Polyoxometalate clusters embedded into hydrogel biobeads may be able to solve the challenges posed by free proton generation during remediation of trichloroethylene by acting as buffers and reducing protons to hydrogen gas. In this thesis, the challenges posed by systems that contain both diffusion and reaction processes for protons are considered mathematically, and a computer simulation to was developed to prove the relationship between diaphragm cell lag period and reactive capabilities of membranes. Two polyoxometalate compounds, sodium decavanadate and alumina sulfate, were successfully incorporated into a poly(vinyl alcohol) hydrogel membrane, and the diffusivity changes associated with each compound was determined. It was found that the diffusivity of protons through an unmodified 10% w/v poly(vinyl alcohol) membrane was 1.76 × 10^-5 cm² s^-1 , the diffusivity through a 10%/2% w/w/v poly(vinyl alcohol)/sodium decavanadate membrane was 3.10 × 10^-6 cm² s^-1 , and the diffusivity through a 10%/2% w/w/v poly(vinyl alcohol)/alumina sulfate membrane was 3.32 × 10^-7 cm² s^-1 . Through analysis of the diaphragm cell lag period, it was found the incorporation of sodium decavanadate did not increase the reactivity of a poly(vinyl alcohol) hydrogel, and incorporation of alumina sulfate lowered the reactivity. These results indicate that polyoxometalate integration into hydrogel membranes is feasible, but does not provide any advantage to a bioremediation scenario.

Trichloroethylene (TCE), a toxic and carcinogenic contaminant, presents unique challenges for cleanup because of its water solubility, density, and volatility. Bioremediation of TCE is a promising cleanup method; however, metabolism of TCE results in acid generation that inhibits remediating microorganisms. Calcium alginate(CA)-polyvinylalcohol (PVA) hydrogels show promise for protecting remediating microbes, however diffusion of TCE or its byproducts through these polymers is unknown. To measure the effective diffusion coefficient of TCE and byproducts through hydrogel membranes, we used a modified diaphragm cell. Measured effective diffusion coefficient of each species was (cm ² /s × 10⁶ ): 14.0 ± 1.91 for H⁺ ions, 12.4 ± 1.64 for TCE, 7.83 ± 0.54 for cis-1,2-dichloroethylene (DCE), and 4.68 ± 4.14 for vinyl chloride. These results aid in engineering biobeads and suggest that CA-PVA hydrogel blends are effective in slowing diffusion of protons, buffering acids produced by trichloroethylene metabolism, and remains suitable for encapsulation of microorganisms involved in bioremediation.