ML23107A295
| ML23107A295 | |
| Person / Time | |
|---|---|
| Site: | PROJ0734 |
| Issue date: | 12/31/2022 |
| From: | Crawford C, Harry Felsher NRC/NMSS/DDUWP/LLWPB, Savannah River National Lab, US Dept of Energy (DOE) |
| To: | |
| Felsher H | |
| References | |
| SRNL-STI-2022-00526, Rev. 0 | |
| Download: ML23107A295 (22) | |
Text
AU.S.DEPARTMENTOFENERGYNATIONALLAB*SAVANNAHRIVERSITE*AIKEN,SC*USA Results for the July 2022 Semiannual Tank 50 Salt Solution Sample C. L. Crawford December 2022 SRNL-STI-2022-00526, Revision 0
SRNL-STI-2022-00526 Revision 0 ii DISCLAIMER This work was prepared under an agreement with and funded by the U.S. Government. Neither the U.S.
Government or its employees, nor any of its contractors, subcontractors or their employees, makes any express or implied:
- 1. warranty or assumes any legal liability for the accuracy, completeness, or for the use or results of such use of any information, product, or process disclosed; or
- 2. representation that such use or results of such use would not infringe privately owned rights; or
- 3. endorsement or recommendation of any specifically identified commercial product, process, or service.
Any views and opinions of authors expressed in this work do not necessarily state or reflect those of the United States Government, or its contractors, or subcontractors.
Printed in the United States of America Prepared for U.S. Department of Energy
SRNL-STI-2022-00526 Revision 0 iii Keywords: Tank 50, Waste Acceptance Criteria, Saltstone Retention: Permanent Results for the July 2022 Semiannual Tank 50 Salt Solution Sample C. L. Crawford December 2022 Savannah River National Laboratory is operated by Battelle Savannah River Alliance for the U.S. Department of Energy under Contract No. 89303321CEM000080.
CHARLES CRAWFORD (Affiliate)
Digitally signed by CHARLES CRAWFORD (Affiliate)
Date: 2022.12.12 10:51:00 -05'00' JOHN DEKARSKE (Affiliate)
Digitally signed by JOHN DEKARSKE (Affiliate)
Date: 2022.12.12 11:07:03 -05'00' ALEX COZZI (Affiliate)
Digitally signed by ALEX COZZI (Affiliate)
Date: 2022.12.15 10:37:03 -05'00' FRANK PENNEBAKER (Affiliate) Digitally signed by FRANK PENNEBAKER (Affiliate)
Date: 2022.12.19 13:59:24 -05'00' R.M. Hoeppel Digitally signed by R.M. Hoeppel Date: 2023.01.25 22:34:35 -05'00' Cliff Conner Digitally signed by Cliff Conner Date: 2023.01.26 07:51:30 -05'00'
SRNL-STI-2022-00526 Revision 0 v
EXECUTIVE
SUMMARY
In this Technical Report, the chemical and radionuclide contaminant results from the July 2022 Semiannual sample of Tank 50 salt solution are presented in tabulated form. The information from this characterization will be used by Savannah River Mission Completion (SRMC) for the transfer of aqueous waste from Tank 50 to the Saltstone Production Facility (SPF), where the waste will be treated and disposed in the Saltstone Disposal Facility. This Technical Report compares results, where applicable, to SPF Waste Acceptance Criteria (WAC) LIMITS and TARGETS that were established at the time the Tank 50 sample was obtained.1 The chemical and radionuclide contaminant results from the characterization of the July 2022 semiannual sampling of Tank 50 were requested by SRMC personnel via a Task Technical Request (TTR)2 and details of the testing are presented in the Savannah River National Laboratory (SRNL) Task Technical and Quality Assurance Plan (TTQAP).3 This Technical Report is part of Deliverable 2 relating to Task 1 from the SRMC request.2 Data pertaining to the regulatory limits for Resource Conservation and Recovery Act (RCRA) metals per Task 2 from the SRMC request, will be obtained semiannually for the January 2022 and July 2022 Tank 50 samples.
The following facts pertaining to the WAC are drawn from the analytical results provided in this report.
WAC TARGETS and LIMITS were met for all analyzed chemical and radioactive contaminants for which the detection limits are below the WAC TARGETS and LIMITS.1 Nitrosamines were not detected in the Tank 50 salt solution sample above the instrument detection limits of <1 mg/L.
The minimum detection limit (<2.81E-01 pCi/mL) is reported for 94Nb as determined from the minimum detectable activity associated with the radiochemical method used for this radionuclide.
The reported detection limit is above the requested SRMC target minimum detection limit concentration.4 However, the minimum detection limit reported for the July 2022 semiannual Tank 50 sample for 94Nb is lower than the estimated detection limit of 4.38E-01 pCi/mL initially established by SRNL in 2009.5 Thus, per guidance from SRMC,4 SRNL continues to achieve as low as practical detection limits for this radionuclide.
