Tanks 18 And 19-F Structural Flowable Grout Fill Material Evaluation And Recommendations

Cementitious grout will be used to close Tanks 18-F and 19-F. The functions of the grout are to: 1) physically stabilize the final landfill by filling the empty volume in the tanks with a non-compressible material; 2) provide a barrier for inadvertent intrusion into the tank; 3) reduce contaminant mobility by a) limiting the hydraulic conductivity of the closed tank and b) reducing contact between the residual waste and infiltrating water; and 4) providing an alkaline, chemically reducing environment in the closed tank to control speciation and solubility of selected radionuclides. The objective of this work was to identify a single (all-in-one) grout to stabilize and isolate the residual radionuclides in the tank, provide structural stability of the closed tank and serve as an inadvertent intruder barrier. This work was requested by V. A. Chander, High Level Waste (HLW) Tank Engineering, in HLW-TTR-2011-008. The complete task scope is provided in the Task Technical and QA Plan, SRNL-RP-2011-00587 Revision 0. The specific objectives of this task were to: 1) Identify new admixtures and dosages for formulating a zero bleed flowable tank fill material selected by HLW Tank Closure Project personnel based on earlier tank fill studies performed in 2007. The chemical admixtures used for adjusting the flow properties needed to be updated because the original admixture products are no longer available. Also, the sources of cement and fly ash have changed, and Portland cements currently available contain up to 5 wt. % limestone (calcium carbonate). 2) Prepare and evaluate the placement, compressive strength, and thermal properties of the selected formulation with new admixture dosages. 3) Identify opportunities for improving the mix selected by HLW Closure Project personnel and prepare and evaluate two potentially improved zero bleed flowable fill design concepts; one based on the reactor fill grout and the other based on a shrinkage compensating flowable fill mix design. 4) Prepare samples for hydraulic property measurements for comparison to the values in the F and H- Tank Farm Performance Assessments (PAs). 5) Identify a grout mix for the Tanks 18-F and 19-F Grout Procurement Specification [Forty, 2011 a, b, c]. Results for two flowable zero bleed structural fill concepts containing 3/8 inch gravel (70070 Series and LP#8 Series) and a sand only mix (SO Series) are provided in this report. Tank Farm Engineering and SRNL Project Management selected the 70070 mix as the base case for inclusion in Revision 0 of the Tanks 18-F and 19-F grout procurement specification [Forty 2011 a] and requested admixture recommendations and property confirmation for this formulation [Forty, 2011 b]. Lower cementitious paste mixes were formulated because the 70070 mix is over designed with respect to strength and generates more heat from hydration reactions than is desirable for mass pour application. Work was also initiated on a modification of the recommended mix which included shrinkage compensation to mitigate fast pathways caused by shrinkage cracking and poor physical bonding to the tank and ancillary equipment. Testing of this option was postponed to FY12. Mix, LP#8-16 is recommended for inclusion in the specification for furnishing and delivering tank closure grout for Tanks 18-F and 19-F [Forty, 2011 c]. A shrinkage compensating variation of this mix, LP#16C, has not been fully developed and characterized at this time

