The Geochemistry of Technetium: A Summary of the Behavior of an Artificial Element in the Natural Environment

Interest in the chemistry of technetium has only increased since its discovery in 1937, mainly because of the large and growing inventory of 99Tc generated during fission of 235U, its environmental mobility in oxidizing conditions, and its potential radiotoxicity. For every ton of enriched uranium fuel (3% 235U) that is consumed at a typical burn-up rate, nearly 1 kg of 99Tc is generated. Thus, the mass of 99Tc produced since 1993 has nearly quadrupled, and will likely to continue to increase if more emphasis is placed on nuclear power to slow the accumulation of atmospheric greenhouse gases. In order to gain a comprehensive understanding of the interaction of 99Tc and the natural environment, we review the sources of 99Tc in the nuclear fuel cycle, its chemical properties, radiochemistry, and biogeochemical behavior. We include an evaluation of the use of Re as a chemical analog of Tc, as well as a summary of the redox potential, thermodynamics, sorption, colloidal behavior, and interaction of humic substances with Tc, and the potential for re-oxidation and remobilization of Tc(IV). What emerges is a more complicated picture of Tc behavior than that of an easily tractable transition of Tc(VII) to Tc(IV) with consequent immobilization. Reducing conditions (+200 to +100 mV Eh) are generally thought necessary to cause reduction of Tc(VII) to Tc(IV), but far more important are the presence of reducing agents, such as Fe(II) sorbed onto mineral grains. Catalysis of Tc(VII) by surface-mediated Fe(II) will bring the mobile Tc(VII) species to a lower oxidation state and will form the relatively insoluble Tc(IV)O2∙nH2O, but even as a solid, equilibrium concentrations of aqueous Tc are nearly a factor of 20× above the EPA set drinking water standards. However, sequestration of Tc(IV) into Fe(III)-bearing phases, such as goethite or other hydrous oxyhydroxides of iron, may ameliorate concerns over the mobility of Tc. Further, the outcome of many studies on terrestrial and marine sediments that are oxidizing overall indicate that Tc is relatively immobile, due to formation of oxygen-depleted microenvironments that develop in response to bacteriological activities. The rate of re-mobilization of Tc from these microenvironments is just beginning to be assessed, but with no firm consensus. Reassessment of the simple models in which Tc is mobilized and immobilized is therefore urged

Phosphate Barriers for Immobilization of Uranium Plumes

Uranium contamination of the subsurface remains a persistent problem plaguing remedial design at sites across the U.S. that were involved with production, handling, storage, milling, and reprocessing of uranium for both civilian and defense related purposes. Remediation efforts to date have relied upon excavation, pump-and-treat, or passive remediation barriers (PRB?s) to remove or attenuate uranium mobility. Documented cases convincingly demonstrate that excavation and pump-and-treat methods are ineffective for a number of highly contaminated sites. There is growing concern that use of conventional PRB's, such as zero-valent iron, may be a temporary solution to a problem that will persist for thousands of years. Alternatives to the standard treatment methods are therefore warranted. The core objective of our research is to demonstrate that a phosphorous amendment strategy will result in a reduction of dissolved uranium to below the proposed drinking water standard. Our hypothesis is that long-chain sodium polyphosphate compounds forestall precipitation of sparingly soluble uranyl phosphate compounds, which is paramount to preventing fouling of wells at the point of injection

Corrosion of the International Simple Glass under acidic to hyperalkaline conditions

Assessment of glass dissolution kinetics, under disposal relevant temperature and pH environments, is required to credibly estimate radionuclide release rates from vitrified radioactive waste. Leaching of the International Simple Glass (ISG) under acidic to hyperalkaline conditions was examined. Forward rate measurements have been obtained using the dynamic leaching SPFT protocol and rate parameters for B, Na and Si in the basic regime; errors in rates predicted using these parameters at high pH and temperature are significant because the fitting uses logarithmic data. Longer term behaviour under hyperalkaline conditions, representative of some disposal environments, was investigated using the PCT and MCC-1 static leaching protocols with Ca(OH)2 solutions for up to 120 days (PCT) and 720 days (MCC-1). In hyperalkaline conditions dissolution was incongruent for all elements and the presence of alternating zirconia-rich and zirconia-poor alteration layers was observed on all leached monoliths, indicating the occurrence of a self-organisation phenomenon during leaching

Waste Form Release Data Package for the 2001 Immobilized Low-Activity Waste Performance Assessment

