The authors wish to express appreciation to the following staff members of the ORNL Chemical and Analytical Sciences Division who made important contributions to this work:

Inorganic and Radiochemical Analytical Support

L. D. Bible

R. D. Canaan

D. A. Caquelin

K. M. Hoyle^a

C. L. Kay^a

E. H. McBay

T. P. Mills^a

D. H. Smith

N. A. Teasley

Organic Analytical Support

S. H. Harmon

R. L. Schenley

L. T. Worthy^b

^a Subcontractor staff, Oak Ridge Research Institute.

^b Subcontractor staff, Midwest Technical Inc.

The authors also wish to express appreciation to the following staff members of the Liquid and Gaseous Waste Operation Department of the Office of Waste Management and Remedial Actions for tank sampling support:

Sampling Radioactive Waste Tanks

J. D. Brewer

C. B. Scott

ABBREVIATIONS AND ACRONYMS

ALARA As Low As Reasonably Achievable

CAO Carlsbad Area Office

CASD Chemical and Analytical Sciences Division

CVAA Cold Vapor Atomic Absorption

DOT Department of Transportation

DQO Data Quality Objective

EPA Environmental Protection Agency

GC/MS Gas Chromatography/Mass Spectrometry

GC Gas Chromatography

GFAA Graphite Furnace Atomic Absorption

IC Ion Chromatography

ICP Inductively Coupled Plasma

ICP-AES Inductively Coupled Plasma - Atomic Emission Spectroscopy

ICP-MS Inductively Coupled Plasma - Mass Spectrometry

IDL Instrument Detection Limit

LCS Laboratory Control Sample

LLLW Liquid Low-Level Waste

LMER Lockheed Martin Energy Research, Corp.

LMES Lockheed Martin Energy Systems, Inc.

MDL Method Detection Limit

MS Matrix Spike

MSD Matrix Spike Duplicate

MVST Melton Valley Storage Tanks

NHVOA Non-halogenated Volatile Organic Analysis

NTS Nevada Test Site

ORNL Oak Ridge National Laboratory

PCB Polychlorinated Biphenyls

QA Quality Assurance

QAPjP Quality Assurance Project Plan

QAPP Quality Assurance Program Plan

QC Quality Control

RCRA Resource Conservation and Recovery Act

RMAL Radioactive Materials Analytical Laboratory (Building 2026)

SVOA Semivolatile Organic Analysis

TC Total Carbon

TCLP Toxicity Characteristic Leaching Procedure

TDS Total Dissolved Solids

TIC Total Inorganic Carbon or Tentatively Identified Compounds

TIMS Thermal Ionization Mass Spectrometry

TOC Total Organic Carbon

TRU Transuranic

TWCP Transuranic Waste Characterization Program

VOA Volatile Organic Analysis

WAC Waste Acceptance Criteria

WIPP Waste Isolation Pilot Plant

EXECUTIVE SUMMARY

During the fall of 1996 there was a major effort to sample and analyze the Active Liquid Low-Level Waste (LLLW) tanks at ORNL which include the Melton Valley Storage Tanks (MVST) and the Bethel Valley Evaporator Service Tanks (BVEST). The characterization data summarized in this report was needed to address waste processing options, address concerns of the performance assessment (PA) data for the Waste Isolation Pilot Plant (WIPP), evaluate the waste characteristics with respect to the waste acceptance criteria (WAC) for WIPP and Nevada Test Site (NTS), address criticality concerns, and meet DOT requirements for transporting the waste. This report only discusses the analytical characterization data for the MVST waste tanks (except for W-29 and W-30). There will be a companion report on the BVEST waste tanks that will include the analytical data and the results from rheometry experiments on the BVEST sludge.

The isotopic data presented in this report supports the position that fissile isotopes of uranium (²³³U and ²³⁵U) and plutonium (²³⁹Pu and ²⁴¹Pu) were "denatured" as required by the administrative controls stated in the ORNL LLLW waste acceptance criteria (WAC). In general, the MVST sludge was found to be both hazardous by RCRA characteristics and the transuranic alpha activity was well above the 100 nCi/g limit for TRU waste. The characteristics of the MVST sludge relative to the WIPP WAC limits for fissile gram equivalent, plutonium equivalent activity, and thermal power from decay heat, were estimated from the data in this report and found to be far below the upper boundary for any of the remote-handled transuranic waste (RH-TRU) requirements for disposal of the waste in WIPP.

Characterization of the MVST Waste Tanks

Located at ORNL

J. M. Keller, J. M. Giaquinto, A. M. Meeks

1.0 Introduction

The active ORNL Liquid Low Level Waste (LLLW) system consists of the set of waste tanks summarized in Table 1. As indicated in Table 1, this report only discusses the analytical characterization data for the MVST waste tanks (except for W-29 and W-30). There will be a companion report on the BVEST waste tanks in the near future. The characterization data summarized in this report was needed to address waste processing options, address concerns of the performance assessment (PA) for the Waste Isolation Pilot Plant (WIPP), evaluate the waste characteristics with respect to the waste acceptance criteria (WAC) for WIPP and Nevada Test Site (NTS), address criticality concerns, and to meet DOT requirements for transporting the waste.

The data was collected during a sampling and analysis campaign performed during the late summer and fall of 1996. The sampling and waste characterization requirements were documented in a Sampling and Analysis Plan¹ (SAP). The level of quality assurance approximates that required for regulatory measurements with the understanding that, when needed, sample size requirements were reduced, and steps were taken to reduce sample handling to ensure radiation exposures were as-low-as-reasonably-achievable (ALARA). Some procedure modifications were required to handle chemical matrix problems due to the high levels of sodium nitrate, uranium, and thorium present. Any deviations from procedures or problems observed with the tank samples were documented in the data files maintained by the laboratory. The regulatory holding time requirements for mercury and the organic measurements were complied with unless noted differently in the data tables. The Quality Control (QC) Acceptance Criteria for measurement used on this project are summarized in Appendix A.

