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Title: ANALYSIS OF SAMPLES FROM TANK 6F CHEMICAL CLEANING

Abstract

Savannah River Remediation (SRR) is preparing Tank 6F for closure. The first step in preparing the tank for closure is mechanical sludge removal. In mechanical sludge removal, personnel add liquid (e.g., inhibited water or supernate salt solution) to the tank to form a slurry. They mix the liquid and sludge with pumps, and transfer the slurry to another tank for further processing. Mechanical sludge removal effectively removes the bulk of the sludge from a tank, but is not able to remove all of the sludge. In Tank 6F, SRR estimated a sludge heel of 5,984 gallons remained after mechanical sludge removal. To remove this sludge heel, SRR performed chemical cleaning. The chemical cleaning included two oxalic acid strikes, a spray wash, and a water wash. SRR conducted the first oxalic acid strike as follows. Personnel added 110,830 gallons of 8 wt % oxalic acid to Tank 6F and mixed the contents of Tank 6F with two submersible mixer pumps (SMPs) for approximately four days. Following the mixing, they transferred 115,903 gallons of Tank 6F material to Tank 7F. The SMPs were operating when the transfer started and were shut down approximately five hours after the transfer started. SRR collected amore » sample of the liquid from Tank 6F and submitted it to SRNL for analysis. Mapping of the tank following the transfer indicated that 2,400 gallons of solids remained in the tank. SRR conducted the second oxalic acid strike as follows. Personnel added 28,881 gallons of 8 wt % oxalic acid to Tank 6F. Following the acid addition, they visually inspected the tank and transferred 32,247 gallons of Tank 6F material to Tank 7F. SRR collected a sample of the liquid from Tank 6F and submitted it to SRNL for analysis. Mapping of the tank following the transfer indicated that 3,248 gallons of solids remained in the tank. Following the oxalic acid strikes, SRR performed Spray Washing with oxalic acid to remove waste collected on internal structures, cooling coils, tank top internals, and tank walls. The Acid Spray Wash was followed by a Water Spray Wash to remove oxalic acid from the tank internals. SRR conducted the Spray Wash as follows. Personnel added 4,802 gallons of 8 wt % oxalic acid to Tank 6F through the spray mast installed in Riser 2, added 4,875 gallons of oxalic acid through Riser 7, added 5,000 gallons of deionized water into the tank via Riser 2, and 5,000 gallons of deionized water into the tank via Riser 7. Following the Spray Wash, they visually inspected the tank and transferred 22,430 gallons of Tank 6F material to Tank 7F. SRR collected a sample of the liquid from Tank 6F and submitted it to SRNL for analysis. Following the Spray Wash and transfer, Savannah River Site (SRS) added 113,935 gallons of well water to Tank 6F. They mixed the tank contents with a single SMP and transferred 112,699 gallons from Tank 6F to Tank 7F. SRR collected a sample of the liquid from Tank 6F and submitted to SRNL for analysis. Mapping of the tank following the transfer indicated that 3,488 gallons of solids remained in the tank. Following the Water Wash, SRR personnel collected a solid sample and submitted it to SRNL for analysis to assess the effectiveness of the chemical cleaning and to provide a preliminary indication of the composition of the material remaining in the tank.« less

Authors:
;
Publication Date:
Research Org.:
SRS
Sponsoring Org.:
USDOE
OSTI Identifier:
1009567
Report Number(s):
SRNL-STI-2009-00493
TRN: US1101555
DOE Contract Number:
DE-AC09-08SR22470
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
12 MANAGEMENT OF RADIOACTIVE WASTES, AND NON-RADIOACTIVE WASTES FROM NUCLEAR FACILITIES; STORAGE FACILITIES; WASTE RETRIEVAL; SLUDGES; SLURRIES; CLEANING; OXALIC ACID; SAVANNAH RIVER PLANT; WASHING; SAMPLING; CHEMICAL COMPOSITION; RESIDUES

