Modeling Small Molecule Elution From a Hydrogel using a Microfluidic Technique

Drug release from a fluid-contacting biomaterial is simulated using a microfluidic device with channels defined by solute-loaded hydrogel. In order to mimic a drug delivery device, a solution of poly(ethylene glycol) diacrylate (PEG-DA), solute, and photoinitiator is cured inside a microfluidic device with a channel through the center ofthe hydrogel. As water is pumped through the channel, solute diffuses out of the hydrogel and into the water. Channel sizes within the devices range from 300 µm to 1000 µm to simulate vessels within the body. The properties of the PEG hydrogel were characterizedby the extent of crosslinking, the swelling ratio, and the mesh size of the gel. The structure of the hydrogel was related to the UV exposure dosage and the initial water and solute content in the PEG-DA solution.

Chemical compatibility of soil-bentonite cutoff wall backfills containing modified bentonites

This study examined the chemical compatibility of several model soil-bentonite(SB) backfills with an inorganic salt solution (CaCl2). First, bentonite-water slurry was created using a natural sodium-bentonite, as well as two modified bentonites –multiswellable bentonite (MSB) and a “salt-resistant” bentonite (SW101). Once slurries that met typical construction specifications had been created using the various bentonites,the model SB backfills were prepared for each type of bentonite. These backfills werealso designed to meet conventional construction and design requirements. The SB backfills were then subjected to permeation with tap water and/or CaCl2 solutions of various concentrations in order to evaluate the compatibility of the SB backfills with inorganic chemicals. The results indicate that SB backfill experiences only minor compatibility issues (i.e., no large differences between the hydraulic conductivity of the SB backfill to tap water and CaCl2) compared to many other types of clay barriers. In addition, SB backfills show no major change in final hydraulic conductivity to CaCl2 when permeated with tap water before CaCl2 versus being permeated with CaCl2 directly. These results may be due to the ability of the bentonite in the SB backfills to undergo osmotic swelling before permeation begins, and the inability of the CaCl2 solutions to undo the osmotic swelling. Similar results were obtained for all three clays tested, and while MSB did show less compatibility issues than the natural bentonite and SW101, it appears that the differences in performance may generally be negligible. Overall, thisstudy makes a significant addition to the understanding of SB cutoff wall compatibility.

Microscopic and Spectroscopic Methods for Probing the Clay Water Interface

Clay minerals have a fundamental importance in many processes in soils and sediments such as the bioavailability of nutrients, water retention, the adsorption of common pollutants, and the formation of an impermeable barrier upon swelling. Many of the properties of clay minerals are due to the unique environment present at the clay mineral/water interface. Traditional techniques such as X-ray diffraction (XRD) and absorption isotherms have provided a wealth of information about this interface but have suffered from limitations. The methods and results presented herein are designed to yield new experimental information about the clay mineral/water interface.A new method of studying the swelling dynamics of clay minerals was developed using in situ atomic force microscopy (AFM). The preliminary results presented here demonstrate that this technique allows one to study individual clay mineral unit layers, explore the natural heterogeneities of samples, and monitor swelling dynamics of clay minerals in real time. Cation exchange experiments were conducted monitoring the swelling change of individual nontronite quasi-crystals as the chemical composition of the surrounding environment was manipulated several times. A proof of concept study has shown that the changes in swelling are from the exchange of interlayer cations and not from the mechanical force of replacing the solution in the fluid cell. A series of attenuated total internal reflection Fourier transform infrared spectroscopy (ATR-FTIR) experiments were performed to gain a better understanding of the organization of water within the interlayer region of two Fe-bearing clay minerals. These experiments made use of the Subtractive Kramers-Kronig (SKK) Transform and the calculation of difference spectra to obtain information about interfacial water hidden within the absorption bands of bulk water. The results indicate that the reduction of structural iron disrupts the organization of water around a strongly hydrated cation such as sodium as the cation transitions from an outer-sphere complex with the mineral surface to an inner-sphere complex. In the case of a less strongly hydrated cation such as potassium, reduction of structural iron actually increases the ordering of water molecules at the mineral surface. These effects were only noticed with the reduction of iron in the tetrahedral sheet close to the basal surface where the increased charge density is localized closer to the cations in the interlayer.

Investigating The Fate Of Positively Charged Nanoparticles In A Soil Environment

The recent increase in the amount of nanoparticles incorporated into commercial products is accompanied by a rising concern of the fate of these nanoparticles. Once released into the environment, it is inevitable that the nanoparticles will come into contact with the soil, introducing them to various routes of environmental contamination. One route that was explored in this research was the interaction between nanoparticles and clay minerals. In order to better define the interactions between clay minerals and positively charged nanoparticles, in situ atomic force microscopy (AFM) was utilized. In situ AFM experiments allowed interactions between clay minerals and positively charged nanoparticles to be observed in real time. The preliminary results demonstrated that in situ AFM was a reliable technique for studying the interactions between clay minerals and positively charged nanoparticles and showed that the nanoparticles affected the swelling (height) of the clay quasi-crystals upon exposure. The preliminary AFM data were complemented by batch study experiments which measured the absorbance of the nanoparticle filtrate after introduction to clay minerals in an effort to better determine the mobility of the positively charged nanoparticles in an environment with significant clay contribution. The results of the batch study indicated that the interactions between clay minerals and positively charged nanoparticles were size dependent and that the interactions of the different size nanoparticles with the clay may be occurring to different degrees. The degree to which the different size nanoparticles were interacting with the clay was further probed using FTIR (Fourier transform infrared) spectroscopy experiments. The results of these experiments showed that interactions between clay minerals and positively charged nanoparticles were size dependent as indicated by a change in the FTIR spectra of the nanoparticles upon introduction to clay.