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Title: Getter Incorporation into Cast Stone and Solid State Characterizations

Abstract

Washington River Protection Solutions (WRPS) is collecting relevant available data on waste forms for use as a supplemental immobilization technology, to provide the additional capacity needed to treat low-activity waste (LAW) in Hanford Site tanks and complete the tank waste cleanup mission in a timely and cost-effective manner. One candidate supplemental waste form, fabricated using a low-temperature process, is a cementitious grout called Cast Stone. Cast Stone has been under investigation for this application at Pacific Northwest National Laboratory (PNNL) since initial screening tests in FY13. This report is the culmination of work to lower the diffusivities of Tc and I from Cast Stone using getters. Getters are compounds added to a system designed to selectively sequester a species of interest to provide increased stability to the species. The work contained within this report is related to waste form development and testing, and does not directly support the 2017 integrated disposal facility (IDF) performance assessment. However, this work contains valuable information which may be used in performance assessment maintenance past FY17, and in future waste form development. This report on performance characterization of Tc and I getters in Cast Stone fabricated with simulated LAW covers several areas of interest andmore » major findings to WRPS: investigating performance of potassium metal sulfide (KMS-2-SS) and tin (II) apatite (Sn-A) as Tc getters when incorporated into Cast Stone; investigating performance of silver exchanged zeolite (Ag-Z) and argentite (Arg) as I getters when incorporated into Cast Stone; utilizing sequential addition of Tc and I getters to overcome any deleterious interactions between the getters in solution; determining, for the first time, Tc distribution within the cured Cast Stone and its evolution during leaching; and performing solid state characterization of getters and Cast Stone samples to support leach test findings and develop a mechanistic understanding of the processes that control Tc and I release into solution.« less

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1]
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1334894
Report Number(s):
PNNL-25577 Rev. 0; RPT-SLAW-003 Rev A
830403000; TRN: US1700816
DOE Contract Number:
AC05-76RL01830
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE WASTES FROM NUCLEAR FACILITIES; WASTE FORMS; GETTERS; TANKS; TEMPERATURE RANGE 0273-0400 K; PERFORMANCE; HANFORD RESERVATION; LOW-LEVEL RADIOACTIVE WASTES; RADIOACTIVE WASTE PROCESSING; DIFFUSION; GROUTING; SIMULATION; REMEDIAL ACTION; IMMOBILIZATION

Citation Formats

Asmussen, Robert M., Lawter, Amanda R., Stephenson, John R., Bowden, Mark E., Washton, Nancy M., Neeway, James J., Du, Yingge, Pearce, Carolyn I., Clayton, Ray E., Saslow, Sarah A., Buck, Edgar C., Cordova, Elsa, and Qafoku, Nikolla. Getter Incorporation into Cast Stone and Solid State Characterizations. United States: N. p., 2016. Web. doi:10.2172/1334894.
Asmussen, Robert M., Lawter, Amanda R., Stephenson, John R., Bowden, Mark E., Washton, Nancy M., Neeway, James J., Du, Yingge, Pearce, Carolyn I., Clayton, Ray E., Saslow, Sarah A., Buck, Edgar C., Cordova, Elsa, & Qafoku, Nikolla. Getter Incorporation into Cast Stone and Solid State Characterizations. United States. doi:10.2172/1334894.
Asmussen, Robert M., Lawter, Amanda R., Stephenson, John R., Bowden, Mark E., Washton, Nancy M., Neeway, James J., Du, Yingge, Pearce, Carolyn I., Clayton, Ray E., Saslow, Sarah A., Buck, Edgar C., Cordova, Elsa, and Qafoku, Nikolla. 2016. "Getter Incorporation into Cast Stone and Solid State Characterizations". United States. doi:10.2172/1334894. https://www.osti.gov/servlets/purl/1334894.
@article{osti_1334894,
title = {Getter Incorporation into Cast Stone and Solid State Characterizations},
author = {Asmussen, Robert M. and Lawter, Amanda R. and Stephenson, John R. and Bowden, Mark E. and Washton, Nancy M. and Neeway, James J. and Du, Yingge and Pearce, Carolyn I. and Clayton, Ray E. and Saslow, Sarah A. and Buck, Edgar C. and Cordova, Elsa and Qafoku, Nikolla},
abstractNote = {Washington River Protection Solutions (WRPS) is collecting relevant available data on waste forms for use as a supplemental immobilization technology, to provide the additional capacity needed to treat low-activity waste (LAW) in Hanford Site tanks and complete the tank waste cleanup mission in a timely and cost-effective manner. One candidate supplemental waste form, fabricated using a low-temperature process, is a cementitious grout called Cast Stone. Cast Stone has been under investigation for this application at Pacific Northwest National Laboratory (PNNL) since initial screening tests in FY13. This report is the culmination of work to lower the diffusivities of Tc and I from Cast Stone using getters. Getters are compounds added to a system designed to selectively sequester a species of interest to provide increased stability to the species. The work contained within this report is related to waste form development and testing, and does not directly support the 2017 integrated disposal facility (IDF) performance assessment. However, this work contains valuable information which may be used in performance assessment maintenance past FY17, and in future waste form development. This report on performance characterization of Tc and I getters in Cast Stone fabricated with simulated LAW covers several areas of interest and major findings to WRPS: investigating performance of potassium metal sulfide (KMS-2-SS) and tin (II) apatite (Sn-A) as Tc getters when incorporated into Cast Stone; investigating performance of silver exchanged zeolite (Ag-Z) and argentite (Arg) as I getters when incorporated into Cast Stone; utilizing sequential addition of Tc and I getters to overcome any deleterious interactions between the getters in solution; determining, for the first time, Tc distribution within the cured Cast Stone and its evolution during leaching; and performing solid state characterization of getters and Cast Stone samples to support leach test findings and develop a mechanistic understanding of the processes that control Tc and I release into solution.},
doi = {10.2172/1334894},
journal = {},
number = ,
volume = ,
place = {United States},
year = 2016,
month = 9
}

