Reactive transport modeling of column experiments on the evolution of saline-alkaline waste solutions.

Leakage of saline-alkaline tank waste solutions often creates a serious environmental contamination problem. To better understand the mechanisms controlling the fate of such waste solutions in the Hanford vadose zone, we simulated reactive transport in columns designed to represent local site conditions. The Pitzer ion interaction module was used, with principal geochemical processes considered in the simulation including quartz dissolution, precipitation of brucite, calcite, and portlandite, multi-component cation exchange, and aqueous complexation reactions. Good matches were observed between the simulated and measured column data at ambient temperature ( approximately 21 degrees C). Relatively good agreement was also obtained at high temperature ( approximately 70 degrees C). The decrease of pH at the plume front is examined through formation of secondary mineral phases and/or quartz dissolution. Substantial formation of secondary mineral phases resulting from multi-component cation exchange suggests that these phases are responsible for a decrease in pH within the plume front. In addition, a sensitivity analysis was conducted with respect to cation exchange capacity, selectivity coefficient, mineral assemblage, temperature, and ionic strength. This study could serve as a useful guide to subsequent experimental work, to thermodynamic models developed for the concentrated solutions at high ionic strength and to other types of waste plume studies.

Reoxidation of bioreduced uranium under reducing conditions.

Nuclear weapons and fuel production have left many soils and sediments contaminated with toxic levels of uranium (U). Although previous short-term experiments on microbially mediated U(VI) reduction have supported the prospect of immobilizing the toxic metal through formation of insoluble U(IV) minerals, our longer-term (17 months) laboratory study showed that microbial reduction of U can be transient, even under sustained reducing conditions. Uranium was reduced during the first 80 days, but later (100-500 days) reoxidized and solubilized, even though a microbial community capable of reducing U(VI) was sustained. Microbial respiration caused increases in (bi)-carbonate concentrations and formation of very stable uranyl carbonate complexes, thereby increasing the thermodynamic favorability of U(IV) oxidation. We propose that kinetic limitations including restricted mass transfer allowed Fe-(III) and possibly Mn(IV) to persist as terminal electron acceptors (TEAs) for U reoxidation. These results show that in-situ U remediation by organic carbon-based reductive precipitation can be problematic in sediments and groundwaters with neutral to alkaline pH, where uranyl carbonates are most stable.

Influence of calcium carbonate on U(VI) sorption to soils.

The high stability of calcium uranyl carbonate complexes in the circumneutral pH range has a strong impact on U(VI) sorption in calcareous soils. To quantify this influence, sorption of U(VI) to soils in the presence of naturally occurring calcium carbonate was investigated by conducting batch experiments in which either U(VI) concentration or solution pH was varied. Two soils containing different calcium carbonate concentrations were selected, one from Oak Ridge, TN, and another from Altamont Pass, CA. The results show that the presence of calcium carbonate in soils strongly affects U(VI) sorption. Higher concentrations of soil calcium carbonate lead to a pronounced suppression of the pH-dependent sorption curve in the neutral pH range because of the formation of a very stable neutral complex of calcium uranyl carbonate in solution. A surface complexation model considering both strong and weak sites for ferrihydrite and ionizable hydroxyl sites for clay minerals was compared with experimental results, and U(VI) binding parameters were reasonably estimated. Fair agreement was found between the model predictions and sorption data, which span a wide range of U(VI) concentrations and pH. The results also show that appropriate solution-to-solid ratios need to be used when measuring distribution coefficients in calcareous soils to avoid complete CaCO3 dissolution and consequent dilution of calcium uranyl carbonate complexes.

pH neutralization and zonation in alkaline-saline tank waste plumes.

At the Hanford Site in Washington State, the pH values of contaminant plumes resulting from leaking of initially highly alkaline-saline radioactive waste solutions into the subsurface are now found to be substantially neutralized. However, the nature of plume pH neutralization has not previously been understood. As a master geochemical variable, pH needs to be understood in order to predict the fate and transport of contaminants carried by the waste plumes. Through this laboratory study, we found that the plume pH values spanned a broad range from 14 (within the near-source region) down to the value of 7 (lower than the pH value of the initial soil solution) while the plume was still connected to an actively leaking source. We defined two zones within a plume: the silicate dissolution zone (SDZ, pH 14-10) and the neutralized zone (NZ, pH 10-7). Quartz dissolution at elevated temperature and precipitation of secondary silicates (including sodium metasilicate, cancrinite, and zeolites) are the key reactions responsible for the pH neutralization within the SDZ. The rapid and thorough cation exchange of Na+ replacing Ca2+/Mg2+, combined with transport, resulted in a dynamic Ca2+/Mg2+-enriched plume front. Subsequent precipitation of calcite, sodium silicate, and possibly talc led to dramatically reduced pH within the plume front and the neutralized zone. During aging (after the plume source became inactive), continued quartz dissolution and the secondary silicate precipitation drove the pH value lower, toward pH 11 at equilibrium within the SDZ, whereas the pH values in the NZ remained relatively unchanged with time. A pH profile of 11 from the plume source to pH 7 at the plume front is expected for a historical plume. This laboratory-based study provided realistic plume pH profiles (consistent with that measured from borehole samples) and identified underlying mechanisms responsible for pH evolution.

Colloid formation at waste plume fronts.

Highly saline and caustic tank waste solutions containing radionuclides and toxic metals have leaked into sediments at U.S. Department of Energy (DOE) facilities such as the Hanford Site (Washington state). Colloid transport is frequently invoked to explain migration of radionuclides and metals in the subsurface. To understand colloid formation during interactions between highly reactive fluids and sediments and its impact on contaminant transport, we simulated tank waste solution (TWS) leakage processes in laboratory columns at ambient and elevated (70 degrees C) temperatures. We found that maximum formation of mobile colloids occurred at the plume fronts (hundreds to thousands times higher than within the plume bodies or during later leaching). Concentrations of suspended solids were as high as 3 mass %, and their particle sizes ranged from tens of nanometers to a few micrometers. Calcium carbonate is always one of the dominant phases of the plume front colloids, while the other phases varied with solution pH and temperature. During infiltration of the leaked high-Na+ waste solution, rapid and completed Na+ replacement of exchangeable Ca2+ and Mg2+ from the sediment caused accumulation of these divalent cations at the moving plume front. Precipitation of supersaturated Ca2+/Mg2+-bearing minerals caused dramatic pH reduction atthe plume front. In turn, the reduced pH caused precipitation of other minerals. This understanding can help predict the behavior of contaminant trace elements carried by the tank waste solutions and could not have been obtained through conventional batch studies.