Biomedical subjects

Jeffrey H Harwell

Publications and source records attributed to Jeffrey H Harwell.

8 recordsLinked to original sources

PubMed2005

Field demonstration of surfactant-enhanced solubilization of DNAPL at Dover Air Force Base, Delaware.

This study reports on a surfactant-based flood for tetrachloroethylene (PCE) removal from a control test cell at the Dover National Test Site. The surfactant formulation (sodium dihexyl sulfosuccinate (Aerosol-MA or AMA), isopropanol and calcium chloride) was able to achieve a high concentration of PCE in swollen micelles (supersolubilization) without vertical PCE migration. The hydraulic system included eight screened wells that were operated in both vertical circulation and line drive configurations. After 10 pore volumes of flushing, the overall PCE removal was 68% (65% of which corresponded to the surfactant flooding alone). In addition, the residual PCE saturation was reduced from 0.7% to 0.2%, and the concentration of PCE in the groundwater was reduced from 37-190 mg/L before the flushing to 7.3 mg/L after flooding. Recycling the surfactant solution reduced the required surfactant mass (and thus cost, and waste) by 90%. Close to 80% of the total PCE removal was obtained during the first five pore volumes which were operated in an upward vertical circulation flow scheme. No free oil phase was observed during the test. Further analysis of multilevel sampler data suggests that most of the trapped oil remaining in the cell was likely localized in secluded regions of the aquifer, which helps explain the lower PCE groundwater concentration after remedial activities. In summary, this field study demonstrated the feasibility of surfactant-enhanced remediation to reduce the mass in the source zone and significantly reduce the PCE aqueous concentration and therefore the risk associated with the contaminant plume.

2-Propanol↗

PubMed2005

Modeling solubilization of oil mixtures in anionic microemulsions II. Mixtures of polar and non-polar oils.

Polar/amphiphilic oils, called lipophilic linkers, are sometimes added to oil-water-ionic surfactant microemulsions in order to increase the solubilization of hydrophobic oils. The solubilization increase has been well documented for a number of systems. However, mathematical models to calculate the solubilization increase have been proposed only for optimum microemulsions (i.e., middle phase microemulsions solubilizing equal volumes of oil and water). In this paper we propose a model, which predicts solubilization enhancement for non-optimum microemulsion systems as well. The model is an extension of the net-average curvature model of microemulsion. The net-average curvature model is combined with a surface activity model to account for the increased palisade layer solubilization due to the presence of the polar/amphiphilic oil component. New non-linear mixing rules are also incorporated to account for the optimum salinity and the characteristic length variation of the anionic surfactant microemulsion as a function of the lipophilic linker concentration. The model predicts the effect of the lipophilic linker and the electrolyte concentration on the oil solubilization in accordance with the experimental results.

Journal Article↗

PubMed2005

Preferential solubilization of dodecanol from dodecanol-limonene binary oil mixture in sodium dihexyl sulfosuccinate microemulsions: effect on optimum salinity and oil solubilization capacity.

Solubilization of dodecanol-limonene binary oil mixtures has been studied in saturated Winsor type I and III sodium dihexyl sulfosuccinate microemulsions. The systems showed different oil solubilization behavior below and above dodecanol volume fraction 0.2. Below 0.2 dodecanol volume fraction regular Winsor type microemulsions formed. The oil solubilization was characterized in this concentration range by the optimum salinity and the maximum characteristic length. Dodecanol showed Langmuirian-type surface excess adsorption at the vicinity of the surfactant layer. Variation of the optimum salinity and middle phase characteristic length with increasing dodecanol concentration could be linked to changes in the dodecanol surface excess. These relationships were used to develop new mathematical models for the optimum salinity and characteristic length as a function of oil phase composition. Both models yield excellent agreement with the data. Above dodecanol volume fraction 0.2 regular Winsor type III microemulsions are not formed. Therefore our new models are not applicable in this concentration range.

Journal Article↗

PubMed2005

Linker-based bio-compatible microemulsions.

In this work we have studied the formulation of biocompatible microemulsions using lecithin as the main surfactant and bio-compatible linker molecules (hexyl polyglucoside asthe hydrophilic linker and sorbitan monoleate as the lipophilic linker). These bio-compatible systems are discussed as potential substitutes for chlorinated solvents in dry-cleaning applications and as solvent delivery systems for pharmaceutical applications. Formulation parameters and conditions were evaluated using isopropyl myristate (IPM) as the model oil. It was found that the proposed linker-based formulations were able to form alcohol-free microemulsions while achieving higher solubilization capacity than similar systems reported in the literature. In addition, these lecithin/linker formulations were able to form microemulsions with a wide range of oils, from polar chlorinated hydrocarbons to hydrophobic oils such as squalene. These microemulsions were achieved under isotonic conditions (0.9% NaCl) by only varying the relative proportions of the linkers. The "solvency" power of these bio-compatible formulations was tested for the removal of hexadecane (used as model oil) from cotton fabrics and compared to the solvency power of a typical dry cleaning solvent tetrachloroethylene (PCE). While PCE and the linker-based lecithin formulation removed the same amount of hexadecane at low loading ratios (less than 1% oil volume fraction), at higher loading ratios the linker-based lecithin formulation retained its oil removal capacity while the efficiency of the PCE system declined rapidly. These initial results thus demonstrate the remarkable oil solubilization capacity of these bio-compatible linker-based lecithin formulations and illustrate their potential as environmentally friendly replacements for organic solvents.

Biocompatible Materials↗

PubMed2004

A two-state model for selective solubilization of benzene-limonene mixtures in sodium dihexyl sulfosuccinate microemulsions.