Technical Report:

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  • This report describes the results from the solid phase characterization of six Cast Stone monoliths from the extended leach tests recently reported on (Serne et al. 2016),that were selected for characterization using multiple state-of-the-art approaches. The Cast Stone samples investigated were leached for > 590 d in the EPA Method 1315 test then archived for > 390 d in their final leachate. After reporting the long term leach behavior of the monoliths (containing radioactive 99Tc and stable 127I spikes and for original Westsik et al. 2013 fabricated monoliths, 238U), it was suggested that physical changes to the waste forms andmore » a depleting inventory of contaminants of potential concern may mean that effective diffusivity calculations past 63 d should not be used to accurately represent long-term waste form behavior. These novel investigations, in both length of leaching time and application of solid state techniques, provide an initial arsenal of techniques which can be utilized to perform such Cast Stone solid phase characterization work, which in turn can support upcoming performance assessment maintenance. The work was performed at Pacific Northwest National Laboratory (PNNL) for Washington River Protection Solutions (WRPS) to characterize several properties of the long- term leached Cast Stone monolith samples.« less
  • Laboratory testing and technical evaluation activities on Containerized Cast Stone (CCS) were conducted under the Scope of Work (SOW) contained in CH2M HILL Hanford Group, Inc. (CHG) Contract No. 18548 (CHG 2003a). This report presents the results of testing and demonstration activities discussed in SOW Section 3.1, Task I--''Process Development Testing'', and described in greater detail in the ''Containerized Grout--Phase I Testing and Demonstration Plan'' (CHG, 2003b). CHG (2003b) divided the CCS testing and evaluation activities into six categories, as follows: (1) A short set of tests with simulant to select a preferred dry reagent formulation (DRF), determine allowable liquidmore » addition levels, and confirm the Part 2 test matrix. (2) Waste form performance testing on cast stone made from the preferred DRF and a backup DRF, as selected in Part I, and using low activity waste (LAW) simulant. (3) Waste form performance testing on cast stone made from the preferred DRF using radioactive LAW. (4) Waste form validation testing on a selected nominal cast stone formulation using the preferred DRF and LAW simulant. (5) Engineering evaluations of explosive/toxic gas evolution, including hydrogen, from the cast stone product. (6) Technetium ''getter'' testing with cast stone made with LAW simulant and with radioactive LAW. In addition, nitrate leaching observations were drawn from nitrate leachability data obtained in the course of the Parts 2 and 3 waste form performance testing. The nitrate leachability index results are presented along with other data from the applicable activity categories.« less
  • PNNL is conducting screening tests on the candidate waste forms to provide a basis for comparison and to resolve the formulation and data needs identified in the literature review. This report documents the screening test results on the Cast Stone cementitious waste form and the Geopolymer waste form. Test results suggest that both the Cast Stone and Geopolymer appear to be viable waste forms for the solidification of the secondary liquid wastes to be treated in the ETF. The diffusivity for technetium from the Cast Stone monoliths was in the range of 1.2 × 10-11 to 2.3 × 10-13 cm2/smore » during the 63 days of testing. The diffusivity for technetium from the Geopolymer was in the range of 1.7 × 10-10 to 3.8 × 10-12 cm2/s through the 63 days of the test. These values compare with a target of 1 × 10-9 cm2/s or less. The Geopolymer continues to show some fabrication issues with the diffusivities ranging from 1.7 × 10-10 to 3.8 × 10-12 cm2/s for the better-performing batch to from 1.2 × 10-9 to 1.8 × 10-11 cm2/s for the poorer-performing batch. In the future more comprehensive and longer term performance testing will be conducted, to further evaluate whether or not these waste forms will meet the regulation and performance criteria needed to cost-effectively dispose of secondary wastes.« less