Table 1 Summary of Tanks in the Active ORNL LLLW System

Tanks	Data Presented in this report
Tanks	Liquid	Sludge
BVEST TANKS
C-1 (HLW)	none	none
C-2 (HLW)	none	none
W-21 (PWTP)	none	none
W-22 (BVCT)	none	none
W-23 (LLLW)	none	none
MVST TANKS
W-24
W-25
W-26
W-27
W-28
W-29	none	none
W-30	none	none
W-31

The earlier waste tank characterization work performed, in 1985 by Peretz² et. al. and 1990 by Sears³ et. al., did not specifically address criticality concerns. There was limited radiochemical data on ²³³U, ²³⁵U and ²³⁹Pu; which was taken from gross radiochemical screening measurements. This previous data for fissile actinide elements in the LLLW waste tanks had relatively large analytical errors and should be used with caution. More recent data, reported by Keller⁵ et.al. and Sears⁶, which was collected in early 1996, addresses some of the criticality concerns but did not address all the tanks of interest. The analytical data for fissile isotopes in this report are based on mass spectrometry measurements, similar to the data collected in early 1996, but includes a more complete set of LLLW waste tanks. The uranium and plutonium were each chemically separated from the waste matrix prior to measurement of the isotopic ratios by mass spectrometry. The mass spectrometry measurements yield more detailed and accurate information than radiochemical measurements for the major fissile isotopes present. The isotopic mass ratio measurements on the sludge samples may not represent the average isotopic ratios due to the heterogeneous nature of the sludge. The isotopic data for each liquid sample should be more representative of the overall supernatant present than comparable measurements for the sludge. Based upon physical observations, the tank sludge tends to be segregated into vertical layers which indicates minimal mixing of the sludge material as it was added to the tanks. Due to limited access to the waste tanks, there is no analytical data available to evaluate segregation horizontally across the tank at the time of this report.

An inventory of radioactive liquid waste and sludge stored in each tank are shown in Table 2 and includes estimates for the volumes through October 1996. The volume data⁴ is based on estimates by the Chemical Technology Division (CTD).

Table 2 Volumes Estimates for Liquid and Sludge in the LLLW System

Tank	Total Waste Volume		Sludge Volume		Supernatant Volume
Tank	(gal)	(L)	(gal)	(L)	(gal)	(L)
W-21	23100	87500	6500	24600	16600	62900
W-22	13100	49600	6800	25800	6300	23800
W-23	21800	82600	10600	40100	11200	42400
W-24	22300	84400	8700	32900	13600	51500
W-25	44100	167000	17300	65500	26800	101500
W-26	44600	168900	11800	44700	32800	124200
W-27	26000	98500	16000	60600	10000	37900
W-28	44200	167400	4500	17000	39700	150300
W-29	44300	167800	11000	41700	33300	126100
W-30	41200	156000	11000	41700	30200	114300
W-31	43900	166200	10600	40100	33300	126100

2.0 Sample Collection Activities

A detailed description on the background, operation of the LLLW system, and the sample collection techniques has been presented in previous reports and will not be discussed here (see Sections 2 and 3 of Reference 3). The staff from the Liquid and Gaseous Waste Operations (LGWO) provided all sample collection support and delivered the samples to the analytical laboratory. A good description of the sampling procedures is provided in Appendix A of the Sampling and Analysis Plan¹; a current copy of these procedures are available from the LGWO group. The documentation for chain-of-custody was prepared, maintained for each sample collected, and stored with the data files by the analytical laboratory.

3.0 Analytical Methodology

The information and data collected from these studies are used to support various activities. The activities include demonstration of regulatory compliance, measurements to support future processing options, and to meet data needs for risk assessments and other safety related assessments such as criticality. Standardized analytical procedures are used to the extent possible to ensure broad acceptance of the data generated. Unless stated otherwise, the U. S. Environmental Protection Agency (EPA) methods are used for the analyses of constituents listed as hazardous under the Resource Conservation and Recovery Act (RCRA), which includes all the inorganic and organic measurements presented in this report. In general the EPA Guidance Manual, Test Methods for Evaluating Solid Waste⁷ (SW-846), is used for inorganic and organic methods. Some modifications of the standard procedures are necessary to handle the high radiation levels and the high salt/solids content. Some procedure modifications are required to generate valid data, these changes were usually needed to correct for chemical or other matrix related interferences. All deviations from the standard procedures are documented in the raw data files and can be provided upon request to data users.

3.1 Sample Preparation

The aqueous supernatant samples from the waste tanks were filtered or centrifuged to remove suspended particles. The clarified liquids were then digested by the SW-846 Method 3015, Microwave Assisted Acid Digestion of Aqueous Samples and Extracts. This sample preparation for aqueous samples was then used for all subsequent metal analyses by ICP-AES and GFAA, and most of the radiochemical analyses. Based upon results from a collaborative study⁸ with Argonne National Laboratory - East (ANL-E), Method 3015/3051 demonstrated excellent recovery for mercury and was used to prepare tank samples for mercury determination.

