No abstract

129I is commonly either the top or among the top risk drivers, along with 99Tc, at radiological waste disposal sites and contaminated groundwater sites where nuclear material fabrication or reprocessing has occurred. The risk stems largely from 129I having a high toxicity, a high bioaccumulation factor (90% of all the body's iodine concentrates in the thyroid), a high inventory at source terms (due to its high fission yield), an extremely long half-life (16M years), and rapid mobility in the subsurface environment. Another important reason that 129I is a key risk driver is that there is uncertainty regarding its biogeochemical fate and transport in the environment. We typically can define 129I mass balance and flux at sites, but cannot predict accurately its response to changes in the environment. As a consequence of some of these characteristics, 129I has a very low drinking water standard, which is set at 1 pCi/L, the lowest of all radionuclides in the Federal Register. Recently, significant advancements have been made in detecting iodine species at ambient groundwater concentrations, defining the nature of the organic matter and iodine bond, and quantifying the role of naturally occurring sediment microbes to promote iodine oxidation and reduction. These recent studies have led to a more mechanistic understanding of radioiodine biogeochemistry. The objective of this review is to describe these advances and to provide a state of the science of radioiodine biogeochemistry relevant to its fate and transport in the terrestrial environment and provide information useful for making decisions regarding the stewardship and remediation of 129I contaminated sites. As part of this review, knowledge gaps were identified that would significantly advance the goals of basic and applied research programs for accelerating 129I environmental remediation and reducing uncertainty associated with disposal of 129I waste. Together the information gained from addressing these knowledge gaps will not alter the observation that 129I is primarily mobile, but it will likely permit demonstration that the entire 129I pool in the source term is not moving at the same rate and some may be tightly bound to the sediment, thereby smearing the modeled 129I peak and reducing maximum calculated risk.

[1] Developing a predictive understanding of subsurface contaminant plume evolution and natural attenuation capacity is hindered by the inability to tractably characterize controlling reactive transport properties over field-relevant scales. Here we explore a concept of reactive facies, which is based on the hypothesis that subsurface units exist that have unique distributions of properties that influence reactive transport. We further hypothesize that geophysical methods can be used to identify and spatially distribute reactive facies and their associated parameters. We test the reactive facies concept at a U.S. Department of Energy uranium-contaminated groundwater site, where we have analyzed the relationships between laboratory and field (including radar and seismic tomographic) data sets. Our analysis suggests that there are two reactive facies that have unique distributions of mineralogy, texture, hydraulic conductivity, and geophysical attributes. We use these correlations within a Bayesian framework to integrate the dense geophysical data sets with the sparse corebased measurements. This yields high-resolution (0.25 m  0.25 m) estimates of reactive facies and their associated properties and uncertainties along the 2-D tomographic transects.Comparison with colocated samples shows that the estimated properties fall within 95% uncertainty bounds. To illustrate the value of reactive facies characterization approach, we used the geophysically estimated properties to parameterize reactive transport models, which were then used to simulate migration of an acidic-U plume through the domain. Modeling results suggest that each identified reactive facies exerts a unique control on plume evolution, highlighting the usefulness of the reactive facies concept for spatially distributing properties that control reactive transport over field-relevant scales.Citation: Sassen, D. S., S. S. Hubbard, S. A. Bea, J. Chen, N. Spycher, and M. E. Denham (2012), Reactive facies: An approach for parameterizing field-scale reactive transport models using geophysical methods, Water Resour. Res., 48, W10526,

Well-defined solid sources of Pu(III) (PuCl3), Pu(IV) (Pu (NO3)4 and Pu (C2O4)2), and Pu(VI) (Pu02(NO3)2) were placed in lysimeters containing vadose zone sediments and exposed to natural weather conditions for 2 or 11 years. The objective of this study was to measure the release rate of Pu and the changes in the Pu oxidation states from these Pu sources with the intent to develop a reactive transport model source-term. Pu(III) and Pu(IV) sources had identical Pu concentration depth profiles and similar Pu release rates. Source release data indicate that PuIV(C2O4)2 was the least mobile, whereas Pu(VI)O2(NO3)2 was the most mobile. Synchrotron X-ray fluorescence (SXRF) revealed that Pu was very unevenly distributed on the sediment and Mn concentrations were too low (630 mg kg(-1)) and perhaps of the wrong mineralogy to influence Pu distribution. The high stability of sorbed Pu(IV) is proposed to be due to the formation of a stable hydrolyzed Pu(IV) surface species. Plutonium X-ray absorption near-edge spectroscopy (XANES) analysis conducted on sediment recovered at the end of the studyfrom the Pu(IV)(NO3)4- and Pu(III)(III)Cl3-amended lysimeters contained essentially identical Pu distributions: approximately 37% Pu(III), 67% Pu(IV), 0% Pu(V), and 0% Pu(VI). These results were similar to those using a wet chemistry Pu oxidation state assay, except the latter method did not detect any Pu(III) present on the sediment but instead indicated that 93-98% of the Pu existed as Pu(IV). This discrepancy was likely attributable to incomplete extraction of sediment Pu(III) by the wet chemistry method. Although Pu has been known to exist in the +3 oxidation state under microbially induced reducing conditions for decades, to our knowledge, this is the first observation of steady-state Pu(III) in association with natural sediments. On the basis of thermodynamic considerations, Pu(III) has a wide potential distribution, especially in acidic environments, and as such may warrant further investigation.