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Title: STATISTICAL REVIEW OF CESIUM CARBONATE FUSION MEASUREMENTS OF ARCHIVED GLASS SAMPLES FROM THE DWPF PROCESS

Abstract

This technical report provides a statistical review of measurements that the Defense Waste Processing Facility (DWPF) Laboratory (Lab) generated by Inductively-Coupled Plasma--Atomic Emission Spectroscopy (ICP-AES) for samples of archived Slurry Mix Evaporator (SME) glass that were prepared using a cesium carbonate (Cs{sub 2}CO{sub 3}) fusion dissolution method. Measurements were generated by both of the Lab's ICPs, which are designated as M-13 and M-14. Comparisons between the two ICPs suggest that for the ARG-1 measurements the M-14 provided lower (on average) concentration measurements for about 13 of the 16 elements reported by DWPF with Cr, Mn, Ni, and Zr being statistically lower (at a 5% significance level) for the ARG-1 samples. One of the three exceptions is Li, for which the M-14 yielded (on average) higher concentration measurements than the M-13. For the SME samples, the M-14 and M-13 measurements had statistically different (at the 5% significance level) means for B, Ca, Cr, Cu, Fe, Li, Mg, Mn, Na, Ni, Si, Ti, U, and Zr with the M-14 being lower than the M-13 for all of these elements except for Li. For the screened SME samples, statistically significant (at the 5% level) differences between the means of the Cs{sub 2}CO{sub 3}more » and prototypic preparations are seen for Ca (Cs{sub 2}CO{sub 3} higher for both ICPs), Cr (Cs{sub 2}CO{sub 3} higher for both ICPs), Cu (Cs{sub 2}CO{sub 3} higher for M-13), K (Cs{sub 2}CO{sub 3} higher for M-13), Mn (Cs{sub 2}CO{sub 3} lower for M-14), Ni (Cs{sub 2}CO{sub 3} lower for M-14), Si (Cs{sub 2}CO{sub 3} lower for M-14), Ti (Cs{sub 2}CO{sub 3} higher for M-13), U (Cs{sub 2}CO{sub 3} higher for both ICPs), and Zr (Cs{sub 2}CO{sub 3} lower for M-14). The Cs{sub 2}CO{sub 3} fusion method provided elemental of glass samples made from SME batches that were statistically comparable to the DWPF prototypic dissolution methods when the Cs{sub 2}CO{sub 3} solutions were analyzed by the M-13. However, when the same solutions were analyzed with the M-15, the elemental analyses from the Cs{sub 2}CO{sub 3} method were slightly lower and more prone to fail the 95% sum of oxides criterion imposed by DWPF's Product Composition Control System (PCCS). The Cs{sub 2}CO{sub 3} fusion method dissolutions also provided slightly lower waste loading values than the prototypic dissolutions because of slightly higher lithium values when the M-14 was used. In essence, subtle differences in the analyses form the M-13 and M-14 ICPs make it difficult to assess the viability of the Cs{sub 2}CO{sub 3} fusion method to replace the prototypic dissolution methods. The DWFP Laboratory should investigate the causes of these subtle differences between the M-13 and M-14 ICPs as the effort to employ the Cs{sub 2}CO{sub 3} fusion method for SME elemental analyses continues.« less

Authors:
Publication Date:
Research Org.:
SRS
Sponsoring Org.:
USDOE
OSTI Identifier:
891683
Report Number(s):
WSRC-STI-2006-00069
TRN: US0605437
DOE Contract Number:
DE-AC09-96SR18500
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
12 MANAGEMENT OF RADIOACTIVE WASTES, AND NON-RADIOACTIVE WASTES FROM NUCLEAR FACILITIES; CESIUM CARBONATES; DISSOLUTION; GLASS; RADIOACTIVE WASTE PROCESSING; VITRIFICATION; WASTE FORMS; MULTI-ELEMENT ANALYSIS; CHEMICAL COMPOSITION

