W. Shane Walker

Competitive separation of di- vs. mono-valent cations in electrodialysis: effects of the boundary layer properties.

In electrodialysis desalination, the boundary layer near ion-exchange membranes is the limiting region for the overall rate of ionic separation due to concentration polarization over tens of micrometers in that layer. Under high current conditions, this sharp concentration gradient, creating substantial ionic diffusion, can drive a preferential separation for certain ions depending on their concentration and diffusivity in the solution. Thus, this study tested a hypothesis that the boundary layer affects the competitive transport between di- and mono-valent cations, which is known to be governed primarily by the partitioning with cation-exchange membranes. A laboratory-scale electrodialyzer was operated at steady state with a mixture of 10mM KCl and 10mM CaCl(2) at various flow rates. Increased flows increased the relative calcium transport. A two-dimensional model was built with analytical solutions of the Nernst-Planck equation. In the model, the boundary layer thickness was considered as a random variable defined with three statistical parameters: mean, standard deviation, and correlation coefficient between the thicknesses of the two boundary layers facing across a spacer. Model simulations with the Monte Carlo method found that a greater calcium separation was achieved with a smaller mean, greater standard deviation, or more negative correlation coefficient. The model and experimental results were compared for the cationic transport number as well as the current and potential relationship. The mean boundary layer thickness was found to decrease from 40 to less than 10 μm as the superficial water velocity increased from 1.06 to 4.24 cm/s. The standard deviation was greater than the mean thickness at slower water velocities and smaller at faster water velocities.

Aqueous-Processed, High-Capacity Electrodes for Membrane Capacitive Deionization

Membrane capacitive deionization (MCDI) is a low-cost technology for desalination. Typically, MCDI electrodes are fabricated using a slurry of nanoparticles in an organic solvent along with polyvinylidene fluoride (PVDF) polymeric binder. Recent studies of the environmental impact of CDI have pointed to the organic solvents used in the fabrication of CDI electrodes as key contributors to the overall environmental impact of the technology. Here, we report a scalable, aqueous processing approach to prepare MCDI electrodes using water-soluble polymer poly(vinyl alcohol) (PVA) as a binder and ion-exchange polymer. Electrodes are prepared by depositing aqueous slurry of activated carbon and PVA binder followed by coating with a thin layer of PVA-based cation- or anion-exchange polymer. When coated with ion-exchange layers, the PVA-bound electrodes exhibit salt adsorption capacities up to 14.4 mg/g and charge efficiencies up to 86.3%, higher than typically achieved for activated carbon electrodes with a hydrophobic polymer binder and ion-exchange membranes (5-13 mg/g). Furthermore, when paired with low-resistance commercial ion-exchange membranes, salt adsorption capacities exceed 18 mg/g. Our overall approach demonstrates a simple, environmentally friendly, cost-effective, and scalable method for the fabrication of high-capacity MCDI electrodes.

A Process for Optimizing Gradation of Marginal Backfill of Mechanically Stabilized Earth Walls to Achieve Acceptable Resistivity

The service life of mechanically stabilized earth walls depends on the corrosion rate of the metallic reinforcement used in their construction. The resistivity of the backfill aggregates needs to be measured accurately to estimate realistically the corrosion rate of the reinforcement. Resistivity testing is usually performed using the traditional soil box on the portion of the aggregates that passes a No. 10 or No. 8 sieve to either select or reject the backfill. For a more reasonable characterization of the corrosivity of coarse backfills, it is desirable to use their actual gradations. To that end, several resistivity boxes that were double and quadruple the dimensions of the original box were constructed. In addition to the three standard gradations specified by the Texas Department of Transportation, over 20 backfill materials sampled from sources throughout Texas were fractionated to fines, fine sand, coarse sand, and gravel. Resistivity tests were performed separately on each of these four constituents for each backfill. The results were used to evaluate a relationship that would allow the estimation of the resistivity of any desired backfill gradations from the resistivity values of these four constituents. The proposed model looks promising since the resistivity of the backfill composed of the actual gradation can be estimated with reasonable certainty. The results of this study can potentially help highway agencies and contractors use a number of local quarries that are currently disqualified based on the resistivity values obtained from only testing materials that pass a No. 8 or No. 10 sieve.

Mass balance and mass loading of polybrominated diphenyl ethers (PBDEs) in a tertiary wastewater treatment plant using SBSE-TD-GC/MS.

A mass loading and mass balance analysis was performed on selected polybromodiphenyl ethers (PBDEs) in the first full-scale indirect potable reuse treatment plant in the United States. Chemical analysis of PBDEs was performed using an environmentally friendly sample preparation technique, called stir-bar sorptive extraction (SBSE), coupled with thermal desorption and gas chromatography/mass spectrometry (GC/MS). The three most dominant PBDEs found in all the samples were: BDE-47, BDE-99 and BDE-100. In the wastewater influent, the concentrations of studied PBDEs ranged from 94 to 775 ng/L, and in the effluent, the levels were below the detection limit. Concentrations in sludge ranged from 50 to 182 ng/g. In general, a removal efficiency of 92-96% of the PBDEs in the plant was accomplished through primary and secondary processes. The tertiary treatment process was able to effectively reduce the aforementioned PBDEs to less than 10 ng/L (>96% removal efficiency) in the effluent. If PBDEs remain in the treated wastewater effluent, they may pose environmental and health impacts through aquifer recharge, irrigation, and sludge final disposal.