Saltstone Oxidation Study: Leaching Method -13092

ABSTRACT Cementitious waste forms can be designed to chemically stabilize selected contaminants, such as Tc +7 and Cr +6 , by chemically reduction to lower valance states, Tc +4 and Cr +3 , respectively, and precipitation of these species in alkaline media as low solubility solid phases. Data for oxidation of this type of cementitious waste form cured under field conditions as a function of time is required for predicting the performance of the waste form and disposal facility. The rate of oxidation (oxidation front advancement) is an important parameter for predicting performance because the solubilities of some radionuclide contaminants, e.g., technetium, are a function of the oxidation state. A non-radioactive experiment was designed for quantifying the oxidation front advancement using chromium, as an approximate redox-sensitive surrogate (Cr +6 / Cr +3 ) for technetium (Tc +7 / Tc +4 ). Nonradioactive cementitious waste forms were prepared in the laboratory and cured under both laboratory and "field conditions." Laboratory conditions were ambient temperature and sealed sample containers. Field conditions were approximated by curing samples in open containers which were placed inside a plastic container stored outdoors at SRS. The container had a lid and was instrumented with temperature and humidity probes. Subsamples as thin as 0.2 mm were taken as a function of distance from the exposed surface of the as-cast sample. The subsamples were leached and the leachates were analyzed for chromium, nitrate, nitrite and sodium. Nitrate, nitrite, and sodium concentrations were used to provide baseline data because these species are not chemically retained in the waste form matrix to any significant extent and are not redox sensitive. "Effective" oxidation fronts for Cr were measured for samples containing 1000, 500 and 20 mg/kg Cr added as soluble sodium chromate, Na 2 CrO 4 . For a sample cured for 129 days under field conditions, leachable Cr (assumed to be the oxidized form, i.e., Cr +6 was detected in the top 15 to 20 mm of the sample spiked with 1000 mg/kg Cr. Below about 20 mm, the Cr concentrations in leachates were below the detection limit (< 0.010 mg/L) which indicates that the oxidation as the result of exposure to air was limited to the top 20 mm of the sample after exposure for 129 days and that the bulk of the waste form was not affected, i.e., the Cr was stabilized and insoluble. For samples cured in the laboratory, leachable Cr was detected in the top 8 mm of the Cr 1000 sample cured in the laboratory for 37 days. Between 8 and 14 mm, the concentration Cr in the leachate dropped by a factor of about 20 to just above the detection limit. These depth of penetration results indicate that the rate of advancement of the oxidation front for samples spiked with 1000 mg/kg Cr cured under "field conditions" for 129 days is less than that for the sample cured in the laboratory for 37 days, i.e., 0.156 and 0.216 mm/day, respectively. Additional data are presented for samples spiked with 500 and 20 mg/kg Cr

Effect Of Oxidation On Chromium Leaching And Redox Capacity Of Slag-Containing Waste Forms

The rate of oxidation is important to the long-term performance of reducing salt waste forms because the solubility of some contaminants, e.g., technetium, is a function of oxidation state. TcO{sub 4}{sup −} in the salt solution is reduced to Tc(IV) and has been shown to react with ingredients in the waste form to precipitate low solubility sulfide and/or oxide phases [Shuh, et al., 1994, Shuh, et al., 2000, Shuh, et al., 2003]. Upon exposure to oxygen, the compounds containing Tc(IV) oxidize to the pertechnetate ion, Tc(VII)O{sub 4}{sup −}, which is very soluble. Consequently the rate of technetium oxidation front advancement into a monolith and the technetium leaching profile as a function of depth from an exposed surface are important to waste form performance and ground water concentration predictions. An approach for measuring contaminant oxidation rate (effective contaminant specific oxidation rate) based on leaching of select contaminants of concern is described in this report. In addition, the relationship between reduction capacity and contaminant oxidation is addressed. Chromate was used as a non-radioactive surrogate for pertechnetate in simulated waste form samples. Depth discrete subsamples were cut from material exposed to Savannah River Site (SRS) ''field cured'' conditions. The subsamples were prepared and analyzed for both reduction capacity and chromium leachability. Results from field-cured samples indicate that the depth at which leachable chromium was detected advanced further into the sample exposed for 302 days compared to the sample exposed to air for 118 days (at least 50 mm compared to at least 20 mm). Data for only two exposure time intervals is currently available. Data for additional exposure times are required to develop an equation for the oxidation front progression. Reduction capacity measurements (per the Angus-Glasser method, which is a measurement of the ability of a material to chemically reduce Ce(IV) to Ce(III) in solution) performed on depth discrete samples could not be correlated with the amount of chromium leached from the depth discrete subsamples or with the oxidation front inferred from soluble chromium (i.e., effective Cr oxidation front). Exposure to oxygen (air or oxygen dissolved in water) results in the release of chromium through oxidation of Cr(III) to highly soluble chromate, Cr(VI). Residual reduction capacity in the oxidized region of the test samples indicates that the remaining reduction capacity is not effective in re-reducing Cr(VI) in the presence of oxygen. Consequently, this method for determining reduction capacity may not be a good indicator of the effective contaminant oxidation rate in a relatively porous solid (40 to 60 volume percent porosity). The chromium extracted in depth discrete samples ranged from a maximum of about 5.8 % at about 5 mm (118 day exposure) to about 4 % at about 10 mm (302 day exposure). The use of reduction capacity as an indicator of long-term performance requires further investigation. The carbonation front was also estimated to have advanced to at least 28 mm in 302 days based on visual observation of gas evolution during acid addition during the reduction capacity measurements. Depth discrete sampling of materials exposed to realistic conditions in combination with short term leaching of crushed samples has potential for advancing the understanding of factors influencing performance and will support conceptual model development