SRNL-STI-2022-00526 Revision 0 vi TABLE OF CONTENTS LIST OF TABLES...................................................................................................................................... vii LIST OF ABBREVIATIONS.................................................................................................................... viii 1.0 Introduction............................................................................................................................................. 1 2.0 Experimental........................................................................................................................................... 1 2.1 Technical............................................................................................................................................. 1 2.2 Quality Assurance............................................................................................................................... 3 3.0 Results and Discussion........................................................................................................................... 3 4.0 Conclusions........................................................................................................................................... 11 5.0 References............................................................................................................................................. 12
SRNL-STI-2022-00526 Revision 0 vii LIST OF TABLES Table 3-1. Chemical Contaminants from July 2022 Semiannual Tank 50 Samples and SPF WAC,.1 LIMITS........................................................................................................................ 5 Table 3-2. Chemical Contaminants from July 2022 Semiannual Tank 50 Samples and SPF WAC,.2 TARGETS.................................................................................................................... 6 Table 3-3. Radionuclide Contaminants from July 2022 Semiannual Tank 50 Samples and SPF WAC,.3 LIMITS........................................................................................................................ 7 Table 3-4. Radionuclide Contaminants from July 2022 Semiannual Tank 50 Samples and SPF WAC,.4 TARGETS.................................................................................................................... 8 Table 3-5. Chemical Contaminants Impacting Saltstone Disposal Unit (SDU) Flammability from July 2022 Semiannual Tank 50 Samples and WAC Table 2 LIMITS and TARGETS.......................................... 9 Table 3-6. Other Organics Impacting SDU Flammability from July 2022 Semiannual Tank 50 Samples and WAC Table 4 Concentrations....................................................................................................... 10 Table 3-7. Processing Constituents from July 2022 Semiannual Tank 50 Samples and WAC Table 5 LIMITS................................................................................................................................................ 10 Table 3-8. Additional Measured Constituents........................................................................................... 11
SRNL-STI-2022-00526 Revision 0 viii LIST OF ABBREVIATIONS CP&C Chemical Processing & Characterization CVAFS Cold Vapor Atomic Fluorescence Spectroscopy DMA Direct Mercury Analyzer EDTA ethylenediaminetetraacetate GC/MS Gas Chromatographic/Mass Spectrometric HDPE high-density polyethylene HPLC High Performance Liquid Chromatography IC Ion Chromatography ICP-AES Inductively Coupled Plasma Atomic Emission Spectroscopy ICP-MS Inductively Coupled Plasma Mass Spectrometry LSC Liquid Scintillation Counting MRL Minimum Reporting Limit NDMA-d6 N-nitrosodimethylamine-d6 P&T-TD-CVAFS Purge & Trap, Thermal Desorption, Cold Vapor Atomic Fluorescence Spectroscopy Pu alpha PHA Plutonium alpha Pulse Height Analysis RCRA Resource Conservation and Recovery Act SDI Salt Disposition Integration SDU Saltstone Disposal Unit SPF Saltstone Production Facility SRMC Savannah River Mission Completion SRNL Savannah River National Laboratory SVOA Semi-Volatile Organic Analysis TIC/TOC Total Inorganic Carbon/Total Organic Carbon TPB tetraphenylborate TTQAP Task Technical and Quality Assurance Plan TTR Technical Task Request VDS Variable Depth Sample VOA Volatile Organic Analysis WAC Waste Acceptance Criteria
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1.0 Introduction Tank 50 aqueous waste is analyzed on a semiannual basis and the results are compared to the Waste Acceptance Criteria (WAC) of the Z-Area Saltstone Production Facility (SPF).1 The information from this characterization will be used by Savannah River Mission Completion (SRMC) for the transfer of aqueous waste from Tank 50 to SPF, where the waste will be treated and disposed in the Saltstone Disposal Facility.
This Technical Report compares results, where applicable, to SPF WAC LIMITS and TARGETS.1 A memorandum reporting the average Cs-137 value and comparison to WAC LIMITS has been previously issued.6 The semiannual Tank 50 analysis is to occur in January and July of each year. A reduced set of analyses will also be obtained on a planned bimonthly basis to occur in March, May, September and November of each year.7 Current planning is to change the reduced set of analyses on a bimonthly basis from Tank 50 sampling to the same reduced set of analyses that will derive from Salt Waste Processing Facility and occur on a quarterly basis.
2.0 Experimental 2.1 Technical The July 2022 semiannual Tank 50 samples [a 200-mL sample obtained 6 below the surface (HTF-50 59) and a 1-L variable depth sample (VDS) obtained 66 from the tank bottom (HTF-50-22-60)] were obtained and received at Savannah River National Laboratory (SRNL) on July 19, 2022.8 The contents of the 1-L slurry in the steel variable depth sampler were initially mixed by recycling some of the slurry using the transfer pump with both ends of the transfer line submerged in the sample. After initial mixing, a 30-mL aliquot and a 15-mL aliquot of the Tank 50 sample were pumped into a Teflon and a glass container, respectively, with zero headspace. These two samples were used for Hg speciation measurement. The remaining contents were then transferred by pumping into two different high-density polyethylene (HDPE) 1-L bottles. The transferred slurry was left to settle in the bottles and no suspended or settled solids were observed during the brief storage in the Shielded Cells. Therefore, no clear supernate was returned to the sampler for rinsing. The entire sample was promptly transferred out of the Shielded Cells on the same day as it was collected from the steel variable depth sampler and placed in a radiochemical hood. The two small zero headspace vials for Hg speciation testing were put in shrouded containers and transferred to storage in a refrigerator. All transfers out of the Shielded Cells were made on the same day as sample collection. After receipt in a radiochemical hood for processing, the 1-L bottles were agitated by hand to thoroughly disperse any extremely limited suspended solids into the supernate. These suspended solids are typically only visible as trace solids at the bottom of the container upon prolonged storage of the material under static conditions. Aliquots of slurry samples were promptly collected with slurry pipettes to minimize settling effects and placed into HDPE bottles. Samples for volatile organic analysis (VOA) and semi-volatile organic analysis (SVOA) were removed from the 200-mL surface sample from within a radiochemical hood and were transferred using glass pipettes into clean amber glass sample vials with Teflon-lined caps. Amber colored glass sample vials were used for the samples that were analyzed for nitrosamines to minimize exposure to light.
Unless otherwise stated, all concentrations presented in the tables (except upper limits) are averages based on analyses of triplicate aliquots of the July 2022 semiannual Tank 50 sample. The 1-sigma standard deviation of each average is also presented. Several of the contaminants were either not detected in the slurry samples or detected at values below the method reporting limit (MRL). For contaminants not detected or detected below the MRL, the result is preceded by a <, which indicates the result is an upper limit based on the sensitivity of the method used to analyze the individual analyte. If only one value out of the triplicate analysis is above the detection limit, then that single value is reported and noted in the tables.
Also, if only two values out of the triplicate analyses are above the detection limit, then the average of those two values is reported and noted in the tables.