When surfactants are used to solubilize oil, the oil to be solubilized is often a mixture of components with differing properties, for example, solubilization of drug molecules in microemulsion formulations, remediation of organic polluted aquifers using surfactants, and so forth. Previous research has demonstrated that selective solubilization of one organic component over the other may occur if the organic components are dissimilar. In this research, we investigated selective solubilization from benzene-limonene mixtures in Winsor type I and III microemulsion systems containing water, sodium di-n-hexyl sulfosuccinate, and NaCl. The effect of the oil phase composition and the electrolyte concentration on the selectivity was studied. It was found that the selectivity toward benzene was highest at low electrolyte and benzene concentrations, decreasing as the electrolyte or benzene concentration increased. The results are discussed on the basis of the two-state solubilization theory and by correlating the curvature of the surfactant film in the microemulsion with changes of the electrolyte concentration and the oil phase composition. A simple mathematical model is developed for the selectivity, which combines the two-state solubilization theory and the net-average curvature model of microemulsion solubilization to yield close agreement with the experimental data.

Journal Article↗

PubMed2004

Self-assembly in linker-modified microemulsions.

Linker molecules are added to microemulsion systems to enhance the interaction between the surfactant and oil (lipophilic linkers) or water (hydrophilic linkers) phases. Previous results suggest that when lipophilic and hydrophilic linkers are combined they behave as a self-assembled surfactant at the oil/water interface. In this work we investigate this self-assembly phenomenon as a function of surfactant, linker and electrolyte concentration. We find that middle phase microemulsion appears at a specific concentration higher than the critical micelle concentration (CMC), which we denote as the critical middle phase microemulsion concentration (CmicroC). When the lipophilic linker dodecanol is added in equimolar ratio to the hydrophilic linker sodium mono- and dimethyl naphthalene sulfonate (SMDNS), the middle phase microemulsion did not appear until the surfactant sodium dihexyl sulfosuccinate (SDHS) concentration was larger than the CmicroC of the SDHS-alone system. Dodecanol is shown to segregate near the surfactant tails following a Langmuir-type adsorption process. This segregation is not affected by the electrolyte concentration but is significantly reduced when the surfactant (SDHS) concentration approaches the CmicroC. The data suggest that the self-assembly between hydrophilic and lipophilic linkers to form middle phase microemulsions is only possible if a minimum amount of surfactant is present.

Journal Article↗

PubMed2004

Improving the extraction of tetrachloroethylene from soil columns using surfactant gradient systems.

In this work, we extend the recently developed gradient approach for surfactant-enhanced remediation of dense non-aqueous phase liquid (DNAPL)-impacted sites. The goal of the gradient approach is to maximize the DNAPL solubilization capacity in swollen micelles (Type I aqueous microemulsions) while at the same time minimizing the potential for DNAPL mobilization. In this work, we introduce a modified version of the capillary/trapping curve that we refer to as the gradient curve to help interpret and/or design the gradient approach. The gradient curve presents the residual DNAPL saturation as a function of interfacial tension and microemulsion viscosity. This approach demonstrates that keeping a low viscosity of the microemulsion phase is not only important for keeping a low head loss during surfactant flooding but also to prevent oil mobilization. Eight microemulsion systems were evaluated in this research; these systems were evaluated based on their tetrachloroethylene (PCE) solubilization capacity, interfacial tension (IFT), viscosity, density, and coalescence kinetics. Two of these systems were chosen for evaluation in site-specific column tests using an increasing electrolyte gradient to produce a decreasing IFT/increasing solubilization gradient system. The column studies were conducted with media from Dover Air Force Base in Dover, DE. Both solubilized and mobilized DNAPL were quantified. During the column studies, we observed that substantial PCE was mobilized when the residual level of PCE in the column was significantly higher than the steady-state residual saturation level being approach (as predicted from the gradient curve). Four column studies were performed, three of which were used to asses the validity of the gradient curve in predicting the residual saturation after each gradient step. From these tests we observed that starting IFTs of less than 1 mN/m all produced the same mobilization potential. In the last column, we used an additional gradient step with an initial IFT above 1 mN/m to dramatically reduce the amount of PCE mobilize. Based on the good agreement between column results and projections based on the gradient curve, we propose this as a preferred method for designing gradient surfactant flushing systems.

Environmental Pollutants↗

PubMed2002

Formulating chlorinated hydrocarbon microemulsions using linker molecules.

Previously we reported on the use of lipophilic, hydrophilic, and combined linkers for formulating microemulsions of trichloroethylene and tetrachloroethylene. These linker molecules augment the interaction between the surfactant and oil phase (lipophilic linkers) or between the surfactant and water phase (hydrophilic linkers). Combining both linkers can increase the solubilization capacity several-fold. This formulation technique shows potential advantage in reducing surfactant costs and remedial times, as well as allowing the use of more environmentally friendly additives when designing surfactant-enhanced remediation systems. In this paper, we evaluate the relative importance of the surfactant and each linker in increasing the system's solubilization capacity. This interpretation is based on solubilization curves, partitioning studies, and formulation studies. The solubilization curves show that optimum linker performance is reached at an equimolar ratio of dodecanol, used as a lipophilic linker, and sodium mono and dimethyl naphthalene sulfonate, used as a hydrophilic linker. Furthermore, this equimolar combination was able to replace the anionic surfactant sodium dihexylsulfosuccinate. Dodecanol partitioning at optimum formulation shows that the poor performance of lipophilic linkers alone is due to their low partitioning into the middle phase. Adding hydrophilic linkers into this system increases the fraction of dodecanol in the middle phase, thereby further enhancing the solubilization capacity of the system. A variation of the combined linker approach is introduced by changing a lipophilic linker, oleic acid, into a surfactant (soap), with further increases in the solubilization capacity by 4- to 5-fold.

Oleic Acid↗