Relationship Between Flowability And Tank Closure Grout Quality

After completion of waste removal and chemical cleaning operations, Tanks 5-F and 6-F await final closure. The project will proceed with completing operational closure by stabilizing the tanks with grout. Savannah River Remediation's (SRR) experience with grouting Tanks 18-F and 19-F showed that slump-flow values were correlated with flow/spread inside these tanks. Less mounding was observed when using grouts with higher slump-flow. Therefore, SRNL was requested to evaluate the relationship between flowability and cured properties to determine whether the slump-flow maximum spread of Mix LP#8-16 could be increased from 28 inches to 30 inches without impacting the grout quality. A request was also made to evaluate increasing the drop height from 5 feet to 10 feet with the objective of enhancing the flow inside the tank by imparting more kinetic energy to the placement. Based on a review of the grout property data for Mix LP#8-16 collected from Tank 18-F and 19-F quality control samples, the upper limit for slump-flow measured per ASTM C 1611 can be increased from 28 to 30 inches without affecting grout quality. However, testing should be performed prior to increasing the drop height from 5 to 10 feet or observations should be made during initial filling operations to determine whether segregation occurs as a function of drop heights between 5 and 10 feet. Segregation will negatively impact grout quality. Additionally, increasing the delivery rate of grout into Tanks 5-F and 6-F by using a higher capacity concrete/grout pump will result in better grout spread/flow inside the tanks

Relationship Between Flowability And Tank Closure Grout Quality

After completion of waste removal and chemical cleaning operations, Tanks 5-F and 6-F await final closure. The project will proceed with completing operational closure by stabilizing the tanks with grout. Savannah River Remediation's (SRR) experience with grouting Tanks 18-F and 19-F showed that slump-flow values were correlated with flow/spread inside these tanks. Less mounding was observed when using grouts with higher slump-flow. Therefore, SRNL was requested to evaluate the relationship between flowability and cured properties to determine whether the slump-flow maximum spread of Mix LP#8-16 could be increased from 28 inches to 30 inches without impacting the grout quality. A request was also made to evaluate increasing the drop height from 5 feet to 10 feet with the objective of enhancing the flow inside the tank by imparting more kinetic energy to the placement. Based on a review of the grout property data for Mix LP#8-16 collected from Tank 18-F and 19-F quality control samples, the upper limit for slump-flow measured per ASTM C 1611 can be increased from 28 to 30 inches without affecting grout quality. However, testing should be performed prior to increasing the drop height from 5 to 10 feet or observations should be made during initial filling operations to determine whether segregation occurs as a function of drop heights between 5 and 10 feet. Segregation will negatively impact grout quality. Additionally, increasing the delivery rate of grout into Tanks 5-F and 6-F by using a higher capacity concrete/grout pump will result in better grout spread/flow inside the tanks

Method Evaluation And Field Sample Measurements For The Rate Of Movement Of The Oxidation Front In Saltstone

The objective of this work was to develop and evaluate a series of methods and validate their capability to measure differences in oxidized versus reduced saltstone. Validated methods were then applied to samples cured under field conditions to simulate Performance Assessment (PA) needs for the Saltstone Disposal Facility (SDF). Four analytical approaches were evaluated using laboratory-cured saltstone samples. These methods were X-ray absorption spectroscopy (XAS), diffuse reflectance spectroscopy (DRS), chemical redox indicators, and thin-section leaching methods. XAS and thin-section leaching methods were validated as viable methods for studying oxidation movement in saltstone. Each method used samples that were spiked with chromium (Cr) as a tracer for oxidation of the saltstone. The two methods were subsequently applied to field-cured samples containing chromium to characterize the oxidation state of chromium as a function of distance from the exposed air/cementitious material surface