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All VOA, SVOA and nitrosamines analyses were performed on the surface sample and all other analyses were performed on the variable depth sample. The VOA method is performed per SRNL Chemical Processing & Characterization (CP&C) Procedure L16.1, ADS-2656.9 This method is based upon a purge-and-trap, Gas Chromatographic/Mass Spectrometric (GC/MS) process that involves dilution of 1 mL of Tank 50 supernate with 4 mL of reagent water. The SVOA method is performed per SRNL CP&C Procedure L16.1, ADS-2657. 10 Both of these methods use discrete standards as detailed in the procedures.9,10 The SVOA method uses organic solvents to extract SVOA analytes that are subsequently measured by GC/MS. A 3 mL dichloromethane (also known as methylene chloride, CH2Cl2) volume is used to initially extract 10 mL of Tank 50 supernate for phenol. The same Tank 50 supernate is then extracted with 2 additional 3-mL volumes of dichloromethane. The dichloromethane extracts are all combined and concentrated to 1 mL before analysis for phenol. Tributyl phosphate is analyzed from a 0.01 mL hexane (C6H14) extract of 10 mL of Tank 50 supernate. Isopar La and Norpar 13 are analyzed from a 2.5 mL hexane extraction of 10 mL of Tank 50 supernate. Nitrosamines are analyzed by a separate SVOA method that uses 2 mL of dichloromethane as extractant and 10 mL of Tank 50 supernate with deuterated N-nitrosodimethylamine-d6 (NDMA-d6) as a standard along with a separate GC/MS analysis methodology.
Data reported for inductively coupled plasma atomic emission spectroscopy (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS) are derived from the digested Tank 50 supernate (1 mL supernate diluted to 50 mL total volume) by the aqua regia method.11 The aqua regia method heats the Tank 50 supernate mixed with a 1:3 mixture of nitric acid/hydrochloric acid for 2 hours2.314815e-5 days <br />5.555556e-4 hours <br />3.306878e-6 weeks <br />7.61e-7 months <br /> in sealed Teflon containers in an oven at 115 ºC. Anion and the ammonium cation analyses are determined from Ion Chromatography (IC). Total Inorganic Carbon/Total Organic Carbon (TIC/TOC) analysis was used to measure the TIC (carbonate) and TOC components. The tetraphenylborate (TPB) anion and ethylenediaminetetraacetate (EDTA) were analyzed using High Performance Liquid Chromatography (HPLC). The IC, TIC/TOC and HPLC methods all used undiluted samples. All the above analyses, excluding VOA and SVOA, used approximately 150 mL of the 1-L variable depth sample. Densities were measured on triplicate samples of the Tank 50 slurry by SRNL CP&C. Total and soluble weight percent solids were determined on quadruplicate portions of the Tank 50 sample, without filtration and with filtration, respectively, using the Weight Percent Solids Determination Using a Furnace or Oven procedure.12 Approximately 630 mL of the VDS were used to determine all the measured radionuclide concentrations in triplicate. Radionuclides reported using the ICP-MS method are converted from a reported mass per volume basis to activity per volume units using the specific activities (Ci/g) reported from the Department of Energy 1996 Integrated Data Base Report.13 The Cs-137 and C-134 radionuclides are determined from gamma spectroscopy. Total beta is measured from a radscreen method using Liquid Scintillation Counting (LSC). The total alpha is measured from the same method after removal of Cs-137 from the sample using ammonium phosphomolybdate. No other radiochemical species in the matrix are removed. This methodology for measuring total alpha concentrations typically results in upper limits rather than minimum detectable activities when other peaks from competing radionuclides, e.g., Sr-90, in the matrix prevent detection of the alpha emitters. Plutonium isotopes (Pu-238, Pu-239 and Pu-240) are determined from a Plutonium alpha Pulse Height Analysis (Pu alpha PHA) method.
Mercury analyses performed at SRNL by CP&C included Total mercury using the Direct Mercury Analyzer (DMA) method 14 and monomethyl mercury and ethyl mercury by Cold Vapor Atomic Fluorescence Spectroscopy (CVAFS).15 Soluble elemental mercury (Hg(0)) was measured by CP&C using a Purge &
Trap, Thermal Desorption, CVAFS (P&T-TD-CVAFS) method.16 A variation of this method was also developed by CP&C to analyze for inorganic mercury (Hg(I/II)).17 Dimethyl mercury was analyzed using a semi-quantitative CP&C VOA method that involves extraction followed by GC/MS.9 The parent sample a Isopar L is a trademark chemical (Isopar' L) manufactured by ExxonMobil. It is a synthetic isoparaffinic hydrocarbon that is manufactured from a petroleum based raw material.
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for all mercury analyses performed at SRNL was obtained from the original Tank 50 sample within two days of sample receipt. As discussed above, the parent Tank 50 sample was obtained in near zero-headspace containers that were immediately refrigerated after removal from the Shielded Cells Facility on the same day of preparation.18 Total mercury, Monomethyl and ethyl mercury are determined from the Tank 50 parent sample obtained in the 30-mL Teflon bottle. All other species are determined from the 15-mL Tank 50 parent stored in the glass bottle. Samples of Tank 50 submitted to SRNL CP&C analytical laboratories for mercury speciation analysis were submitted without dilution. These samples were diluted within the SRNL CP&C analytical laboratories to meet the targeted calibration range of either the DMA instrument for total Hg or the CVAFS instrument for other Hg species and for VOA analysis for dimethyl mercury.