This data package documents the experimentally derived input data on the representative waste glasses LAWABP1 and HLP-31 that will be used for simulations of the immobilized lowactivity waste disposal system with the Subsurface Transport Over Reactive Multiphases (STORM) code. The STORM code will be used to provide the near-field radionuclide release source term for a performance assessment to be issued in March of 2001. Documented in this data package are data related to 1) kinetic rate law parameters for glass dissolution, 2) alkali-H ion exchange rate, 3) chemical reaction network of secondary phases that form in accelerated weathering tests, and 4) thermodynamic equilibrium constants assigned to these secondary phases. The kinetic rate law and Na+-H+ ion exchange rate were determined from single-pass flow-through experiments. Pressurized unsaturated flow and vapor hydration experiments were used for accelerated weathering or aging of the glasses. The majority of the thermodynamic data were extracted from the thermodynamic database package shipped with the geochemical code EQ3/6. However, several secondary reaction products identified from laboratory tests with prototypical LAW glasses were not included in this database, nor are the thermodynamic data available in the open literature. One of these phases, herschelite, was determined to have a potentially significant impact on the release calculations and so a solubility product was estimated using a polymer structure model developed for zeolites. Although this data package is relatively complete, final selection of ILAW glass compositions has not been done by the waste treatment plant contractor. Consequently, revisions to this data package to address new ILAW glass formulations are to be regularly expected

GaMin’11 – an International Inter-laboratory Comparison for Geochemical CO2 - Saline Fluid - Mineral Interaction Experiments

Due to the strong interest in geochemical CO2-fluid-rock interaction in the context of geological storage of CO2 a growing number of research groups have used a variety of different experimental ways to identify important geochemical dissolution or precipitation reactions and – if possible – quantify the rates and extent of mineral or rock alteration. In this inter-laboratory comparison the gas-fluid-mineral reactions of three samples of rock-forming minerals have been investigated by 11 experimental labs. The reported results point to robust identification of the major processes in the experiments by most groups. The dissolution rates derived from the changes in composition of the aqueous phase are consistent overall, but the variation could be reduced by using similar corrections for changing parameters in the reaction cells over time. The comparison of experimental setups and procedures as well as of data corrections identified potential improvements for future gas-fluid-rock studies

The Status of Radiation Damage Experiments

Experiments have been on-going for about two years to determine the effects that radiation damage have on the physical and chemical properties of candidate titanate ceramics for the immobilization of plutonium. We summarize the results of these experiments in this document

Immobilization and Limited Reoxidation of Technetium-99 by Fe(II)-Goethite

This report summarizes the methodology used to test the sequestration of technetium-99 present in both deionized water and simulated Hanford Tank Waste Treatment and Immobilization Plant waste solutions

Characterization of Direct-Push Vadose Zone Sediments from the 241-B and 241-BX Tank Farms

Geochemical tests provide evidence for the transit of a plume of caustic waste solution through the sediment column at the Hanford 241-B and -BX Tank Farms. Direct-push samples recovered from boreholes surrounding Tanks 241-B-110 and 241-BX-102 and related waste transfer lines and diversion boxes included sediments typical of those previously recovered from other localities on the Hanford Site. The Hanford formation sediments are dominantly quartzo-feldspathic sands strewn with lithic fragments, displaying a range of particle size distributions and sorting characteristics. Some moderately well-sorted, fine-grained lithologies are interpreted as lenticular bodies irregularly dispersed in coarser-grained, more poorly sorted sediments. Tier I tests conducted on the vadose zone sediments revealed an inverse correlation between moisture content and sediment size fraction (i.e., there is greater moisture content in finer-grained sediments). The Tier I tests also showed that the pore water solutions were likely sodium-rich, moderately saline, and possessed higher pH values than background (untainted) sediments. These data are characteristic of sediments that have encountered sodium-rich, saline, caustic waste solution, as documented in other reports at other suspect contamination sites around Hanford. Analyses of solutions from 1:1 water extracts reveal relatively balanced cation and anion concentrations, indicating that most of the geochemical species have been accounted for. The water extract data for affected sediments also indicate unusually high concentrations of aluminum, iron, and phosphorus. The relatively high concentrations of aluminum and iron may be the result of dissolution of secondary amorphous phases that precipitated after a reactive plume partially dissolved aluminum- and iron-bearing phases as it migrated through the sediment column. On the other hand, the presence of elevated concentrations of phosphorous may be the tell-tale signature of wastes derived from the bismuth phosphate separation process. Elements typically mobile in the geosphere, such as technetium-99, are present at either low concentrations or are below the analytical detection limit. However, we expect that the mobile elements would be present mainly along a narrow plume front, and if this front had passed deeper into the sediment profile than depths sampled, the retention of these elements would be minor. On the other hand for the direct push sediments from around BX Tank Farm, uranium-238 was detected in nearly all sediment specimens (by acid extract experiments) at concentrations above the natural crustal average (0.763 pCi/g), and we also detected the presence of several anthropogenic radioisotopes, such as cobalt-60, cesium-137, europium-154, and europium-155 (by gamma energy analysis). These data are direct confirmation of contamination of the sediments