Grout long radius flow testing to support Saltstone disposal Unit 5 design

The Saltstone Facility, located within the Savannah River Site (SRS) near Aiken, South Carolina, consists of two facility segments: The Saltstone Production Facility (SPF) and the Saltstone Disposal Facility (SDF). The SPF receives decontaminated legacy low level sodium salt waste solution that is a byproduct of prior nuclear material processing. The salt solution is mixed with cementitious materials to form a grout slurry known as “Saltstone”. The grout is pumped to the SDF where it is placed in a Saltstone Disposal Unit (SDU) to solidify. SDU 6 is referred to as a “mega vault” and is currently in the design stage. The conceptual design for SDU 6 is a single cell, cylindrical geometry approximately 114.3 meters in diameter by 13.1 meter high and is larger than previous cylindrical SDU designs, 45.7 meters in diameter by 7.01 meters high (30 million gallons versus 2.9 million gallons of capacity). Saltstone slurry will be pumped into the new waste disposal unit through roof openings at a projected flow rate of about 34.1 cubic meters per hour. Nine roof openings are included in the design to discharge material into the SDU with an estimated grout pour radius of 22.9 to 24.4 meters and initial drop height of 13.1 meters. The conceptual design for the new SDU does not include partitions to limit the pour radius of the grout slurry during placement other than introducing material from different pour points. This paper addresses two technical issues associated with the larger diameter of SDU 6; saltstone flow distance in a tank 114.3 meters in diameter and quality of the grout. A long-radius flow test scaled to match the velocity of an advancing grout front was designed to address these technology gaps. The emphasis of the test was to quantify the flow distance and to collect samples to evaluate cured properties including compressive strength, porosity, density, and saturated hydraulic conductivity. Two clean cap surrogate mixes (saltstone premix plus water) were designed to simulate slurry with the reference saltstone rheology and a saltstone with extra water from the process flushing operation. Long-radius flow tests were run using approximately 4.6 cubic meters of each of these mixes. In both tests the pump rate was 0.063 liters/second (1 gpm). A higher pump rate, 0.19 liters/second (3 gpm), was used in a third long-radius flow test. The angle of repose of the grout wedges increased as a function of time in all three tests. The final angles of repose were measured at 3.0º, 2.4º, and 0.72º. The pump rate had the largest effect on the radial flow distance and slope of the grout surface. The slope on the pour placed at 0.19 liters/second (3 gpm) was most representative of the slope on the grout currently being pumped into SDU 2 which is estimated to be 0.7º to 0.9º. The final grout heights at 1/3 of a meter from the discharge point were 115, 105, and 38 cm. Entrapped air (≥ 0.25 cm bubbles) was also observed in all of the mixes. The entrapped air appeared to be released from the flows within about 3.1 meters (10 feet) of the discharge point. The bleed water was clear but had a thin layer of floating particulates. The bleed water should be retrievable by a drain water collection system in SDU 6 assuming the system does not get clogged. Layering was observed and was attributed to intervals when the hopper was being cleaned. Heat from the hydration reactions was noticeable to the touch

CFD [computational fluid dynamics] And Safety Factors. Computer modeling of complex processes needs old-fashioned experiments to stay in touch with reality.

Computational fluid dynamics (CFD) is recognized as a powerful engineering tool. That is, CFD has advanced over the years to the point where it can now give us deep insight into the analysis of very complex processes. There is a danger, though, that an engineer can place too much confidence in a simulation. If a user is not careful, it is easy to believe that if you plug in the numbers, the answer comes out, and you are done. This assumption can lead to significant errors. As we discovered in the course of a study on behalf of the Department of Energy's Savannah River Site in South Carolina, CFD models fail to capture some of the large variations inherent in complex processes. These variations, or scatter, in experimental data emerge from physical tests and are inadequately captured or expressed by calculated mean values for a process. This anomaly between experiment and theory can lead to serious errors in engineering analysis and design unless a correction factor, or safety factor, is experimentally validated. For this study, blending times for the mixing of salt solutions in large storage tanks were the process of concern under investigation. This study focused on the blending processes needed to mix salt solutions to ensure homogeneity within waste tanks, where homogeneity is required to control radioactivity levels during subsequent processing. Two of the requirements for this task were to determine the minimum number of submerged, centrifugal pumps required to blend the salt mixtures in a full-scale tank in half a day or less, and to recommend reasonable blending times to achieve nearly homogeneous salt mixtures. A full-scale, low-flow pump with a total discharge flow rate of 500 to 800 gpm was recommended with two opposing 2.27-inch diameter nozzles. To make this recommendation, both experimental and CFD modeling were performed. Lab researchers found that, although CFD provided good estimates of an average blending time, experimental blending times varied significantly from the average

Magnesia-Based Cements: A Journey of 150 Years, and Cements for the Future?