2.2 Quality Assurance Quality Assurance requirements for performing reviews of technical reports and the extent of review are established in manual E7 2.60.19 SRNL documents the extent and type of review using the SRNL Technical Report Design Checklist contained in WSRC-IM-2002-00011, Rev. 2.20 The customer requested that a Functional Classification of Safety Significant apply to this work.2 Thus, a Design Verification technical review was performed via a document review according to the applicable elements detailed in Section 5.3.1 Design Verification by Document Review of E7 2.60.19 Data collection and analysis methods used in this work comply with this requirement as detailed in the TTQAP.3 3.0 Results and Discussion Analyzed nonradionuclide chemical concentrations, their 1-sigma standard deviations and their corresponding WAC LIMITS1 are shown in Table 3-1 that correspond to the Attachment 8.1 LIMITS in the WAC.1 Per the WAC, the LIMITS shown shall not be exceeded accounting for the analytical uncertainty in each measured concentration.1 Analyzed nonradionuclide chemical concentrations, their standard deviations and their corresponding WAC TARGETS1 are shown in Table 3-2 that correspond to the Attachment 8.2 TARGETS in the WAC.1 Per the WAC, the TARGETS shown shall not be exceeded accounting for the analytical uncertainty in each measured concentration.1 The LIMITS refer to a type of acceptance criteria that, if not satisfied, will have an adverse impact on repository requirements, whereas the TARGETS refer to a type of acceptance criteria that is set as a guideline to protect a LIMIT.1 For the chemical contaminants and the radionuclides given in tables below, an analytical uncertainty of 2 sigma (2) shall be accounted for in sample analyses used to determine the analytical uncertainty vs. either the LIMIT or TARGET.1 The standard deviations given in tables for this WAC report are taken as 1 sigma (1) values that are calculated from the normal standard deviation function for either duplicate or triplicate values from within Excel spreadsheets.
Comparison of the average analyzed detectable values shown in Table 3-1 to the WAC LIMITS indicates that free hydroxide and nitrate anions and total mercury are the highest analytes relative to the WAC LIMITS at 22%, 24% and 18%, respectively. Comparison of the average analyzed values shown in Table 3-2 to the WAC TARGETS indicates that aluminum is the highest analyte relative to the WAC TARGET at 66%, with average TOC at a lower ratio to WAC TARGET of 21%. No VOA analytes (butanol, propanol, benzene and toluene) were detected above the indicated method detection limits from duplicate analyses as shown in Table 3-1 and Table 3-2. Analyzed radionuclide concentrations and the respective radiochemical analysis methods, their standard deviations and their corresponding WAC1 LIMITS and TARGETS are shown in Table 3-3 and Table 3-4, respectively. The minimum detection limit reported for Nb-94 of
(<2.81E-01 pCi/mL) in Table 3-4 is above the requested SRMC TARGET minimum detection limit of 2.8E-03 pCi/mL to meet future inventory reporting requirements4 but is lower than the estimated detection limit initially established by SRNL of 4.38E-01 pCi/mL in 2009.5 All of these Nb-94 values (analyzed, 2013-requested and 2009 estimated detection limit) are orders of magnitude below the WAC TARGET for Nb-94 of 1.53E+02 pCi/mL shown in Table 3-4.
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Comparison of the average analyzed detectable values shown in Table 3-3 to the WAC LIMITS1 indicates that Tc-99 and I-129 are the highest analytes relative to the WAC LIMITS at 20% for both analytes.
Comparison of the average analyzed detectable values shown in Table 3-4 to the WAC TARGETS indicates that none of the radionuclides are higher than 5% of the WAC TARGETS.1 Table 3-4 indicates that the upper limit determined in the triplicate samples analyzed for total alpha for the July 2022 semiannual sample is 7.12E+02 pCi/mL. The total alpha measurement from the cesium removed liquid scintillation counting is a gross semi-quantitative analysis (suffering from the high beta to alpha activity ratio in Tank 50 matrices) and has poor precision compared to the sum of the quantitative radiochemical analyses results for the various actinides. The plutonium isotopes Pu-238, Pu-239 and Pu-240 are the major contributors to the alpha activity in Tank 50 aqueous samples. Some of the standard deviation values for the radiochemical analyses of Sr-90, plutonium isotopes and U-232 show larger than normal values relative to the triplicate average. This observation likely derives from the use of some of the residual surface sample mixed in with the variable depth sample when the three replicates were prepared for radiochemical analyses. However, adding the standard deviation values to the average analyzed detectable values for these isotopes and comparing those values to the WAC LIMITS of Table 3-3 and the WAC TARGETS of Table 3-4 indicates that these values (average plus standard deviation) are still all lower than 10% of the WAC LIMITS or WAC TARGETS for the Sr-90, plutonium isotopes and U-232.
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Table 3-1. Chemical Contaminants from July 2022 Semiannual Tank 50 Samples and SPF WAC,.1 LIMITS Chemical Name (Formula)
Method Average Concentration (mg/L)
Std. Dev.