The primary method for digesting the sludge samples was SW-846 Method 3051, Microwave Assisted Acid Digestion of Sediments, Sludges, Soils, and Oils. This sample preparation is considered to be a total digestion for metals and radionuclides by regulatory agencies and yields good results for most metals and radionuclides of interest. This digestion gave poor performance on two of the metals of interest, silver and silicon. Although nitric acid is excellent for dissolving silver compounds, there is usually enough chloride present in waste samples to form an insoluble silver chloride (AgCl) precipitate. If the chloride concentration is increased sufficiently, a silver chloride complex (AgCl₃^-2) forms which is soluble in the aqueous environment. Improved matrix spike recovery and defensible data for silver were obtained using a separate sample digestion discussed later in this report.

If the total silicon content in the sludge must be known to develop waste treatment options such as vitrification, another sample digestion is required. A simple nitric acid treatment will not dissolve most siliceous materials. The SW-846 Method 3052, Microwave Assisted Acid Digestion of Siliceous and Organically Based Matrices, provides the necessary digestion chemistry to yield good silicon data. Sludge samples were prepared for measurement of total silicon, by taking approximately 0.5 g of sludge and mixing with 7 mL of concentrated nitric acid and 3 mL of hydrofluoric acid in a fluorocarbon microwave vessel. The samples were digested for 10 minutes at 95% full power (570 watts) and then cooled to room temperature. The acid solution was then treated with excess boric acid and heated to 80^oC for ten minutes to complex any free fluoride. This digestion mixture is cooled, filtered into a 50 mL volumetric flask, and diluted to volume with ASTM Type II water. Care must be exercised to ensure the digestion solution is cooled to room temperature prior to opening the sealed microwave vessel or there may be a significant loss of the volatile SiF₄ . The free fluoride is complexed with the boron to protect the sample introduction system to the ICP-AES and to prevent a high silicon background from the instrument glassware. This sample digestion with hydrofluoric acid should not be used for radiochemical measurements, especially for measurement of lanthanides or actinides.

Most of the metal and radionuclide data presented in this report are based upon a Method 3051 digestion with approximately a 0.5 gram sludge sample and 10 mL of concentrated nitric acid. After the microwave digestion is completed and the solution cooled to room temperature, the sample is filtered into a volumetric flask and diluted to 50 mL with ASTM Type II water or better. To ensure valid silver and antimony data, samples were digested in a similar manner except the 10 mL of nitric acid was replaced with 6 mL of concentrated nitric acid plus 4 mL of concentrated hydrochloric acid. Any residue remaining after the nitric acid or nitric-hydrochloric acid digestion consisted of mostly SiO₂ and was discarded.

3.2 Metal Analysis

Three analytical measurement methods were used to determine all of the metals included in this report. Most of the metals are first determined by SW-846 Method 6010A, Inductively Coupled Plasma - Atomic Emission Spectroscopy (ICP-AES). There are several elements of interest for which the ICP-AES has insufficient detection limits, and these elements must be determined by Method 7000A, Atomic Absorption Methods. The Radioactive Materials Analytical Laboratory (RMAL) uses a Graphite Furnace Atomic Absorption (GFAA) Spectrometer for elements that require better sensitivity. The elements that usually require GFAA were antimony (Method 7041), arsenic (Method 7060A), lead (Method 7421), selenium (Method 7740), and thallium (Method 7841). All the mercury measurements are done by either Method 7470A, Mercury in Liquid Waste (Manual Cold-Vapor Technique), or Method 7471A, Mercury in Solid or Semisolid Waste (Manual Cold-Vapor Technique). The samples discussed in this report were prepared for mercury analysis by the microwave technique discussed in section 3.1, the sample preparation specified in the mercury methods (7470A and 7471A) were not used.

The level of radioactivity in most LLLW tank samples required that the analytical systems used for metal measurements be modified for operation in a radiochemical hood or glove box. Custom instrument configurations are necessary to ensure contamination control and worker safety. All work was performed in radiochemical laboratories which are operated under strict radiation protection programs, with the use of protective clothing and routine contamination monitoring. Both an ICP-AES system and a GFAA system can generate dry, dusty particles which are difficult to contain and are highly hazardous when radioactive. A detailed description of the RMAL setup for these instruments are given in Appendix B of Reference 3.

The instrument detection limits (IDL) for various metals with undiluted aqueous samples are listed in data tables along with the results. For sludge samples, these detection limits must be increased by a factor that represents the dilution that results from the sample preparation. For all the MVST sludge samples approximately 0.5 g of sample was digested and then diluted to 50 mL which results in about a 100 fold dilution for the sample, and thus a 100 fold increase in the detection limits.

The analytical error for the metal measurements depends upon the analytical method, the concentration level, and the chemical matrix. Inductively-coupled plasma-atomic emission spectroscopy (ICP-AES) and inductively coupled plasma-mass spectrometry (ICP-MS) are both multi-element measurement techniques that are designed for the best average performance for all elements analyzed. In general, these measurement techniques are not optimized for any single element. The sample introduction system for ICP instruments adds additional variability due to changes in sample density, viscosity, and solids content between samples and/or calibration standards. Overall, the expected analytical error for ICP measurements range from ±4-6% at concentrations above 10 times the detection limit to ±20-50% near the detection limit. These error estimates are typical for both ICP-AES and ICP-MS measurements.

Graphite Furnace AA instruments are generally optimized for a specific element and usually provide lower detection limits and better precision. The expected analytical error for GFAA measurements range from 3-5% for concentrations greater than 10 times the detection limit to 20-40% near the detection limit. One advantage of GFAA analysis is that the measurements are normally well above the method's detection limits. The mercury measurements were done by Cold Vapor Atomic Absorption (CVAA), which is very selective and sensitive for mercury. The analytical errors for CVAA measurements are similar to GFAA work.

