Water-Chemistry Evolution and Modeling of Radionuclide Sorption and Cation Exchange during Inundation of Frenchman Flat Playa (2013)

Atmospheric tests and other experiments with nuclear materials were conducted on the Frenchman Flat playa at the Nevada National Security Site, Nye County, Nevada; residual radionuclides are known to exist in Frenchman Flat playa soils. Although the playa is typically dry, extended periods of winter precipitation or large single-event rainstorms can inundate the playa. When Frenchman Flat playa is inundated, residual radionuclides on the typically dry playa surface may become submerged, allowing water-soil interactions that could provide a mechanism for transport of radionuclides away from known areas of contamination. The potential for radionuclide transport by occasional inundation of the Frenchman Flat playa was examined using geographic information systems and satellite imagery to delineate the timing and areal extent of inundation; collecting water samples during inundation and analyzing them for chemical and isotopic content; characterizing suspended/precipitated materials and archived soil samples; modeling water-soil geochemical reactions; and modeling the mobility of select radionuclides under aqueous conditions. The physical transport of radionuclides by water was not evaluated in this study. Frenchman Flat playa was inundated with precipitation during two consecutive winters in 2009-2010 and 2010-2011. Inundation allowed for collection of multiple water samples through time as the areal extent of inundation changed and ultimately receded. During these two winters, precipitation records from a weather station in Frenchman Flat (Well 5b) provided information that was used in combination with geographic information systems, Landsat imagery, and image processing techniques to identify and quantify the areal extent of inundation. After inundation, water on the playa disappeared quickly, for example, between January 25, 2011 and February 10, 2011, a period of 16 days, 92 percent of the areal extent of inundation receded (2,062,800 m2). Water sampling provided valuable information about chemical processes occurring during inundation as the water disappeared. Important observations from water-chemistry analyses included: 1) total dissolved solids (TDS) and chloride ion (Cl-) concentrations were very low (TDS: < 200 mg/L and Cl-: < 3.0 mg/L, respectively) for all water samples regardless of time or areal extent; 2) all dissolved constituents were at concentrations well below what might be expected for evaporating shallow surface waters on a playa, even when 98 to 99 percent of the water had disappeared; 3) the amount of evaporation for the last water samples collected at the end of inundation, estimated with the stable isotopic ratios δ2H or δ18O, was approximately 60 percent; and 4) water samples analyzed by gamma spectroscopy did not show any man-made radioactivity; however, the short scanning time (24 hours) and relative chemical diluteness of the water samples (TDS ranged between 39 and 190 mg/L) may have contributed to none being detected. Additionally, any low-energy beta emitting radionuclides would not have been detected by gamma spectroscopy. From these observations, it was apparent that a significant portion of water on the playa did not evaporate, but rather infiltrated into the subsurface (approximately 40 percent). Consistent with this water chemistry-based conclusion is particle-size analysis of two archived Frenchman Flat playa soils samples, which showed low clay content in the near surface soil that also suggested infiltration. Infiltration of water from the playa during inundation into the subsurface does not necessarily imply that groundwater recharge is occurring, but it does provide a mechanism for moving residual radionuclides downward into the subsurface of Frenchman Flat playa. Water-mineral geochemical reactions were modeled so that changes in the water chemistry could be identified and the extent of reactions quantified. Geochemical modeling showed that evaporation; equilibrium with atmospheric carbon dioxide and calcite; dissolution of sodium chloride, gypsum, and composite volcanic glass; and precipitation of composite clay and quartz represented changes in water as it disappeared from the playa. This modeling provided an understanding of the water-soil geochemical environment, which was then used to evaluate the potential mobility of residual radionuclides into the playa soils by water. Because there is no information on the chemical forms of anthropogenic radionuclides in Frenchman Flat playa soil, it was assumed that soil radionuclides go into solution when the playa is inundated. In mobility modeling, a select group of radionuclides were allowed to sorb onto, or exchange with, playa soil minerals to evaluate the likelihood that the radionuclides would be removed from water during playa inundation. Radionuclide mobility modeling suggested that there would be minimal sorption or exchange of several important radionuclides (uranium, cesium, and technetium) with playa minerals such that they may be mobile in water when the playa is inundated and could infiltrate into the subsurface. Mobility modeling also showed that plutonium may be much less mobile because of sorption onto calcite, but the amount of reactive surface area of playa soil calcite is highly uncertain. Plutonium is also known to sorb onto colloidal particles suspended in water, suspended colloidal particles will move with the water, providing a mechanism to redistribute plutonium when Frenchman Flat playa is inundated. Water chemistry, stable isotopes, and geochemical modeling showed that residual radionuclides in Frenchman Flat playa soils could be mobilized in water when the playa is inundated with precipitation. Also, there is potential for these radionuclides to infiltrate into the subsurface with water. As a result of the information obtained both during this study and the conclusions drawn from it, additional data collection, investigation, and modeling are recommended. Specifically: sampling the playa soil to search for evidence of surface-water infiltration and the presence of radionuclides; developing a preliminary unsaturated flow and transport model to guide soil sampling; characterizing the chemical forms of radionuclides on the playa surface and any radionuclides that might have migrated into the subsurface; and, refining the unsaturated flow and transport model with data obtained from sampling and analysis of soil samples to guide any future sampling, development of remediation strategies, and defining risk-based boundaries for Frenchman Flat playa.