Bioremediation of chlorinated aliphatic hydrocarbon-contaminated aquifers can be hindered by high contaminant concentrations and acids generated during remediation. Encapsulating microbes in hydrogels may provide a protective, tunable environment from inhibiting compounds; however, current approaches to formulate successful encapsulated systems rely on trial and error rather than engineering approaches because fundamental information on mass-transfer coefficients is lacking. To address this knowledge gap, hydronium ion mass-transfer rates through two commonly used hydrogel materials, poly(vinyl alcohol) and alginic acid, under two solidification methods (chemical and cryogenic) were measured. Variations in hydrogel crosslinking conditions, polymer composition, and solvent ionic strength were investigated to understand how each influenced hydronium ion diffusivity. A three-way ANOVA indicated that the ionic strength, membrane type, and crosslinking method significantly (p < 0.001) contributed to changes in hydronium ion mass transfer. Hydronium ion diffusion increased with ionic strength, counter to what is observed in aqueous-only (no polymer) solutions. Co-occurring mechanisms correlated to increased hydronium ion diffusion with ionic strength included an increased water fraction within hydrogel matrices and hydrogel contraction. Measured diffusion rates determined in this study provide first principal design information to further optimize encapsulating hydrogels for bioremediation.

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.