WAC LIMIT (mg/L)
Aluminate (Al(OH)4-)
ICP-AES 1.62E+04a 1.49E+02 4.08E+05 Ammonium (NH4+)
<5.00E+01 NA 2.12E+02 Carbonate (CO32-)
TIC 1.43E+04b 7.63E+01 1.20E+05 Chloride (Cl-)
<1.00E+02 NA 7.95E+03 Fluoride (F-)
<1.00E+02 NA 4.07E+03 Free Hydroxide (OH-)
Total Base 3.48E+04b 5.47E+02 1.58E+05 Nitrate (NO3-)
IC 1.06E+05 1.53E+03 4.37E+05 Nitrite (NO2-)
IC 2.00E+04 2.65E+02 2.14E+05 Oxalate (C2O42-)
IC 3.97E+02 2.52E+00 2.72E+04 Phosphate (PO43-)
<1.00E+02 NA 3.14E+04 Sulfate (SO42-)
IC 8.30E+03 1.19E+02 5.69E+04 Arsenic (As)
ICP-MS 1.16E-01 1.89E-03 1.97E+02 Barium (Ba)
ICP-AES
<2.28E-01 NA 6.19E+02 Cadmium (Cd)
ICP-AES
<1.60E-01 NA 3.10E+02 Chromium (Cr)
ICP-AES 6.01E+01 1.84E+00 1.50E+03 Lead (Pb)
ICP-MS 4.18E-01 2.75E-02 7.50E+02 Total Mercury (Hg)
DMA 5.92E+01 1.31E+00 3.25E+02 Elemental Mercury (Hg(0))
P&T-TD-CVAFS 1.34E+00 8.14E-02 3.25E+02 Monomethyl Mercury (CH3Hg)
CVAFS 1.73E+01 5.29E-01 3.50E+02 Ethyl Mercury (C2H5Hg)
CVAFS
< 1.00E+00 NA 3.73E+02 Ionic Mercury (Hg(I/II))d P&T-TD-CVAFS 7.59E+00d 3.56E+00 NAd Selenium (Se)
ICP-MS
<9.44E-02 NA 3.75E+02 Silver (Ag)
ICP-AES
<1.94E-01 NA 6.19E+02 Aluminum (Al)
ICP-AES 4.61E+03 4.23E+01 1.16E+05 Potassium (K)
ICP-AES
<4.25E+02 NA 3.03E+04 Butanol (C4H9OH)
VOA
<5.00E-01c NA 7.73E+00 Propanol (C3H7OH)
VOA
<2.50E-01c NA 1.88E+00 Phenol (C6H5OH)
SVOA
<1.00E+01c NA 7.50E+02 Tetraphenylborate [TPB]
(B(C6H5)4-)
HPLC
<5.00E+00 NA 5.00E+00 Total Organic Carbon
(----)
TOC 1.55E+02b 2.31E+00 4.50E+03 Isopar L (----)
SVOA
<3.30E+01c NA 8.75E+01
- a. Result is calculated from the measured Al concentration assuming all the Al is present as the OH compound.
- b. Measurement performed on filtered supernate samples.
- c. Measurement performed on duplicate samples rather than triplicate samples.
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Table 3-2. Chemical Contaminants from July 2022 Semiannual Tank 50 Samples and SPF WAC,.2 TARGETS Chemical Name (Formula)
Method Average Concentration (mg/L)
Std. Dev.
WAC TARGET (mg/L)
Aluminum (Al)
ICP-AES 4.61E+03 4.23E+01 7.00E+03e Boron (B)
ICP-AES 3.66E+01 9.24E-01 7.43E+02 Cobalt (Co)
ICP-MSa 3.64E-02 1.04E-02 1.45E+02 Copper (Cu)
ICP-AES
<8.29E-01 NA 7.43E+02 Iron (Fe)
ICP-AES 1.24E+01 7.35E+00 4.95E+03 Lithium (Li)
ICP-AES
<7.82E+00 NA 7.43E+02 Manganese (Mn)
ICP-AES
<6.81E-01 NA 7.43E+02 Molybdenum (Mo)
ICP-AES 1.51E+01 4.23E-01 7.43E+02 Nickel (Ni)
ICP-AES
<5.50E-01 NA 7.43E+02 Silicon (Si)
ICP-AES
<2.60E+01 NA 1.07E+04 Strontium (Sr)
ICP-AES
<1.65E-01 NA 7.43E+02 Zinc (Zn)
ICP-AES 4.77E+00 2.98E-01 8.03E+02 Dimethyl Mercury
((CH3)2Hg)
VOAb
<2.50E-01 NA 1.00E+00 Benzene (C6H6)
VOA
<1.50E-01c NA 3.10E+02 Methanol (CH3OH)
VOA d
NA 1.88E+00 Toluene (C6H5CH3)
VOA
<1.50E-01c NA 3.10E+02 Dibutylphosphate [DBP]
(C8H19O4P)
<2.50E+02 NA 3.47E+02 Tributylphosphate [TBP]
((C4H9O)3PO)
SVOA
<7.50E-01c NA 7.50E+00 Total Organic Carbon (TOC)
TOC 1.55E+02 2.31E+00 7.50E+02e EDTA (C10H12N2O84-)
HPLC
<1.00E+02 NA 3.10E+02 NORPAR 13 (CnH2.n)
SVOA
<7.50E-01c NA 7.50E-01 Formate (CHOO-)
<1.00E+02 NA 6.38E+03
- a. Cobalt based on the stable Co-59 isotope.
- b. This method is a semi-quantitative method due to lack of a dimethyl mercury standard.
- c. Measurement performed on duplicate samples rather than triplicate samples.
- d. Currently, a routine method for detecting this species does not exist within the SRNL CP&C organization.
- e. The WAC TARGETS for Al and TOC shown in this table are more restrictive than the corresponding WAC LIMITS shown in Table 3-1 to protect assumptions associated with thermolytic hydrogen generation.1
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Table 3-3. Radionuclide Contaminants from July 2022 Semiannual Tank 50 Samples and SPF WAC, Attachment 8.3 LIMITS Radionuclide Method Average Concentration (pCi/mL)
Std. Dev.
WAC LIMIT (pCi/mL)
Tritium (3H)
Tritium Counting 1.69E+03 5.51E+01 5.63E+05 Carbon-14 (14C)
C-14 Liquid Scintillation 6.56E+02 1.38E+01 1.13E+05 Nickel-63 (63Ni)
Ni-59/63
<5.05E+00 NA 1.13E+05 Strontium-90 (90Sr)
Sr-90 Liquid Scintillation 3.49E+03 2.76E+03 2.62E+06 Technetium-99 (99Tc)
Tc-99 Liquid Scintillation 4.26E+04 2.89E+03 2.11E+05 Iodine-129 (129I)
I-129 (w/ separation)
Liquid Scintillation 1.98E+01 2.12E+00 1.00E+02 Cesium-137 (137Cs)
Gamma Scan 1.15E+04 1.47E+03 1.29E+06 Uranium-233 (233U)
ICP-MS 2.50E+01 2.48E-01 1.13E+04 Uranium-235 (235U)
ICP-MS 1.88E-01 3.90E-03 1.13E+02 Plutonium-241 (241Pu)
Pu238/241 Liquid Scintillation 1.06E+03 1.17E+03 8.38E+05 Total Alpha Liquid Scintillation Counting (Cs removed)
<7.12E+02 NA 2.13E+05
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Table 3-4. Radionuclide Contaminants from July 2022 Semiannual Tank 50 Samples and SPF WAC, Attachment 8.4 TARGETS Radionuclide Method Average Concentration (pCi/mL)
Std. Dev.