  • To support the selection of a waste form for the liquid secondary wastes from WTP, Washington River Protection Solutions has initiated secondary-waste-form testing work at Pacific Northwest National Laboratory (PNNL). In anticipation of a down-selection process for a waste form for the Solidification Treatment Unit to be added to the ETF, PNNL is conducting tests on four candidate waste forms to evaluate their ability to meet potential waste acceptance criteria for immobilized secondary wastes that would be placed in the IDF. All three waste forms demonstrated compressive strengths above the minimum 3.45 MPa (500 psi) set as a target formore » cement-based waste forms. Further, none of the waste forms showed any significant degradation in compressive strength after undergoing thermal cycling (30 cycles in a 10 day period) between -40 C and 60 C or water immersion for 90 days. The three leach test methods are intended to measure the diffusion rates of contaminants from the waste forms. Results are reported in terms of diffusion coefficients and a leachability index (LI) calculated based on the diffusion coefficients. A smaller diffusion coefficient and a larger LI are desired. The NRC, in its Waste Form Technical Position (NRC 1991), provides recommendations and guidance regarding methods to demonstrate waste stability for land disposal of radioactive waste. Included is a recommendation to conduct leach tests using the ANS 16.1 method. The resulting leachability index (LI) should be greater than 6.0. For Hanford secondary wastes, the LI > 6.0 criterion applies to sodium leached from the waste form. For technetium and iodine, higher targets of LI > 9 for Tc and LI > 11 for iodine have been set based on early waste-disposal risk and performance assessment analyses. The results of these three leach tests conducted for a total time between 11days (ASTM C1308) to 90 days (ANS 16.1) showed: (1) Technetium diffusivity: ANSI/ANS 16.1, ASTM C1308, and EPA 1315 tests indicated that all the waste forms had leachability indices better than the target LI > 9 for technetium; (2) Rhenium diffusivity: Cast Stone 2M specimens, when tested using EPA 1315 protocol, had leachability indices better than the target LI > 9 for technetium based on rhenium as a surrogate for technetium. All other waste forms tested by ANSI/ANS 16.1, ASTM C1308, and EPA 1315 test methods had leachability indices that were below the target LI > 9 for Tc based on rhenium release. These studies indicated that use of Re(VII) as a surrogate for 99Tc(VII) in low temperature secondary waste forms containing reductants will provide overestimated diffusivity values for 99Tc. Therefore, it is not appropriate to use Re as a surrogate 99Tc in future low temperature waste form studies. (3) Iodine diffusivity: ANSI/ANS 16.1, ASTM C1308, and EPA 1315 tests indicated that the three waste forms had leachability indices that were below the target LI > 11 for iodine. Therefore, it may be necessary to use a more effective sequestering material than silver zeolite used in two of the waste forms (Ceramicrete and DuraLith); (4) Sodium diffusivity: All the waste form specimens tested by the three leach methods (ANSI/ANS 16.1, ASTM C1308, and EPA 1315) exceeded the target LI value of 6; (5) All three leach methods (ANS 16.1, ASTM C1308 and EPA 1315) provided similar 99Tc diffusivity values for both short-time transient diffusivity effects as well as long-term ({approx}90 days) steady diffusivity from each of the three tested waste forms (Cast Stone 2M, Ceramicrete and DuraLith). Therefore, any one of the three methods can be used to determine the contaminant diffusivities from a selected waste form.« less