3.3 Anion Analysis

The determination of the inorganic anions was needed for the development of process treatment options, to provide information to explain the distribution and chemical behaviors observed in the waste tanks, and to ensure the major chemical constituents were identified in the waste for which data was used to calculate the mass and charge balance for each sample. The common inorganic anions; including fluoride, chloride, bromide, phosphate, nitrate, nitrite, and sulfate; were measured by ion chromatography (IC) with a Dionex Model 4500i system. In addition, several water soluble organic acids were measured along with the inorganic anions. These organic acids were measured in their ionized form and included formate, acetate, citrate, and oxalate. Both the citrate and the oxalate can form strong complexes with many metals and change the solution chemistry of these metals in the waste. The ion chromatography system used for measurements on these radioactive samples was configured such that the components that come into contact with radioactivity were isolated in a radiochemical hood for contamination control.

From past observations, the nitrate content dominates both the mass and charge balance calculations with both the supernatant and sludge samples taken from the active LLLW tanks. There are many other anions present in the waste, some of which are measured directly by ion chromatography and others which can be estimated from the metal data such as chromate, dichromate, permanganate, and others. The carbonate is estimated from the total inorganic carbon measurement.

The liquid samples were always analyzed directly by ion chromatography after an appropriate dilution with water. Accounting for the mass and charge balance with the aqueous samples requires less assumptions about the solution chemistry compared to the precipitation chemistry for the sludge samples. The mass/charge balance checks for aqueous samples should agree within the analytical error (approximately ±10%) of the measurements. The performance of balance checks for sludge samples is not expected to be as good as the liquid samples because of the large content of mixed oxides, hydrated hydroxides (heavy metals and actinides), and insoluble carbonates (calcium carbonate, etc.) present in the sludge. The complex precipitation chemistry of the sludge complicates the measurements of total anions and makes estimates for the mass and charge balance more difficult. Analytical techniques such as x-ray fluorescence (XRF) are useful for solid samples but are limited to total element measurements (total sulfur vs. sulfate, total phosphorus vs. phosphate). Another technique, x-ray diffraction (XRD), is useful for the determination of compounds present but only provides qualitative information such as the identification of crystal structures. For this report, the primary sludge anion data is based on a water leach which represents the sum of the anions in the interstitial liquid and the water soluble anions from the solids. For these measurements the sludge samples were prepared by adding approximately 1 gram of sludge to 10 mL of water, mixing for several minutes at room temperature on a vortex mixer, and separating the solids. The resulting solution was analyzed by ion chromatography and the anion concentration was normalized back to the wet weight of the sludge.

Based on conversations with chemists from the Savannah River Site (SRS) and the Hanford site, who have been involved with similar waste characterization work and the experience over the past five years by the RMAL laboratory, the water leach preparation of the caustic sludge samples provides the best total anion data for the halides, nitrites, nitrates, and fair data for sulfate. To resolve questions concerning the total anion content of the sludge two additional sample preparation methods were tested on the MVST sludge samples. The two preparation methods used were 1) Parr bomb combustion of the sludge, and 2) sodium peroxide/hydroxide fusion of the sludge.

Method for Parr Bomb Combustion of Sludges

The procedure used for the bomb combustion is outlined below.

1. Approximately 0.25 g of sludge was weighed into the combustion crucible.

2. 0.5 mL of mineral oil was added to the crucible with the sample.

3. 1 mL of 1 M sodium hydroxide was placed on the bottom of the bomb.

4. The bomb was assembled, charged to 30 atm. with UHP oxygen, and vented. This flush was repeated two more times to remove the nitrogen contribution from air. The bomb was charged to a final pressure of 30 atm with UHP oxygen, placed into a water bath and then the sample was ignited with an electronic spark.

5. The bomb was allowed to stand in the water bath for 4 min. to condense combustion gases.

6. The bomb condensate was rinsed three times into a flask and diluted to 50 mL with water.

The resulting solution was analyzed by ion chromatography for anions.

Method for Sodium Peroxide/Sodium Hydroxide Fusion of Sludges

The procedure used for the fusion is outlined below.

Approximately 0.25 g of sludge was weighed into a nickel crucible.

2. 1.5 g of reagent grade sodium peroxide and 1 g of ultra pure sodium hydroxide was added to the crucible with the sample.

3. The crucible with sample and reagents was covered and placed in a muffle furnace set at 600^o C for 15 min.

4. The samples were removed from the furnace and allowed to cool for 3-4 min.

5. The cover, crucible, and fusion salts were rinsed with water into a flask and diluted to 50 mL.

The final solution was analyzed by ion chromatography for anions.

It is important to note that a bomb combustion or fusion preparation of the MVST sludge samples yields total concentrations of the element measured. An example would be sulfate analysis. A water leach of the sludge will yield a sulfate concentration due to water soluble compounds containing sulfate while a bomb or fusion preparation of the sludge would yield a sulfate concentration due not only to the compounds containing sulfates (both water soluble and insoluble) but any compound containing sulfur. In other words the bomb and fusion preparations yield a total sulfur concentration rather than a total sulfate concentration. In theory, the same principle applies to any anion determined using the bomb or fusion preparation methods.

The final anion measurement technique for all the sample preparation methods was ion chromatography. For simple water samples, without complex chemical matrix problems, the empirical analytical error for ion chromatography measurements ranges from 4-6% for concentrations above 10 times the detection limits to 20-40% near the detection limit. The measurement of anions present at concentration much lower (< 1/25) than other anionic species present may increase the overall error of the measurement.