Citation Formats

Poirier, M., and Fink, S. ANALYSIS OF SAMPLES FROM TANK 6F CHEMICAL CLEANING. United States: N. p., 2010. Web. doi:10.2172/1009567.
Poirier, M., & Fink, S. ANALYSIS OF SAMPLES FROM TANK 6F CHEMICAL CLEANING. United States. doi:10.2172/1009567.
Poirier, M., and Fink, S. Tue . "ANALYSIS OF SAMPLES FROM TANK 6F CHEMICAL CLEANING". United States. doi:10.2172/1009567. https://www.osti.gov/servlets/purl/1009567.
@article{osti_1009567,
title = {ANALYSIS OF SAMPLES FROM TANK 6F CHEMICAL CLEANING},
author = {Poirier, M. and Fink, S.},
abstractNote = {Savannah River Remediation (SRR) is preparing Tank 6F for closure. The first step in preparing the tank for closure is mechanical sludge removal. In mechanical sludge removal, personnel add liquid (e.g., inhibited water or supernate salt solution) to the tank to form a slurry. They mix the liquid and sludge with pumps, and transfer the slurry to another tank for further processing. Mechanical sludge removal effectively removes the bulk of the sludge from a tank, but is not able to remove all of the sludge. In Tank 6F, SRR estimated a sludge heel of 5,984 gallons remained after mechanical sludge removal. To remove this sludge heel, SRR performed chemical cleaning. The chemical cleaning included two oxalic acid strikes, a spray wash, and a water wash. SRR conducted the first oxalic acid strike as follows. Personnel added 110,830 gallons of 8 wt % oxalic acid to Tank 6F and mixed the contents of Tank 6F with two submersible mixer pumps (SMPs) for approximately four days. Following the mixing, they transferred 115,903 gallons of Tank 6F material to Tank 7F. The SMPs were operating when the transfer started and were shut down approximately five hours after the transfer started. SRR collected a sample of the liquid from Tank 6F and submitted it to SRNL for analysis. Mapping of the tank following the transfer indicated that 2,400 gallons of solids remained in the tank. SRR conducted the second oxalic acid strike as follows. Personnel added 28,881 gallons of 8 wt % oxalic acid to Tank 6F. Following the acid addition, they visually inspected the tank and transferred 32,247 gallons of Tank 6F material to Tank 7F. SRR collected a sample of the liquid from Tank 6F and submitted it to SRNL for analysis. Mapping of the tank following the transfer indicated that 3,248 gallons of solids remained in the tank. Following the oxalic acid strikes, SRR performed Spray Washing with oxalic acid to remove waste collected on internal structures, cooling coils, tank top internals, and tank walls. The Acid Spray Wash was followed by a Water Spray Wash to remove oxalic acid from the tank internals. SRR conducted the Spray Wash as follows. Personnel added 4,802 gallons of 8 wt % oxalic acid to Tank 6F through the spray mast installed in Riser 2, added 4,875 gallons of oxalic acid through Riser 7, added 5,000 gallons of deionized water into the tank via Riser 2, and 5,000 gallons of deionized water into the tank via Riser 7. Following the Spray Wash, they visually inspected the tank and transferred 22,430 gallons of Tank 6F material to Tank 7F. SRR collected a sample of the liquid from Tank 6F and submitted it to SRNL for analysis. Following the Spray Wash and transfer, Savannah River Site (SRS) added 113,935 gallons of well water to Tank 6F. They mixed the tank contents with a single SMP and transferred 112,699 gallons from Tank 6F to Tank 7F. SRR collected a sample of the liquid from Tank 6F and submitted to SRNL for analysis. Mapping of the tank following the transfer indicated that 3,488 gallons of solids remained in the tank. Following the Water Wash, SRR personnel collected a solid sample and submitted it to SRNL for analysis to assess the effectiveness of the chemical cleaning and to provide a preliminary indication of the composition of the material remaining in the tank.},
doi = {10.2172/1009567},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Tue Feb 02 00:00:00 EST 2010},
month = {Tue Feb 02 00:00:00 EST 2010}
}

Technical Report:

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  • Following chemical cleaning, a solid sample was collected and submitted to Savannah River National Laboratory (SRNL) for analysis. SRNL analyzed this sample by X-ray Diffraction (XRD) and scanning electron microscopy (SEM) to determine the composition of the solids remaining in Tank 6F and to assess the effectiveness of the chemical cleaning process.
  • The Savannah River Site (SRS) is preparing Tank 5F for closure. The first step in preparing the tank for closure is mechanical sludge removal. Following mechanical sludge removal, SRS performed chemical cleaning with oxalic acid to remove the sludge heel. Personnel are currently assessing the effectiveness of the chemical cleaning. SRS personnel collected liquid samples during chemical cleaning and submitted them to Savannah River National Laboratory (SRNL) for analysis. Following chemical cleaning, they collected a solid sample (also known as 'process sample') and submitted it to SRNL for analysis. The authors analyzed these samples to assess the effectiveness of themore » chemical cleaning process. The conclusions from this work are: (1) With the exception of iron, the dissolution of sludge components from Tank 5F agreed with results from the actual waste demonstration performed in 2007. The fraction of iron removed from Tank 5F by chemical cleaning was significantly less than the fraction removed in the SRNL demonstrations. The likely cause of this difference is the high pH following the first oxalic acid strike. (2) Most of the sludge mass remaining in the tank is iron and nickel. (3) The remaining sludge contains approximately 26 kg of barium, 37 kg of chromium, and 37 kg of mercury. (4) Most of the radioactivity remaining in the residual material is beta emitters and {sup 90}Sr. (5) The chemical cleaning removed more than {approx} 90% of the uranium isotopes and {sup 137}Cs. (6) The chemical cleaning removed {approx} 70% of the neptunium, {approx} 83% of the {sup 90}Sr, and {approx} 21% of the {sup 60}Co. (7) The chemical cleaning removed less than 10% of the plutonium, americium, and curium isotopes. (8) The chemical cleaning removed more than 90% of the aluminium, calcium, and sodium from the tank. (9) The cleaning operations removed 61% of lithium, 88% of non-radioactive strontium, and 65% of zirconium. The {sup 90}Sr and non-radioactive strontium were measured by different methods, and the differences in the fraction removed are not statistically significant. (10) Chemical cleaning removed 10-50% of the barium, chromium, iron, magnesium, manganese, and silicon. (11) Chemical cleaning removed only {approx}1% of the nickel.« less
  • The Savannah River Remediation (SRR) is preparing Tank 6F for closure. The first step in preparing the tank for closure is mechanical sludge removal. Following mechanical sludge removal, SRS performed chemical cleaning with oxalic acid to remove the sludge heel. Personnel are currently assessing the effectiveness of the chemical cleaning to determine whether the tank is ready for closure. SRR personnel collected liquid samples during chemical cleaning and submitted them to Savannah River National Laboratory (SRNL) for analysis. Following chemical cleaning, they collected a solid sample (also known as 'process sample') and submitted it to SRNL for analysis. The authorsmore » analyzed these samples to assess the effectiveness of the chemical cleaning process. Analysis of the anions showed the measured oxalate removed from Tank 6F to be approximately 50% of the amount added in the oxalic acid. To close the oxalate mass balance, the author collected solid samples, leached them with nitric acid, and measured the concentration of cations and anions in the leachate. Some conclusions from this work are: (1) Approximately 65% of the oxalate added as oxalic acid was removed with the decanted liquid. (2) Approximately 1% of the oxalate (added to the tank as oxalic acid) formed precipitates with compounds such as nickel, manganese, sodium, and iron (II), and was dissolved with nitric acid. (3) As much as 30% of the oxalate may have decomposed forming carbon dioxide. The balance does not fully account for all the oxalate added. The offset represents the combined uncertainty in the analyses and sampling.« less