WAC TARGET (pCi/mL)
Aluminum-26 (26Al)
Gamma Scan (Cs removed)
<8.06E-02 N/A 2.88E+03 Potassium-40 (40K)
Gamma Scan (Cs removed)
<1.92E+00 NA 1.00E+02 Cobalt-60 (60Co)
Gamma Scan (Cs removed)
<1.38E-01 NA 9.75E+02 Nickel-59 (59Ni)
Ni-59/63
<5.77E-01 NA 1.13E+03 Selenium-79 (79Se)
Se-79 5.71E+01 1.22E+01 1.90E+04 Yttrium-90 (90Y)
Secular Equilibrium w/ 100% of Sr-90 3.49E+03 2.76E+03 2.62E+06 Zirconium-93 (93Zr)
ICP-MS 2.18E+01 4.26E+00 1.00E+05 Niobium-94 (94Nb)
Nb-94
<2.81E-01 NA 1.53E+02 Rhodium-106 (106Rh)
Secular Equilibrium w/ 100% of Ru-106
<1.98E+00 NA 3.12E+05 Ruthenium-106 (106Ru)
Gamma Scan (Cs removed)
<1.98E+00 NA 3.12E+05 Antimony-125 (125Sb)
Gamma Scan (Cs removed) 9.92E+01 1.38E+00 7.99E+03 Tellurium-125m (125mTe)
Secular Equilibrium w/ 100% of Sb-125 9.92E+01 1.38E+00 1.83E+03 Tin-126 (126Sn)
Gamma Scan (Cs removed) 5.06E+02 9.38E+00 1.80E+04 Cesium-134 (134Cs)
Gamma Scan
<5.81E+01 NA 5.93E+03 Cesium-135 (135Cs)
Cs-135
<2.23E+00 NA 2.50E+02 Barium-137m (137mBa)
Calculation (Secular Equilibrium w/ 94.6%
of Cs-137) 1.09E+04 1.39E+03 1.22E+06 Cerium-144 (144Ce)
Gamma Scan (Cs removed)
<2.79E+00 NA 3.12E+04 Praseodymium-144 (144Pr)
Secular Equilibrium w/ 100% of Ce-144
<2.79E+00 NA 3.12E+04 Promethium-147 (147Pm)
Pm-147/Sm-151 Liquid Scintillation
<1.08E+02 NA 1.57E+06 Samarium-151 (151Sm)
Pm-147/Sm-151 Liquid Scintillation
<3.65E+01 NA 2.25E+04 Europium-154 (154Eu)
Gamma Scan (Cs removed)
<4.45E-01 NA 1.62E+03 Radium-226 (226Ra)
<3.90E+00 NA 1.00E+03 Radium-228 (228Ra)
Gamma Scan (Cs removed)
<1.09E+00 NA 1.00E+04 Actinium-227 (227Ac)
Th-229/230 6.35E-02a NA 1.00E+04 Thorium-229 (229Th)
Th-229/230
<8.47E-02 NA 1.63E+05 Thorium-230 (230Th)
Th-229/230
<8.47E-02 NA 6.26E+03 Thorium-232 (232Th)
ICP-MS 8.11E-04a N/A 2.88E+03 Protactinium-231 (231Pa)
Pa-231
<1.15E+01 NA 1.00E+03 Uranium-232 (232U)
U-232 2.17E+00 1.28E+00 2.27E+03 Uranium-233 (233U)
ICP-MS 2.50E+01 2.48E-01 3.12E+03 Uranium-234 (234U)
ICP-MS 7.69E+01 9.57E-01 3.12E+03 Uranium-236 (236U)
ICP-MS 1.28E+00 4.37E-02 3.12E+03 Uranium-238 (238U)
ICP-MS 1.19E+00 2.05E-02 3.12E+03
SRNL-STI-2022-00526 Revision 0 9
Table 3-4. Radionuclide Contaminants from July 2022 Semiannual Tank 50 Samples and SPF WAC,.4 TARGETS, continued Radionuclide Method Average Concentration (pCi/mL)
Std. Dev.
WAC TARGET (pCi/mL)
Neptunium-237 (237Np)
ICP-MS
<1.66E+00 NA 1.00E+04 Plutonium-238 (238Pu)
Pu238/241 Pu alpha PHA 2.65E+03 3.17E+03 6.67E+04 Plutonium-239 (239Pu)
Pu238/241 Pu alpha PHA 8.79E+01 1.06E+02 6.67E+04 Plutonium-240 (240Pu)
Pu238/241 Pu alpha PHA 8.79E+01 1.06E+02 6.67E+04 Plutonium-242 (242Pu)
ICP-MS
<9.01E+00 NA 6.67E+04 Plutonium-244 (244Pu)
ICP-MS
<4.18E-02 NA 7.02E+04 Americium-241 (241Am)
Am/Cm
<1.68E+00 NA 6.67E+04 Americium-242m (242mAm)
Am/Cm
<1.73E-01 NA 4.50E+05 Americium-243 (243Am)
Am/Cm
<3.24E-01 NA 6.67E+04 Curium-242 (242Cm)
Am/Cm
<1.43E-01 NA 1.13E+04 Curium-244 (244Cm)
Am/Cm
<4.43E-01 NA 6.67E+04 Curium-245 (245Cm)
Am/Cm
<9.19E-01 NA 2.25E+05 Total Alpha Liquid Scintillation Counting (Cs removed)
<7.12E+02 NA 6.67E+04
- a.
Only a single detectable value was determined in the triplicate analysis.