3.4 Radiochemical Analysis

The only standard radiochemical methods useful for radioactive waste characterization are EPA Method 600/900.0, Gross Alpha and Beta Radioactivity in Drinking Water, and EPA Method 600/901.1: Gamma Emitting Radionuclides in Drinking Water. The EPA Method 600/905.0, Radioactive Strontium in Drinking Water, gave poor performance with the chemical matrix found in ORNL LLLW supernatant and sludge samples. The EPA method for gross alpha/beta measurements uses gas-flow proportional counting. In general, this counting technique requires drying a sample at elevated temperatures onto a metal (usually stainless steel) plate, which resulted in the loss of cesium chloride from the MVST samples and yielded poor gross beta results. To avoid this problem, all gross beta measurements reported are based on measurements by liquid scintillation counting. Other than the gamma spectroscopy measurements, all of the radionuclide measurements were done with in-house procedures. The method detection limits for radiochemical measurements are dependent on both sample matrix and count time and are not listed here. In general, the radiochemical measurements used count times to yield at least 1% (10,000 counts) counting statistics. The expected errors for the radiochemical data range from ±5-10 % for gross alpha/beta and gamma emitter measurements to ±10-20 % for radionuclides that require chemical separations before counting (i.e. ⁹⁹Tc, ⁹⁰Sr, ¹²⁹I, and ²³⁷Np).

The long-lived fission products are typically more difficult and expensive to measure than short lived fission products. Many of these long-lived radionuclides are either pure beta emitters or have weak, low energy, and/or low yield gamma-rays which are not very useful for accurate analytical measurements. In general, good radiochemical data requires that each of these isotopes be chemically separated from all other radioactivity prior to measurement. These chemical separations and measurements are currently being done routinely for⁹⁹Tc and ¹²⁹I because both can exist as anionic species (TcO₄^-, I^-, and IO₃^-) in the waste, and these anions would be highly mobile in the environment. The ⁹⁹Tc is currently being separated by extraction chromatography and measured by ICP-MS which is much more sensitive than counting techniques for radionuclides with a low specific activity. The ¹²⁹I is first extracted into carbon tetrachloride as iodine (I₂), then reduced to iodide (I^-), back-extracted into an aqueous matrix, and loaded onto an anion exchange resin. The ¹²⁹I is then determined by neutron activation analysis. Typically the level of ⁹⁹Tc and ¹²⁹I in the waste is lower than expected from the fission yields, and one possible explanation is that both isotopes form volatile species (HTcO₄, HI, and I₂) when exposed to either acid and/or heat.

The long-lived fission products are a very small fraction of the overall activity present in the waste and there has been little interest in the measurement of these radionuclides in the past. The determination of these isotopes are less routine and are frequently more expensive methods to perform. The judgement of most waste characterization teams has been that the measurement of these radionuclides, with the exception of ⁹⁹Tc, would be interesting but there is insufficient risk to justify the analytical cost.

3.5 Criticality Controls

The current ORNL waste acceptance criteria (WAC) for liquid-low level waste requires that the fissile isotopes of uranium and plutonium be isotopically diluted with ²³⁸U and ²³²Th, respectively. These administrative controls require that the ratio of the ²³⁸U mass divided by the fissile equivalent mass (FEM) for uranium be greater than 100. The ²³⁵U FEM is a useful scale for criticality calculations that normalizes the fission probability for each fissile isotope to ²³⁵U. These FEM factors, designated as f₃₅ for ²³⁵U mass factors, are discussed and listed in the Appendix A, Table 1 of ORNL Procedure NCS-1.0, Nuclear Criticality Safety Program.

The major fissile isotopes of concern in the ORNL waste tanks are ²³³U, ²³⁵U, and ²³⁹Pu. The fissile isotope ²⁴¹Pu is also present in the waste but the mass is usually several orders of magnitude lower and below a level that would influence the isotopic dilution ratio for plutonium. Other fissile isotopes present in the ORNL waste include isotopes of neptunium, americium, and curium, but the actual mass present in the waste has been too low for major concern, and the low concentration would make it difficult and expensive to measure by mass spectrometry.

The data presented in this report for isotopic dilution ratios (also referred to as denature ratios) reflect both the past and current ORNL standard practices for disposal of fissile isotopes of uranium and plutonium. The administrative controls which were in effect when the waste was generated, required that the ²³³U and ²³⁵U be diluted with depleted uranium such that the following condition was true,

	(²³⁸U)
		is > or = to 100
	(1.35)(²³³U)+(²³⁵U)

Because thorium chemistry is more similar to plutonium than uranium chemistry, the administrative procedures required that the ²³⁹Pu be diluted with ²³²Th as follows,

	(²³²Th)
		is > or = to 100
	(²³⁹Pu)

All calculations dealing with isotopic dilution for criticality safety are based on isotope mass ratios and must not be confused with activity ratios. For any data discussed in this report that uses ²³²Th relative to isotopic mass ratios, the total thorium concentration and the ²³²Th concentration are the same value.

The new requirements for administrative criticality control, which should be in effect by the end of this year (1996), are more conservative and require that the following conditions be satisfied for uranium,

	(²³⁸U) - 200 (²³³U)
		is > or = to 110
	(²³⁵U)

	(²³⁸U) - 100 (²³⁵U)
		is > or = to 200
	(²³³U)

The new administrative controls also change requirements for plutonium by increasing the ratio of thorium to plutonium, as given in eq. 2, from a dilution ratio of 100 to a ratio of 200.

3.6 Organic Analysis

The organic sample preparation and analysis methods were based on SW-846 methods which had been adapted for radioactive samples. The performance of these methods had been demonstrated according to the Transuranic Waste Characterization Program (TWCP) Quality Assurance Program Plan (QAPP)⁹ requirements. The amounts of sample extracted and analyzed for this project were limited to ensure contamination control and good ALARA practices. There was some interference problems with the W-25 sludge sample which reduced the sensitivity of the semivolatile organic compound analysis (SVOA) by a factor of two. The sensitivities of the volatile organic compound analysis (VOA), the non-halogenated volatile organic compound analysis (NHVOA), and the polychlorinated biphenyls (PCB) analysis were not reduced for any measurements.

