Results of Laboratory Scale Fracture Tests on Rock/Cement Interfaces

A number of pure cement and cement-basalt interface samples were subjected to a range of compressive loads to form internal fractures. X-ray microtomography was used to visualize the formation and growth of internal fractures in three dimensions as a function of compressive loads. This laboratory data will be incorporated into a geomechanics model to predict the risk of CO2 leakage through wellbores during geologic carbon storage

Characterization of 200-UP-1 and 200-ZP-1 Operable Unit Aquifer Sediments and Batch Adsorption Distribution Coefficients for Contaminants of Concern--Fiscal Year 2006 Progress

A total of six core samples from 200-UP/ZP-1 OUs and two additional outcrop samples were characterized during FY2006 by PNNL. One sample (C4971) was identified as slough and not used, but the five other samples identified as intact core samples were used for further analyses. The C4977 sample is gravel-sandy silt and C4990 samples are fine-sandy silt from the Ringold formation. Although the sediments from these two boreholes have similar mineralogical composition, C4990 samples show higher values of Fe oxide content, clay/silt content, and surface area compared those in C4977. The measured Tc Kd values ranged 0–0.2 mg/L for both samples, while U(VI) Kd for C4990 (4.23 mg/L) is much higher than that for C4977 (0.76 mg/L). A key finding from the Kd measurements is that detailed sediment and pore water characterization is necessary to understand the variation in Kd values seen in the empirical batch tests. Without the ancillary characterization of the sediments and pore waters, one might form misleading interpretations of the mechanisms that control the Kd values. Thus, physical, geochemical, and hydrological characterization of the sediments and pore waters should be conducted to increase our understanding of the site-specific Kd measurements. More details for methods and results will be provided in the formal technical report in FY 2007

Uptake of be(Ii) by cement in degradation stage i: Wet-chemistry and molecular dynamics studies

The uptake of beryllium by hardened cement paste (HCP, with CEM I 42,5 N BV/SR/LA type) in degradation stage I was investigated with a series of batch sorption experiments with 10$^{-6}$ M ≤ [Be(II)]0 ≤ 10$^{-2.5}$ M and 2 g·L$^{-1}$ ≤ [S/L] ≤ 50 g·L$^{-1}$. All experiments were performed under Ar atmosphere at T = (22 ± 2) °C. Solubility limits calculated for α-Be(OH)$_{2}$(cr) in the conditions of the cement pore water were used to define the experimental window in the sorption experiments. Beryllium sorbs strongly on HCP under all of the investigated conditions, with log Rd ≈ 5.5 (Rd in L⋅kg$^{-1}$). Sorption isotherms show a linear behavior with a slope of ≈+1 (log [Be(II)]$_{solid}$ vs. log [Be(II)]$_{aq}$) over four orders of magnitude (10$^{-8}$ M ≤ [Be(II)]$_{aq}$ ≤ 10$^{-4}$ M), which confirm that the uptake is controlled by sorption processes and that solubility phenomena do not play any role within the considered boundary conditions. The similar uptake observed for beryllium in calcium silicate hydrate (C-S-H) phases supports that the C-S-H phases are the main sink of Be(II) in cement. The strong uptake observed for Be(II) agrees with the findings reported for heavier metal ions, e.g., Zn(II), Eu(III), Am(III), or Th(IV). The exceptional sorption properties of beryllium can be partially explained by its small size, which result in a charge-to-size ratio (z/d) of the same order as Eu(III) or Am(III). Kinetic experiments confirm the slow uptake of Be(II), which is characterized by a two-step process. In analogy to other strongly sorbing metal ions such as Zn(II) or Th(IV), a fast surface complexation (t < 4 days) followed by a slower incorporation of Be(II) in the C-S-H structure (t ≥ 60 days) are proposed. The surface complexation was studied in detail with molecular dynamic simulations, and the most common surface species are identified and described. This work provides the first experimental evidence supporting the strong uptake of Be(II) by HCP in degradation stage I, further extending previous findings on C-S-H phases and HCP in degradation stage II. These results overcome previous conservative estimates assuming no or only a weak uptake in cementitious systems and represent a relevant contribution for the quantitative assessment on the retention/mobilization of beryllium in the context of nuclear waste disposal

Uranium Contamination in the 300 Area: Emergent Data and their Impact on the Source Term Conceptual Model

