Groundwater at Oak Ridge National Laboratory's Field Research Center (FRC) is contaminated with U(VI) and Tc(VII), has pH values as low as 3.3, and nitrate concentrations as high as 120 mM. The objective of this research was to determine if in-situ bio-immobilization is a viable treatment alternative for this water. A laboratory column packed with crushed limestone and bicarbonate was used to model in-situ pH adjustment. Denitrification and metal reduction were modeled in columns packed with FRC sediment with ethanol as the electron donor. Two intermediate-scale physical models deployed in the field were packed with limestone and sediment and were stimulated with ethanol to support denitrification, U(VI) reduction, and Tc(VII) reduction of FRC groundwater. The limestone/bicarbonate column maintained a pH of above 5 for nearly one hundred pore volumes without significant loss in hydraulic conductivity. The high-nitrate (~120 mM) column study provided rates of denitrification (~15.25 mM/day), ethanol utilization (~13 mM/day), and technetium reduction (~120 pM/day) by sediment microorganisms, but no uranium reduction was detected. Results of the low nitrate (3 mM) column study indicate that once the pH of FRC water is adjusted to pH ~7 and nitrate is removed, uranium (~3 μM) and technetium (~500 pM) reduction occurred with ethanol as the electron donor at rates of 0.5 μM/day and 57 pM/day. Similar results were obtained in two intermediate-scale (~3 m long) physical models. Data from the high-nitrate, low-pH model indicate that the pH was increased and nitrate and technetium reduction were occurring. Decreased U(VI) concentrations were measured in the presence of high nitrate concentrations. Thus, U(VI) precipitates may form or sorption of U(VI) may occur near the inlet in the pH adjustment region. The maximum pseudo-first order rates of reduction measured during the seventh week of model operation were: nitrate at 0.76 day⁻¹, Tc(VII) at 0.28 day⁻¹, and U(VI) at 0.12 day⁻¹. Ethanol concentrations were reduced from ~180 mM to zero in ~10 days during the seventh week of model operation. No Fe(II) production was measured. Concentration data collected from the low nitrate, neutral pH model indicate that nitrate, uranium, and technetium reduction were occurring, though the model had been operational for only ~6 weeks. No Fe(II) production was detected but sulfate reduction was occurring. The results of the laboratory experiments and the performance of the intermediate-scale physical models suggest that bio-immobilization is a viable treatment alternative for the contaminated groundwater at the FRC. / Graduation date: 2004

Understanding the transport and retention of radionuclides in the environment is important for protecting freshwater supplies and minimizing impact to biologic systems. Technetium-99 (Tc⁹⁹) is a radionuclide of interest due to its long half-life (2.13 x 10⁵ years) and toxicity. In the form of pertechnetate (TcO₄⁻), Tc is expected to move nearly unretarded in the subsurface. Under reducing conditions Tc can precipitate in low solubility Tc oxide (TcO₂·nH₂O) and/or Tc sulfide (Tc₂S[subscript x]) phases. The studies presented in this dissertation investigate the physiochemical mechanisms for the transport and retention of Tc. Transport studies determined that TcO₄⁻ would move at pore water velocity in unsaturated sediments. Geochemical studies of contaminated sediments determined that nearly ~ 25 % of the total Tc was retained in phases associated with iron oxide and aluminosilicate minerals, thus reducing the mobility of Tc. Studies of Tc₂S[subscript x] mineral phases, generated using nano Zero Valent Iron (nZVI) and sulfide (HS-) in sediments, determined that Tc could be stabilized in mineral phases as Tc₂S[subscript x] that were slower to reoxidize than TcO₂·nH₂O phases. / Graduation date: 2013 / Access restricted to the OSU Community at author's request from Feb. 14, 2013 - Feb. 14, 2014