Ice sheets as a missing source of silica to the polar oceans

Ice sheets play a more important role in the global silicon cycle than previously appreciated. Input of dissolved and amorphous particulate silica into natural waters stimulates the growth of diatoms. Here we measure dissolved and amorphous silica in Greenland Ice Sheet meltwaters and icebergs, demonstrating the potential for high ice sheet export. Our dissolved and amorphous silica flux is 0.20 (0.06-0.79) Tmol year(-1), ∼50% of the input from Arctic rivers. Amorphous silica comprises >95% of this flux and is highly soluble in sea water, as indicated by a significant increase in dissolved silica across a fjord salinity gradient. Retreating palaeo ice sheets were therefore likely responsible for high dissolved and amorphous silica fluxes into the ocean during the last deglaciation, reaching values of ∼5.5 Tmol year(-1), similar to the estimated export from palaeo rivers. These elevated silica fluxes may explain high diatom productivity observed during the last glacial-interglacial period

Fractionation of Li, Be, Ga, Nb, Ta, In, Sn, Sb, W and Bi in the peraluminous Early Permian Variscan granites of the Cornubian Batholith: precursor processes to magmatic-hydrothermal mineralisation

The Early Permian Variscan Cornubian Batholith is a peraluminous, composite pluton intruded into Devonian and Carboniferous metamorphosed sedimentary and volcanic rocks. Within the batholith there are: G1 (two-mica), G2 (muscovite), G3 (biotite), G4 (tourmaline) and G5 (topaz) granites. G1-G2 and G3-G4 are derived from greywacke sources and linked through fractionation of assemblages dominated by feldspars and biotite, with minor mantle involvement in G3. G5 formed though flux-induced biotite-dominate melting in the lower crust during granulite facies metamorphism. Fractionation enriched G2 granites in Li (average 315 ppm), Be (12 ppm), Ta (4.4 ppm), In (74 ppb), Sn (18 ppm) and W (12 ppm) relative to crustal abundances and G1 granites. Gallium (24 ppm), Nb (16 ppm) and Bi (0.46 ppm) are not significantly enriched during fractionation, implying they are more compatible in the fractionating assemblage. Sb (0.16 ppm) is depleted in G1-G2 relative to the average upper and lower continental crust. Muscovite, a late-stage magmatic/subsolidus mineral, is the major host of Li, Nb, In, Sn and W in G2 granites. G2 granites are spatially associated with W-Sn greisen mineralisation. Fractionation within the younger G3-G4 granite system enriched Li (average 364 ppm), Ga (28 ppm), In (80 ppb), Sn (14 ppm), Nb (27 ppm), Ta (4.6 ppm), W (6.3 ppm) and Bi (0.61 ppm) in the G4 granites with retention of Be in G3 granites due to partitioning of Be into cordierite during fractionation. The distribution of Nb and Ta is controlled by accessory phases such as rutile within the G4 granites, facilitated by high F and lowering the melt temperature, leading to disseminated Nb and Ta mineralisation. Lithium, In, Sn and W are hosted in biotite micas which may prove favourable for breakdown on ingress of hydrothermal fluids. Higher degrees of scattering on trace element plots may be attributable to fluid–rock interactions or variability within the magma chamber. The G3-G4 system is more boron-rich, evidenced by a higher modal abundance of tourmaline. In this system, there is a stronger increase of Sn compared to G1-G2 granites, implying Sn in tourmaline-dominated mineral lodes may represent exsolution from G4 granites. G1-G4 granite abundances can be accounted for by 20–30% partial melting and 10–40% fractionation of a greywacke source. G5 granites are analogues of Rare Metal Granites described in France and Germany. These granites are enriched in Li (average 1363 ppm), Ga (38 ppm), Sn (21 ppm), W (24 ppm), Nb (52 ppm) and Ta (15 ppm). Within G5 granites, the metals partition into accessory minerals such as rutile, columbite-tantalite and cassiterite, forming disseminated magmatic mineralisation. High observed concentrations of Li, In, Sn, W, Nb and Ta in G4 and G5 granites are likely facilitated by high F, Li and P, which lower melt temperature and promote retention of these elements in the melt, prior to crystallisation of disseminated magmatic mineralisation