-11-7EO/AO shows both the lowest CMC and gamma as well as the best cleaning performance, compared to the other examined dishwashing formulations. However, the results in this study reveal that synergistic behavior of anionic/nonionic SLES/AOS/ethoxylated alcohols/AO formulations significantly improves dishwashing performance and efficiency at both low and regular dishwashing temperatures (17.0 and 42.0 degrees C) and lead to better application properties