This review examines the detailed chemical insights that have been generated through 150 years of work worldwide on magnesium-based inorganic cements, with a focus on both scientific and patent literature. Magnesium carbonate, phosphate, silicate-hydrate, and oxysalt (both chloride and sulfate) cements are all assessed. Many such cements are ideally suited to specialist applications in precast construction, road repair, and other fields including nuclear waste immobilization. The majority of MgO-based cements are more costly to produce than Portland cement because of the relatively high cost of reactive sources of MgO and do not have a sufficiently high internal pH to passivate mild steel reinforcing bars. This precludes MgO-based cements from providing a large-scale replacement for Portland cement in the production of steel-reinforced concretes for civil engineering applications, despite the potential for CO2 emissions reductions offered by some such systems. Nonetheless, in uses that do not require steel reinforcement, and in locations where the MgO can be sourced at a competitive price, a detailed understanding of these systems enables their specification, design, and selection as advanced engineering materials with a strongly defined chemical basis

Tanks 18 And 19-F Structural Flowable Grout Fill Material Evaluation And Recommendations

Cementitious grout will be used to close Tanks 18-F and 19-F. The functions of the grout are to: 1) physically stabilize the final landfill by filling the empty volume in the tanks with a non-compressible material; 2) provide a barrier for inadvertent intrusion into the tank; 3) reduce contaminant mobility by a) limiting the hydraulic conductivity of the closed tank and b) reducing contact between the residual waste and infiltrating water; and 4) providing an alkaline, chemically reducing environment in the closed tank to control speciation and solubility of selected radionuclides. The objective of this work was to identify a single (all-in-one) grout to stabilize and isolate the residual radionuclides in the tank, provide structural stability of the closed tank and serve as an inadvertent intruder barrier. This work was requested by V. A. Chander, High Level Waste (HLW) Tank Engineering, in HLW-TTR-2011-008. The complete task scope is provided in the Task Technical and QA Plan, SRNL-RP-2011-00587 Revision 0. The specific objectives of this task were to: 1) Identify new admixtures and dosages for formulating a zero bleed flowable tank fill material selected by HLW Tank Closure Project personnel based on earlier tank fill studies performed in 2007. The chemical admixtures used for adjusting the flow properties needed to be updated because the original admixture products are no longer available. Also, the sources of cement and fly ash have changed, and Portland cements currently available contain up to 5 wt. % limestone (calcium carbonate). 2) Prepare and evaluate the placement, compressive strength, and thermal properties of the selected formulation with new admixture dosages. 3) Identify opportunities for improving the mix selected by HLW Closure Project personnel and prepare and evaluate two potentially improved zero bleed flowable fill design concepts; one based on the reactor fill grout and the other based on a shrinkage compensating flowable fill mix design. 4) Prepare samples for hydraulic property measurements for comparison to the values in the F and H- Tank Farm Performance Assessments (PAs). 5) Identify a grout mix for the Tanks 18-F and 19-F Grout Procurement Specification [Forty, 2011 a, b, c]. Results for two flowable zero bleed structural fill concepts containing 3/8 inch gravel (70070 Series and LP#8 Series) and a sand only mix (SO Series) are provided in this report. Tank Farm Engineering and SRNL Project Management selected the 70070 mix as the base case for inclusion in Revision 0 of the Tanks 18-F and 19-F grout procurement specification [Forty 2011 a] and requested admixture recommendations and property confirmation for this formulation [Forty, 2011 b]. Lower cementitious paste mixes were formulated because the 70070 mix is over designed with respect to strength and generates more heat from hydration reactions than is desirable for mass pour application. Work was also initiated on a modification of the recommended mix which included shrinkage compensation to mitigate fast pathways caused by shrinkage cracking and poor physical bonding to the tank and ancillary equipment. Testing of this option was postponed to FY12. Mix, LP#8-16 is recommended for inclusion in the specification for furnishing and delivering tank closure grout for Tanks 18-F and 19-F [Forty, 2011 c]. A shrinkage compensating variation of this mix, LP#16C, has not been fully developed and characterized at this time