  • The Savannah River National Laboratory (SRNL) was requested by Savannah River Remediation (SRR) to provide sample preparation and analysis of the Tank 6F final characterization samples to determine the residual tank inventory prior to grouting. Fourteen residual Tank 6F solid samples from three areas on the floor of the tank were collected and delivered to SRNL between May and August 2011. These Tank 6F samples were homogenized and combined into three composite samples based on a proportion compositing scheme and the resulting composite samples were analyzed for radiological, chemical and elemental components. Additional measurements performed on the Tank 6F compositemore » samples include bulk density and water leaching of the solids to account for water soluble components. The composite Tank 6F samples were analyzed and the data reported in triplicate. Sufficient quality assurance standards and blanks were utilized to demonstrate adequate characterization of the Tank 6F samples. The main evaluation criteria were target detection limits specified in the technical task request document. While many of the target detection limits were met for the species characterized for Tank 6F some were not met. In a few cases, the relatively high levels of radioactive species of the same element or a chemically similar element precluded the ability to measure some isotopes to low levels. The isotopes whose detection limits were not met in all cases included Sn-126, Sb-126, Sb-126m, Eu-152, Cm-243 and Cf-249. SRNL, in conjunction with the customer, reviewed all of these cases and determined that the impacts of not meeting the target detection limits were acceptable. Based on the analyses of variance (ANOVA) for the inorganic constituents of Tank 6F, all the inorganic constituents displayed heterogeneity. The inorganic results demonstrated consistent differences across the composite samples: lowest concentrations for Composite Sample 1, intermediate-valued concentrations for Composite Sample 2, and highest concentrations for Composite Sample 3. The Hg and Mo results suggest possible measurement outliers. However, the magnitudes of the differences between the Hg 95% upper confidence limit (UCL95) results with and without the outlier and the magnitudes of the differences between the Mo UCL95 results with and without the outlier do not appear to have practical significance. It is recommended to remove the potential measurement outliers. Doing so is conservative in the sense of producing a higher UCL95 for Hg and Mo than if the potential outliers were included in the calculations. In contrast to the inorganic results, most of the radionuclides did not demonstrate heterogeneity among the three Tank 6F composite sample characterization results.« less
  • The Savannah River National Laboratory (SRNL) was requested by Savannah River Remediation (SRR) to provide sample preparation and analysis of the Tank 6F final characterization samples to determine the residual tank inventory prior to grouting. Fourteen residual Tank 6F solid samples from three areas on the floor of the tank were collected and delivered to SRNL between May and August 2011. These Tank 6F samples were homogenized and combined into three composite samples based on a proportion compositing scheme and the resulting composite samples were analyzed for radiological, chemical and elemental components. Additional measurements performed on the Tank 6F compositemore » samples include bulk density and water leaching of the solids to account for water soluble components. The composite Tank 6F samples were analyzed and the data reported in triplicate. Sufficient quality assurance standards and blanks were utilized to demonstrate adequate characterization of the Tank 6F samples. The main evaluation criteria were target detection limits specified in the technical task request document. While many of the target detection limits were met for the species characterized for Tank 6F some were not met. In a few cases, the relatively high levels of radioactive species of the same element or a chemically similar element precluded the ability to measure some isotopes to low levels. The isotopes whose detection limits were not met in all cases included Sn-126, Sb-126, Sb-126m, Eu-152, Cm-243 and Cf-249. SRNL, in conjunction with the customer, reviewed all of these cases and determined that the impacts of not meeting the target detection limits were acceptable. Based on the analyses of variance (ANOVA) for the inorganic constituents of Tank 6F, all the inorganic constituents displayed heterogeneity. The inorganic results demonstrated consistent differences across the composite samples: lowest concentrations for Composite Sample 1, intermediate-valued concentrations for Composite Sample 2, and highest concentrations for Composite Sample 3. The Hg and Mo results suggest possible measurement outliers. However, the magnitudes of the differences between the Hg 95% upper confidence limit (UCL95) results with and without the outlier and the magnitudes of the differences between the Mo UCL95 results with and without the outlier do not appear to have practical significance. It is recommended to remove the potential measurement outliers. Doing so is conservative in the sense of producing a higher UCL95 for Hg and Mo than if the potential outliers were included in the calculations. In contrast to the inorganic results, most of the radionuclides did not demonstrate heterogeneity among the three Tank 6F composite sample characterization results.« less