Citation Formats

Edwards, T. STATISTICAL REVIEW OF CESIUM CARBONATE FUSION MEASUREMENTS OF ARCHIVED GLASS SAMPLES FROM THE DWPF PROCESS. United States: N. p., 2006. Web. doi:10.2172/891683.
Edwards, T. STATISTICAL REVIEW OF CESIUM CARBONATE FUSION MEASUREMENTS OF ARCHIVED GLASS SAMPLES FROM THE DWPF PROCESS. United States. doi:10.2172/891683.
Edwards, T. Mon . "STATISTICAL REVIEW OF CESIUM CARBONATE FUSION MEASUREMENTS OF ARCHIVED GLASS SAMPLES FROM THE DWPF PROCESS". United States. doi:10.2172/891683. https://www.osti.gov/servlets/purl/891683.
@article{osti_891683,
title = {STATISTICAL REVIEW OF CESIUM CARBONATE FUSION MEASUREMENTS OF ARCHIVED GLASS SAMPLES FROM THE DWPF PROCESS},
author = {Edwards, T},
abstractNote = {This technical report provides a statistical review of measurements that the Defense Waste Processing Facility (DWPF) Laboratory (Lab) generated by Inductively-Coupled Plasma--Atomic Emission Spectroscopy (ICP-AES) for samples of archived Slurry Mix Evaporator (SME) glass that were prepared using a cesium carbonate (Cs{sub 2}CO{sub 3}) fusion dissolution method. Measurements were generated by both of the Lab's ICPs, which are designated as M-13 and M-14. Comparisons between the two ICPs suggest that for the ARG-1 measurements the M-14 provided lower (on average) concentration measurements for about 13 of the 16 elements reported by DWPF with Cr, Mn, Ni, and Zr being statistically lower (at a 5% significance level) for the ARG-1 samples. One of the three exceptions is Li, for which the M-14 yielded (on average) higher concentration measurements than the M-13. For the SME samples, the M-14 and M-13 measurements had statistically different (at the 5% significance level) means for B, Ca, Cr, Cu, Fe, Li, Mg, Mn, Na, Ni, Si, Ti, U, and Zr with the M-14 being lower than the M-13 for all of these elements except for Li. For the screened SME samples, statistically significant (at the 5% level) differences between the means of the Cs{sub 2}CO{sub 3} and prototypic preparations are seen for Ca (Cs{sub 2}CO{sub 3} higher for both ICPs), Cr (Cs{sub 2}CO{sub 3} higher for both ICPs), Cu (Cs{sub 2}CO{sub 3} higher for M-13), K (Cs{sub 2}CO{sub 3} higher for M-13), Mn (Cs{sub 2}CO{sub 3} lower for M-14), Ni (Cs{sub 2}CO{sub 3} lower for M-14), Si (Cs{sub 2}CO{sub 3} lower for M-14), Ti (Cs{sub 2}CO{sub 3} higher for M-13), U (Cs{sub 2}CO{sub 3} higher for both ICPs), and Zr (Cs{sub 2}CO{sub 3} lower for M-14). The Cs{sub 2}CO{sub 3} fusion method provided elemental of glass samples made from SME batches that were statistically comparable to the DWPF prototypic dissolution methods when the Cs{sub 2}CO{sub 3} solutions were analyzed by the M-13. However, when the same solutions were analyzed with the M-15, the elemental analyses from the Cs{sub 2}CO{sub 3} method were slightly lower and more prone to fail the 95% sum of oxides criterion imposed by DWPF's Product Composition Control System (PCCS). The Cs{sub 2}CO{sub 3} fusion method dissolutions also provided slightly lower waste loading values than the prototypic dissolutions because of slightly higher lithium values when the M-14 was used. In essence, subtle differences in the analyses form the M-13 and M-14 ICPs make it difficult to assess the viability of the Cs{sub 2}CO{sub 3} fusion method to replace the prototypic dissolution methods. The DWFP Laboratory should investigate the causes of these subtle differences between the M-13 and M-14 ICPs as the effort to employ the Cs{sub 2}CO{sub 3} fusion method for SME elemental analyses continues.},
doi = {10.2172/891683},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Mon Jul 31 00:00:00 EDT 2006},
month = {Mon Jul 31 00:00:00 EDT 2006}
}

Technical Report:

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  • The measurements derived from samples taken during the processing of batches 19 through 30 at the Defense Waste Processing Facility (DWPF) affords an opportunity for review and comparisons. This report has looked at some of the statistics from these data. Only the data reported by the DWPF lab (that is, the data provided by the lab as representative of the samples taken) are available for this analysis. In some cases, the sample results reported may be a subset of the sample results generated by the analytical procedures. A thorough assessment of the DWPF lab's analytical procedures would require the completemore » set of data. Thus, the statistics reported here, specifically, as they relate to analytical uncertainties, are limited to the reported data for these samples, A fell for the consistency of the incoming slurry is the estimation of the components of variation for the Sludge Receipt and Adjustment Tank (SRAT) receipts. In general, for all of the vessels, the data from batches after 21 show smaller batch-to-batch variation than the data from all the batches. The relative contributions of batch-to-batch versus residual, which includes analytical, are presented in these analyses.« less
  • The measurements derived from samples taken during the processing of macro-batch 1 (MB1) at the Defense Waste Processing Facility (DWPF) have been reviewed and compared in this report. Batches 22 through 93 were the focal point of this study. Statistical control charts were developed for each analyte for each vessel to identify influential or exceptional results in the variation, central tendency, or both for the measurements. These charts should serve as a basis for observing the (expected) impact of some decisions made during the processing of this macro-batch.
  • The measurements derived from samples taken during the processing of batches 19 through 30 at the Defense Waste Processing Facility (DWPF) affords an opportunity for review and comparisons. This report has looked at some of the statistics from these data. Only the data reported by the DWPF lab (that is, the data provided by the lab as representative of the samples taken) are available for this analysis. In some cases, the sample results reported may be a subset of the sample results generated by the analytical procedures. A thorough assessment of the DWPF lab's analytical procedures would require the completemore » set of data. Thus, the statistics reported here, specifically, as they relate to analytical uncertainties, are limited to the reported data for these samples, A fell for the consistency of the incoming slurry is the estimation of the components of variation for the Sludge Receipt and Adjustment Tank (SRAT) receipts. In general, for all of the vessels, the data from batches after 21 show smaller batch-to-batch variation than the data from all the batches. The relative contributions of batch-to-batch versus residual, which includes analytical, are presented in these analyses.« less
  • Measurements of calibration and bench standards as well as samples of ARG-1 that were performed by the DWPF Lab during the processing of batches 94 through 263 were provided to SCS for review. Three datasets, one associated with each of three preparation methods (Cold Chem, Mixed Acid, and Fusion) were included in the review. The review conducted covered several areas of investigation. Biases in these measurements relative to the reference values for the standards including ARG-1 were estimated and found to be of no practical concern. Percent relative standard deviations for these data also were determined. Sources of variation inmore » the measurements (i.e., batch-to-batch and within process batch) were estimated and compared. An investigation into evidence of instrument drift during a group of measurements representing a prototypical block was conducted for each preparation method using pairs of calibration and bench standards. No evidence of instrument drift at levels of practical concern was seen in these data. Also, the replicates of calibration standards at the beginning of each analytical block were found to be unnecessary. The uncertainties of the measurements, which incorporated biases and precision errors, were computed for the calibration standards, bench standards, and ARG-1. The limits for these uncertainties were compared to the current, LIMS operating limits for the errors in the measurements of these standards. These comparisons may provide opportunities for revising the LIMS limits. Comparisons between MFT and SME results were made for both the Mixed Acid and the Fusion prep methods. There was no evidence of differences (in either bias or precision) between the results for these two tanks for either of the two prep methods.« less
  • In this report, the Statistical Consulting Section (SCS) of the Savannah River National Laboratory (SRNL) provides summaries and comparisons of composition measurements for glass samples that were generated during the processing of batches 300 through 356 at the Defense Waste Processing Facility (DWPF). These analyses, which include measurements of samples from the Sludge Receipt and Adjustment Tank (SRAT) and the Slurry Mix Evaporator (SME) as well as samples of glass standards, were provided to SCS by the DWPF Laboratory (DWPF Lab) of Waste Laboratory Services. The comparisons made by SCS were extensive given that these data allowed for contrasts betweenmore » preparation methods and between the two spectrometers that are currently in use at the DWPF Lab. In addition to general comparisons, specific questions that were posed in the Technical Task Request (TTR) behind this effort were addressed in this report.« less