The following tables show various chemical contaminants (Table 3-5), organic species (Table 3-6) and processing constituents (Table 3-7) related to the Salt Disposal Unit (SDU) that are referred to in the WAC per Tables 2, 4 and 5, respectively.1 The reported detection limit for Isopar L of <2.70E+01 ppm in Table 3-5 is lower than the current Isopar LIMIT of 87.5 ppm associated with SDU flammability for the Salt Disposition Integration (SDI) WAC.1 The pH value shown in Table 3-7 is calculated from the pH equation for water (pH + pOH = 14) with the measured [OH-] from Table 3-1 used in the calculation.
Table 3-5. Chemical Contaminants Impacting Saltstone Disposal Unit (SDU) Flammability from July 2022 Semiannual Tank 50 Samples and WAC Table 2 LIMITS and TARGETS Chemical Name (Formula)
Method Average Concentration (mg/L)
Std. Dev.
WAC LIMIT/TARGET Isopar L (----)
SVOA
<2.70E+01 ppma,b NA 8.75E+01 ppm (LIMIT)
Tetraphenylborate [TPB]
(B(C6H5)4-)
HPLC
<5.00E+00 NA 5.00E+00 mg/L (LIMIT)
Ammonium (NH4+)
<5.00E+01 NA 2.12E+02 mg/L (LIMIT)
Total Mercury (Hg)
DMA 5.92E+01 1.31E+00 3.25E+02 mg/L (LIMIT)
Monomethyl Mercury (CH3Hg)
CVAFS 1.73E+01 5.29E-01 3.50E+02 mg/L (LIMIT)
Dimethyl Mercury ((CH3)2Hg)
VOAc
<2.50E-01 NA 1.00E+00 mg/L (TARGET)
- a.
Measurement performed on duplicate samples rather than triplicate samples.
- b.
Result is calculated from the reported concentration of <33 mg/L and the density of the slurry sample listed in Table 3-8.
- c.
This method is a semi-quantitative method due to lack of a dimethyl mercury standard.
SRNL-STI-2022-00526 Revision 0 10 Table 3-6. Other Organics Impacting SDU Flammability from July 2022 Semiannual Tank 50 Samples and WAC Table 4 Concentrations Chemical Name (Formula)
Method Average Concentration (mg/L)
Std. Dev.
WAC Concentrations (mg/L)
Butanol (C4H9OH)a VOA
<5.00E-01 NA 0.75 Tributylphosphate[TBP]
((C4H9O)3PO)a SVOA
<7.50E-01 NA 1.0 Propanol (C3H7OH)a VOA
<2.50E-01 NA 0.25 Methanol (CH3OH) b NA NA 0.05 NORPAR 13 (CnH2.n)a SVOA
<7.50E-01 NA 0.75
- a.
Measurement performed on duplicate samples rather than triplicate samples.
- b.
Currently, a routine method for detecting this species does not exist in AD.
Table 3-7. Processing Constituents from July 2022 Semiannual Tank 50 Samples and WAC Table 5 LIMITS Processing Constituents Method Value Std. Dev.
WAC LIMIT pH Calculated
>13 NA
> 10 Sodium Concentration ICP-AES 4.94 M 9.20E-03 2.5 M < [Na+] < 7.0 M Total Insoluble Solids Calculateda
~0 wt %
NA
< 15 wt %
- a.
Error propagation performed on the measured total solids and dissolved solids gives no credible calculated insoluble solids value, i.e., there is no statistical difference in the two measured values.
Table 3-8 contains additional measured constituents per the TTQAP.3 There were no detectable nitrosamine species in the Tank 50 surface sample via the SVOA analyses shown in Table 3-8.
SRNL-STI-2022-00526 Revision 0 11 Table 3-8. Additional Measured Constituents Constituent Method Average Value Std. Dev.
Density (slurry)
Measured (21.6ºC) 1.221 g/mL
<0.001 g/mL Specific Gravity a
1.223
<0.001 Total Solids Measured 25.16 wt %
0.17 wt %
Total Beta LSC 1.02E+05 pCi/mL 1.21E+04 pCi/mL Total Gamma b
1.20E+04 pCi/mL 8.03E+02 pCi/mLc Beryllium (Be)
ICP-AES
< 1.22E-01 mg/L NA N-Nitrosodimethylamine (C2H6N2O)
SVOAd
<1 mg/L NA N-Dioctylnitrosamine (C16H34N2O)
SVOAd
<1 mg/L NA
- a. Calculated from the measured density of slurry and density of water at 21.5 C.21
- b. Calculated from the sum of gamma emitters (Sb-126, Sn-126, Sb-125, Eu-154, Am-241, Co-60 and Ba-137m).
- c. Value is the standard error of the mean rather than the standard deviation of the measurements since its calculation involves multiple radionuclides.
- d. Measurement performed on duplicate samples rather than triplicate samples 4.0 Conclusions The following conclusions pertaining to the WAC are drawn from the analytical results provided in this report.
WAC TARGETS and LIMITS were met for all analyzed chemical and radioactive contaminants for which the detection limits are below the WAC TARGETS and LIMITS.1 Nitrosamines were not detected in the Tank 50 salt solution sample above the instrument detection limits of <1 mg/L.
The minimum detection limit (<2.81E-01 pCi/mL) is reported for 94Nb as determined from the minimum detectable activity associated with the radiochemical method used for this radionuclide.
The reported detection limit is above the requested SRMC target minimum detection limit concentration.4 However, the minimum detection limit reported for the July 2022 semiannual Tank 50 sample for 94Nb is lower than the estimated detection limit of 4.38E-01 pCi/mL initially established by SRNL in 2009.5 Thus per guidance from SRMC,4 SRNL continues to achieve as low as practical detection limits for this radionuclide.
SRNL-STI-2022-00526 Revision 0 12 5.0 References 1
Harrington, S. J., Waste Acceptance Criteria for Transfers to the Z-Area Saltstone Production Facility During Salt Disposition Integration (SDI) (U), Savannah River Remediation, X-SD-Z-00004, Rev. 4, March 2021.