3.6.1 Non-halogenated Volatile Organic Analysis (NHVOA)

The NHVOA measurements were done by SW-846 Method 8015A, Nonhalogenated Volatile Organics by Gas Chromatography. One gram of sludge or one milliliter of supernatant was extracted by shaking with 1 mL of water. This extraction was reduced two-fold from the method used in the TWCP, but it retained the same method detection limit (MDL) because the relative proportions of sample and solvent were not changed. A volume of 0.001 mL of the extract was injected onto each of two gas chromatography columns, and the organic compounds were detected by flame ionization and quantified using the method of external standards. A surrogate standard was added to all samples and quality control samples. The latter included a laboratory blank, matrix spike (MS) and spike duplicate (MSD) samples, and a laboratory control sample (LCS).

3.6.2 Volatile Organic Analysis (VOA)

The VOA measurements were done by SW-846 Method 8260A, Volatile Organic Compounds by Gas Chromatography/Mass Spectrometry (GC/MS): Capillary Column Technique. For sludge samples 1 g of solids was extracted by shaking with 1 mL of methanol. A 0.05 mL aliquot of the extract was added to 5 mL of water and was subjected to purge and trap gas chromatography-mass spectrometry (GC-MS). For the supernatant samples, the purge and trap GC-MS was done directly on 5 mL of each sample. Quantitation was by the method of internal standards. Surrogate standards were added to all samples and quality control samples. The latter included a laboratory blank, MS and MSD, and a LCS.

3.6.3 Semivolatile Organic Analysis

The SVOA measurements included SW-846 Method 3550A, Ultrasonic Extraction, for sample preparation, and SW-846 Method 8270B, Semivolatile Organic Compounds by Gas Chromatography / Mass Spectrometry (GC/MS): Capillary Column Technique, for sample analysis. For sludge samples, 10 g of solids were mixed with sodium sulfate until a free-flowing matrix was obtained, and the mixture was extracted with 100 mL of methylene chloride using an ultrasonic bath. For supernatant samples, 200 mL of liquid was extracted with 100 mL of methylene chloride according to SW-846 Method 3510, Separatory Funnel Liquid-Liquid Extraction. The methylene chloride was concentrated to 1 mL, and the extract was analyzed by GC-MS using the method of internal standards. Surrogate standards were added to all samples and quality control samples. The latter included a laboratory blank, MS and MSD, and a LCS.

3.6.4 Polychlorinated Biphenyls

The PCB measurements included SW-846 Method 3550A, Ultrasonic Extraction and Method 3665, Sulfuric Acid/Permanganate Cleanup, for sample preparation, and Method 8081, Organochlorine Pesticides and PCBs as Aroclors by Gas Chromatography: Capillary Column Technique, for sample analysis. A fraction of the SVOA methylene chloride extract was used for the PCB sample preparation. The extract was concentrated and solvent-exchanged into hexane, washed with sulfuric acid until the acid washes were colorless and did not contain precipitates, washed with water to remove excess acid, combined with a hexane back-extract of the acid washes, and then were concentrated to 1 mL. Analysis was conducted on a dual capillary column GC equipped with dual electron capture detectors using the method of external standards. A surrogate standard was added to all samples and quality control samples. The latter included a laboratory blank, MS and MSD, and a LCS.

4.0 Quality Assurance

Both the inorganic and organic chemical characterization of the MVST samples followed the method requirements and Data Quality Objectives (DQO) of the TWCP QAPP. The RMAL implements the TWCP QAPP with a flow down RMAL Quality Assurance Project Plan (QAPjP)¹⁰ and implementation procedures. The list of metals determined was expanded from the TWCP requirements to meet ORNL needs. Although the organic target compounds were those listed in the TWCP QAPP, the full set of semivolatile and volatile organic compounds for the EPA Contract Laboratory Program Target Compound List (TCL) were reported as Tentatively Identified Compounds (TIC), if they were detected in the samples.

Quality assurance during the sampling activities was primarily addressed by the use of approved procedures for sampling both the liquid and sludge phase found in each waste tank. These procedures provide detailed instructions for the collection, labeling, and shipping of each sample. Chain-of-custody forms were used to track individual samples from their collection point to the analytical laboratory.

The RMAL also operates under a Radioactive Waste Characterization QA Plan¹¹ which, in conjunction with the TWCP QAPjP, defines the basis for quality assurance and quality control used for the analysis of the waste tank samples. The QA plans discuss staff qualification requirements, laboratory participation in performance demonstration programs, quality control acceptance criteria for analytical methods, sample management, and most other laboratory operations. The set of QA plans implemented for RMAL waste characterization meet both the WIPP and the Nevada Test Site (NTS) QA requirements for inorganic, organic, and radiochemical measurements.

5.0 Summary of Inorganic and Radiochemical Analytical Results

5.1 Description of Data Tables

A summary of the inorganic, physical, and radiochemical analytical results are presented in Table 3 and Table 4 for the MVST supernatant samples, and the data for MVST sludge samples are presented in Table 5 and Table 6. These tables are arranged in a similar format to facilitate comparing data from different tanks and to group information into useful units. The analytical data presented in these tables are the consolidation of data from a single project which had a fixed set of analytical requirements. Any parameter reported with a dash ("-") indicates that the data was not measured for that sample.