The primary objectives of this characterization activity were to: 1) determine the extent of uranium contamination in the sediments, 2) quantify the leachable (labile) concentration of uranium in the sediments, and 3) create a data set that could be used to correlate the present data to existing 300 Area data. In order to meet these objectives, sediments collected from wells 399-2-5 (C5708), 299-3-22 (C5706) and 299-4-14 (C5707) were analyzed for moisture content, 1:1 sediment:water extracts (which provide soil pH, electrical conductivity [EC], cation, and anion data), total carbon and inorganic carbon content, 8 M nitric acid extracts (which provide a measure of the total leachable sediment content of the contaminants), microwave-assisted digestion (which results in total digestion of the sediment), and carbonate leaches (which provide an assessment of the concentration of labile uranium present in the sediments). Additionally, pore waters present in select samples were extracted using ultracentrifugation. The mobility characteristics of uranium vary within the multiple subsurface zones that contain residual contaminant uranium. Principal subsurface zones include 1) the vadose zone, 2) a zone through which the water table rises and falls, 3) the aquifer, and 4) a zone where groundwater and river water interact beneath the river shoreline. Principal controls on mobilization include the form of the residual uranium (e.g., crystalline minerals, amorphous precipitates/coatings, sorbed onto sediment), the transporting medium (e.g., water infiltration from the land surface, groundwater), and the rate of exchange between the form and transporting medium. The bicarbonate content of aqueous media strongly influences the rate of exchange, with relatively higher content enhancing mobility. Groundwater has a higher bicarbonate content than river water or other freshwater sources, such as utility and potable water systems. The variety of processes affecting the mobility of uranium in the subsurface, along with the numerous potential compartments where residual contamination may be located, presents challenges for predicting uranium movement through environmental pathways. The processes responsible for the persistence of the plume may involve cycling of uranium between the aquifer and overlying zone through which the water table fluctuates. Contaminated groundwater is moved upward into the lower vadose zone, and when the water table subsequently falls, contaminated moisture is left behind. Some of the uranium in groundwater may become sorbed to sediment in that zone, to subsequently slowly release. Also, near the Columbia River in the zone of groundwater/river water interaction, where the bicarbonate content is lowered because of infiltrating river water, the tendency for uranium to adsorb onto sediment is enhanced, thus slowing dissipation via the groundwater pathway. Fluctuations in the Columbia River stage are the driving mechanism for the rise and fall of the water table beneath the 300 Area, and also for creating the dynamic hydraulic and geochemical environment found in the zone of interaction beneath the shoreline

Impact of calcium hydroxide on physical characteristics and leaching stability of metakaolin-based geopolymer waste form containing radioactive borate waste

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Technetium Removal Using Tc-Goethite Coprecipitation

This report describes the results from laboratory tests performed at Pacific Northwest National Laboratory for the U.S. Department of Energy (DOE) EM-31 Support Program (EMSP) subtask, “Low temperature waste forms coupled with technetium removal using an alternative immobilization process such as Fe(II) treated-goethite precipitation” to increase our understanding of 99Tc long-term stability in goethite mineral form and the process that controls the 99Tc(VII) reduction and removal by the final Fe (oxy)hydroxide forms. The overall objectives of this task were to 1) evaluate the transformation process of Fe (oxy)hydroxide solids to the more crystalline goethite (α-FeOOH) mineral for 99Tc removal and 2) determine the mechanism that limits 99Tc(IV) reoxidation in Fe(II)-treated 99Tc-goethite mineral and 3) evaluate whether there is a long-term 99Tcoxidation state change for Tc sequestered in the iron solids