2 M. Brown., "Routine Saltstone Support for Salt Solution and Grout Analyses ", Savannah River Remediation, X-TTR-Z-00025, Rev. 0, August 2021.
3 Crawford, C. L., Hill, K. A., "Task Technical and Quality Assurance Plan for Salt Solution Analyses and Grout Sample Preparation and Analyses", Savannah River National Laboratory, SRNL-RP-2021-04610, Rev.
0, December 2021.
4 Dixon, D. B., "Minimum Detection Limits for Saltstone Quarterly WAC Analyses", Savannah River Remediation, SRR-WSE-2013-00005, Rev. 1, January 2013.
5 DiPrete, C. C., "Overview of Capability to Measure Radionuclides of Interest for Saltstone", Savannah River National Laboratory, SRNL-L4000-2009-00028, Rev. 0, June 2009.
6 Crawford, C. L., Results for the July 2022 Semiannual Tank 50 Salt Solution Sample: Cs-137, Savannah River National Laboratory, SRNL-L3100-2022-00007, Rev.0, August 2022.
7 Crawford, C. L. and Hill, K. A., Task Technical and Quality Assurance Plan for Bimonthly Saltstone Support for Salt Solution Performance Assessment Analyses, SRNL-RP-2021-04577, Rev. 0, September 2021.
8 Crawford, C. L., July 2022 Semiannual Tank 50 WAC Characterization, B9108-00327-26, SRNL E-Notebook (Production), Savannah River National Laboratory, July 2022.
9 Gas Chromatography/Mass Spectrometry for Volatile Organics: Contract Laboratory Program Methods, Manual L16.1, Procedure ADS-2656, Rev. 9, October 2016.
10 Gas Chromatography/Mass Spectrometry for Semivolatile Organics Including Polychlorinated Biphenyls, Manual L16.1, Procedure ADS-2657, Rev. 7, May 2016.
11 Aqua Regia Dissolution of Sludge for Elemental Analysis; Savannah River National Laboratory, Manual L16.1, Procedure ADS-2226, Rev. 10, July 2013.
12 Weight Percent Solids Determination Using a Furnace or Oven, Savannah River National Laboratory, Manual L29, Procedure ITS-0078, Rev. 1, October 2012.
13 Integrated Data Base Report - 1996: U.S. Spent Nuclear Fuel and Radioactive Waste Inventories, Projections, and Characteristics, Oak Ridge National Laboratory, DOE/RW-0006, Rev. 13, December 1997.
https://www.nrc.gov/docs/ML1028/ML102850100.pdf (accessed April 28, 2022).
14 White, T. L., Brown, L. W., Looney, B. B. and Jones, M. A., Total Mercury Analysis Comparison Deployment of Analytical Method for the Savannah River Site Liquid Waste System, Savannah River National Laboratory, SRNL-STI-2019-00056, Rev. 0, July 2019.
15 Boggess, A. J., Bannochie, C. J., White, T. L., Jones, M. A. and Edwards, T. B., Methylmercury and Ethylmercury Analytical Performance in SRR Samples Measured by SRNL and Eurofins Frontier Global Sciences, Savannah River National Laboratory, SRNL-STI-2018-00250, Rev. 0, July 2019.
SRNL-STI-2022-00526 Revision 0 13 16 Boggess, A. J., White, T. L., Jones, M. A., Edwards, T. B. and Harris, S. P., Development and Comparison of Purgeable Mercury Values in SRR Samples Measured by SRNL and Eurofins FGS, Savannah River National Laboratory, SRNL-STI-2019-00300, Rev. 0, September 2019.
17 Boggess, A. J., Jones, M. A., White, T. L., Analysis of Ionic Mercury Species in SRR Samples Measured by SRNL and Eurofins FGS, Savannah River National Laboratory, SRNL-STI-2020-00081, Rev. 0, May 2020.
18 Best Handling Practices for Elemental Mercury, Organo-Mercury Compounds, and Inorganic Mercury Compounds, SRNL-TR-2019-00243, Rev. 1, June 2020.
19 Technical Reviews, Savannah River Site, Manual E7, Procedure 2.60, Latest Revision.
20 Savannah River National Laboratory Technical Report Design Check Guidelines, Westinghouse Savannah River Company, WSRC-IM-2002-00011, Rev. 2, August 2004.
21 CRC Handbook of Chemistry and Physics, 103rd Print Edition, Internet Version 2021; Section 6: Fluid Properties. Edited by Rumble, J. R., CRC Press Taylor and Francis Group, Boca Raton, FL, Internet Version 2021. http://hbcponline.com/faces/contents/ContentsSearch.xhtml (accessed October 26, 2022).
SRNL-STI-2022-00526 Revision 0 Distribution:
Name:
F. L. Armstead R. C. Jolly J. P. Arnold A. W. Jung M. J. Barnes D. E. Kucab E. P. Barrowclough C. A. Langton J. M. Benedict J. D. Ledbetter M. N. Borders B. Lee J. M. Bricker K. R. Liner M. A. Broome K. S. Lott N. F. Chapman J. Manna W. A. Condon K. B. Martin J. M. Conley D. J. McCabe C. J. Conner G. A. Morgan A. D. Cozzi P. W. Norris C. L. Crawford J. E. Occhipinti J. R. Dekarske F. M. Pennebaker D. P. Diprete M. M. Potvin K. D. Dixon J. D. Rahming C. M. Gregory W. G. Ramsey S. J. Harrington J. W. Ray E. W. Harrison L. B. Romanowski C. C. Herman K. H. Rosenberger K. A. Hill A. Samadi-Dezfouli P. J. Hill F. M. Smith R. M. Hoeppel A. V. Staub A. T. Hooker M. E. Stone T. H. Huff K. R. Wells H. M. Hunter B. J. Wiedenman J. F. Iaukea T. L. White V. Jain M. L. Whitehead Records Administration (EDWS)