The first section, "Physical properties and miscellaneous data", includes unrelated information that does not fit well into other table groups. The first parameters entered in a column include the RMAL request and sample numbers, which are laboratory filing codes used to track sample information. The next set of data includes information on the moisture or water content and the solids content of the sample. The group is completed with data on the inorganic and organic carbon content. For MVST waste tank samples the inorganic carbon can be assumed to be all carbonate and bicarbonate. The Total Organic Carbon (TOC) provides an upper limit on the organic content in the tank waste but does not include volatile organic compounds. Most of the liquid waste in the active system has been through an evaporator which removes the highly volatile organic compounds from the waste.

The next two sections include groups of metals; the "RCRA metals" are separated out for quick reference. The regulatory limit for the concentrations are listed in parentheses next to each RCRA metal. For the liquid samples the RCRA regulatory limits are used directly, since the supernatant would be defined as the TCLP leachate in the determination of waste characteristics for hazardous waste. The RCRA metal sludge data represents total metal measurements, as defined by EPA. Exceeding the RCRA regulatory limits listed for the sludge samples only indicates that the waste has the potential to be classified as hazardous. The sludge waste should only be classified as RCRA waste if the final waste form fails the TCLP leaching test.

The remaining metals are grouped under "Process metals", which includes the common Group IA & IIA metals along with elements that could effect chemical processing, criticality concerns, and stabilization techniques such as grouting or vitrification. For the sludge data, all the metals are reported on a "as received" (wet weight) basis.

The section "Semi-quantitative metals by ICP-MS" includes additional metals identified in a full mass range scan by inductively-coupled plasma - mass spectrometry. This measurement helps ensure all major elements have been identified in the waste. Each element reported is not calibrated but is based upon a response factor from a curve generated from a few elements across the mass range. Therefore, these elemental concentrations are listed as estimates only.

The "Calculated Alkalinity" and the "Anions by ion chromatography" sections are separate for the supernatant samples, but are combined for the sludge samples. For supernatant samples the pH is measured directly, and the anions are determined on the liquid samples after dilution with water. The pH and anions reported for the sludge samples are based on a water wash of the sludge, as discussed in section 3.3. Along with the inorganic anions, several water soluble organic acids are reported, which includes compounds classified as complexing agents such as citrate and oxalate.

The "Beta/gamma emitters" section summarizes the radionuclides that emit gamma-rays and beta particles. This section includes the gross beta activity, radionuclides identified by gamma spectrometry, and several "pure" beta emitters of interest. Many of the "pure" beta emitters (³H, ¹⁴C, and ⁹⁰Sr) require radiochemical separations prior to measurement by either liquid scintillation or gas-flow proportional counting. The ⁹⁹Tc was measured by ICP-MS without any prior chemical separation and the ¹⁵¹Sm were estimated by ICP-MS after a lanthanide group separation.

The "Alpha emitters" section summarize the actinide elements in the waste. These section includes the gross alpha activity, an estimate of the activity for each alpha emitter identified in a gross alpha spectrum, and plutonium isotopes determined by alpha spectrometry after a radiochemical separation. For supernatant samples, an estimate of the ²³²Th/²³⁹Pu mass ratio is included in this section to address criticality concerns if enough thorium is present to calculate the ratio. For the sludge samples, this mass ratio is included with the plutonium mass spectrometry data.

The remaining sections include "Uranium isotopes by TIMS" , "Plutonium isotopes by TIMS", and "Uranium isotopes by ICP-MS". These sections summarize the uranium and plutonium data measured by thermal ionization mass spectrometry and for comparison to the uranium isotopes measured by ICP-MS. Also, included in these sections are the isotopic mass dilution or "denature" ratios for uranium and plutonium based on the requirements in place when the waste was generated (see section 3.5). The plutonium section for the sludge samples also includes the activity for each plutonium isotope, which was calculated from the mass spectrometry data.

Table 3 Analytical Data for Liquids in Tanks W-24, W-25, and W-26

Characteristic

(Analysis)

W-24 L

W-25 L

W-26 L

IDLⁱ

Physical properties and miscellaneous data

Request number

Sample number

TS^a

TSS^b

Density

TC^c

TIC^d

TOC^e

(mg/mL)

(g/mL)

(mg/L)

7746C

960805-021

320

1.20

3630

3280

350

7746C

960805-022

360

1.22

2340

1730

610

7746B

960725-015

430

1.26

950

7.2

943

RCRA Metals ( ±10%)

Ag^f (5)^g

As (5)

Ba (100)

Cd (1)

Cr (5)

Hg (0.2)

Ni (5)

Pb (5)

Se (1)

Tl (0.9)

(mg/L)

< 0.03

0.0877

0.267

0.615

1.45

0.0763

0.526

0.335

< 0.03

0.0837

1.19

0.503

2.48

0.149

0.613

0.455

< 0.03

0.0942

2.99

0.407

1.03

0.877

4.23

0.0356

< 0.03

0.005

0.001

0.006

0.004

0.0002

0.009

0.005

Process metals ( ±10%)

Cs^h

Siⁱ

(mg/L)

20.0

1.14

0.0284

1.60

< 0.032

0.260

0.266

0.015

21500

< 0.042

< 0.002

70700

30.8

< 0.33

205

0.675

< 0.084

7.10

< 0.17

11.6

0.352

1.19

0.0033

2.01

< 0.032

0.225

0.132

< 0.0067

19000

< 0.042

< 0.002

79800

27.9

< 0.33

222

1.18

< 0.084

3.33

< 0.17

3.67

< 0.057

0.641

< 0.002

1390

0.618

0.516

0.324

0.020

41400

243

0.0134

80200

14.4

< 0.33

87.7

38.0

< 0.084

7.77

< 0.17

0.660

0.02

0.012

0.0009

0.01

0.007

0.005

0.002

0.003

0.08

0.020

0.0009

0.02

0.13

0.07

0.0003

0.04

0.07

0.02

Semi-quantitative metals by ICP-MS ( ±30-50 %)