Effective Permeability Change in Wellbore Cement with Carbon Dioxide Reaction

Portland cement, a common sealing material for wellbores for geological carbon sequestration was reacted with CO{sub 2} in supercritical, gaseous, and aqueous phases at various pressure and temperature conditions to simulate cement-CO{sub 2} reaction along the wellbore from carbon injection depth to the near-surface. Hydrated Portland cement columns (14 mm diameter x 90 mm length; water-to-cement ratio = 0.33) including additives such as steel coupons and Wallula basalt fragments were reacted with CO{sub 2} in the wet supercritical (the top half) and dissolved (the bottom half) phases under carbon sequestration condition with high pressure (10 MPa) and temperature (50 C) for 5 months, while small-sized hydrated Portland cement columns (7 mm diameter x 20 mm length; water-to-cement ratio = 0.38) were reacted with CO{sub 2} in dissolved phase at high pressure (10 MPa) and temperature (50 C) for 1 month or with wet CO{sub 2} in gaseous phase at low pressure (0.2 MPa) and temperature (20 C) for 3 months. XMT images reveal that the cement reacted with CO{sub 2} saturated groundwater had degradation depth of {approx}1 mm for 1 month and {approx}3.5 mm for 5 month, whereas the degradation was minor with cement exposure to supercritical CO{sub 2}. SEM-EDS analysis showed that the carbonated cement was comprised of three distinct zones; the innermost less degraded zone with Ca atom % &gt; C atom %, the inner degraded zone with Ca atom % {approx} C atom % due to precipitation of calcite, the outer degraded zone with C atom % &gt; Ca atom % due to dissolution of calcite and C-S-H, as well as adsorption of carbon to cement matrix. The outer degraded zone of carbonated cement was porous and fractured because of dissolution-dominated reaction by carbonic acid exposure, which resulted in the increase in BJH pore volume and BET surface area. In contrast, cement-wet CO{sub 2}(g) reaction at low P (0.2 MPa)-T (20 C) conditions for 1 to 3 months was dominated by precipitation of micron-sized calcite on the outside surface of cement, which resulted in the decrease in BJH pore volume and BET surface area. Cement carbonation and pore structure change are significantly dependent on pressure and temperature conditions as well as the phase of CO{sub 2}, which controls the balance between precipitation and dissolution in cement matrix. Geochemical modeling result suggests that ratio of solid (cement)-to-solution (carbonated water) has a significant effect on cement carbonation, thus the cement-CO{sub 2} reaction experiment needs to be conducted under realistic conditions representing the in-situ wellbore environment of carbon sequestration field site. Total porosity and air permeability for a duplicate cement column with water-to-cement ratio of 0.38 measured after oven-drying by Core Laboratories using Boyle's Law technique and steady-state method were 31% and 0.576 mD. A novel method to measure the effective liquid permeability of a cement column using X-ray micro-tomography images after injection of pressurized KI (potassium iodide) is under development by PNNL. Preliminary results indicate the permeability of a cement column with water-to-cement ratio of 0.38 is 4-8 mD. PNNL will apply the method to understand the effective permeability change of Portland cement by CO{sub 2}(g) reaction under a variety of pressure and temperature conditions to develop a more reliable well-bore leakage risk model

Coupling Sorption to Soil Weathering During Reactive Transport: Impacts of Mineral Transformation and Sorbate Aging on Contaminant Speciation and Mobility

Our work is aimed at developing a predictive-mechanistic understanding of the coupling between mineral weathering from caustic waste release and contaminant (Cs, Sr, I) fate and transport in waste-impacted sediments across space, time and geochemical gradients that encompass the process-level heterogeneity observed at the Hanford DOE site. Our specific objectives are: (1) to assess the molecular-scale mechanisms responsible for time-dependent sequestration of contaminants (Cs, Sr and I) during penetration of waste-induced weathering fronts through sedimentary media; (2) to determine the rate and extent of contaminant release from the sorbed state; (3) to develop a reactive transport model based on molecular mechanisms and macroscopic flow experiments (from (1) and (2)) that accurately simulates adsorption, aging, and desorption at the bench-scale, and that can be applied to--and validated at--field sites such as Hanford

Characterization of Technetium Speciation in Cast Stone

This report describes the results from laboratory tests performed at Pacific Northwest National Laboratory (PNNL) for the U.S. Department of Energy (DOE) EM-31 Support Program (EMSP) subtask, “Production and Long-Term Performance of Low Temperature Waste Forms” to provide additional information on technetium (Tc) speciation characterization in the Cast Stone waste form. To support the use of Cast Stone as an alternative to vitrification for solidifying low-activity waste (LAW) and as the current baseline waste form for secondary waste streams at the Hanford Site, additional understanding of Tc speciation in Cast Stone is needed to predict the long-term Tc leachability from Cast Stone and to meet the regulatory disposal-facility performance requirements for the Integrated Disposal Facility (IDF). Characterizations of the Tc speciation within the Cast Stone after leaching under various conditions provide insights into how the Tc is retained and released. The data generated by the laboratory tests described in this report provide both empirical and more scientific information to increase our understanding of Tc speciation in Cast Stone and its release mechanism under relevant leaching processes for the purpose of filling data gaps and to support the long-term risk and performance assessments of Cast Stone in the IDF at the Hanford Site