Bi, bismuth

Ce, cerium

Ga, gallium

I, iodine

La, lanthanum

Li, lithium

Mo,molybdenum

Nb, niobium

Rb, rubidium

Sn, tin

Ti, titanium

W, tungsten

Zr, zirconium

(mg/L)

0.005

0.014

0.052

0.005

2.5

0.003

1.7

0.44

0.28

0.23

0.013

0.012

0.015

0.12

< 0.001

2.7

0.003

2.0

0.26

< 0.10

0.19

0.017

0.009

0.019

0.26

0.002

1.9

0.005

3.3

0.036

0.42

0.027

0.051

Calculated Alkalinity

Hydroxide

Carbonate

Bicarbonate

(pH)

(mM)

12.3

12.6

8.44

0.0

< 0.1

Anions by ion chromatography ( ±10%)

Inorganic

Bromide

Chloride

Chromate

Fluoride

Nitrate

Nitrite

Phosphate

Sulphate

Organic

Acetate

Citrate

Formate

Oxalate

Phthalate

(mg/L)

(M)

(mg/L)

(mg/L) (mg/L)

(mg/L)

4490

< 20

74.1

254000

4.10

1790

10.5

2060

332

< 10

169

303

< 10

4590

< 20

64.9

297000

4.79

2000

< 10

2130

297

< 10

167

307

< 10

4540

< 20

< 5.0

361000

5.82

2260

< 10

3170

465

< 10

224

< 10

0.05

0.01

0.05

0.10

0.20

0.10

Beta/gamma emitters ( ±10%)

Gross beta

⁶⁰Co

⁹⁰Sr/⁹⁰Y

⁹⁹Tc

¹²⁹I

¹³⁴Cs

¹³⁷Cs

¹⁵²Eu

¹⁵⁴Eu

¹⁵⁵Eu

(Bq/mL)

1.2e+06

2.0e+02

5.8e+03

7.7e+02

2.5e -01

4.0e+04

1.1e+06

< 6.0e+02

< 4.0e+02

< 2.0e+03

1.3e+06

1.8e+02

1.6e+03

7.4e+02

2.9e -01

4.5e+04

1.1e+06

< 5.0e+02

< 4.0e+02

< 2.0e+03

1.7e+06

2.2e+03

2.5e+04

1.9e+03

7.8e -02

2.0e+04

1.4e+06

< 9.0e+02

< 5.0e+02

< 2.0e+03

Alpha emitters ( ±10%)

Gross alpha

²⁴⁴Cm

²³⁹Pu/²⁴⁰Pu

²³⁸Pu/²⁴¹Am

Total Pu alpha

²³⁸Pu

²³⁹Pu/²⁴⁰Pu

²⁴²Pu

(Bq/mL)

1.8

1.1

0.67

0.01

< 1

0.96

0.59

0.35

0.03

< 1

Uranium isotopics by TIMS ( ±0.5%)

²³³U

²³⁴U

²³⁵U

²³⁶U

²³⁸U

²³³U/MS

²³⁵U/MS

²³⁸U/²³⁵U FEM

(atom %)

(ng/mL)

0.11

< 0.01

0.29

0.01

99.59

7.7

20.3

231

0.11

< 0.01

0.35

0.01

99.53

3.6

11.5

203

0.14

< 0.01

0.26

< 0.01

99.60

10.6

19.9

225

0.01

U activity

²³³U

²³⁴U

²³⁵U

²³⁶U

²³⁸U

(Bq/mL)

2.7

< 0.1

0.1

1.3

< 0.1

3.8

< 0.1

0.1

(a)Total solids, (b) TSS is zero because suspended solids were removed prior to analysis, (c) Total carbon, (d) Total inorganic carbon, (e) Total organic carbon, (f) nitric-hydrochloric acid prep., (g) RCRA regulatory limits, (h) measured by ICP-MS, (i) nitric-hydrofluoric acid prep., (j) Instrument detection limits.

Table 4 Analytical Data for Liquids in Tanks W-27, W-28, and W-31

Characteristic

(Analysis)

W-27 L

W-28 L

W-31 L

IDLⁱ

Physical properties and miscellaneous data

Request number

Sample number

TS^a

TSS^b

Density

TC^c

TIC^d

TOC^e

(mg/mL)

(g/mL)

(mg/L)

7746B

960725-016

390

1.24

401

161

240

7746A

960711-009

580

1.34

811

36.3

775

7746A

960711-028

440

1.26

1156

407

749

RCRA Metals ( ±10%)

Ag^f (5)^g

As (5)

Ba (100)

Cd (1)

Cr (5)

Hg (0.2)

Ni (5)

Pb (5)

Se (1)

Tl (0.9)

(mg/L)

< 0.03

5.21

< 0.03

2.98

0.288

0.919

0.0917

< 0.03

6.13

0.142

0.499

0.205

1.37

< 0.03

0.0316

1.38

0.431

7.74

2.28

0.544

0.154

< 0.03

0.005

0.001

0.006

0.004

0.0002

0.009

0.005

Process metals ( ±10%)

Cs^h

Siⁱ

(mg/L)

< 0.057

0.428

< 0.002

117

< 0.03

0.104

0.008

< 0.007

9970

0.331

< 0.002

91100

12.6

< 0.33

41.0

38.1

< 0.08

0.708

< 0.17

0.220

2.99

0.590

< 0.002

9300

0.0735

0.161

0.586

0.175

32200

1760

0.020

117000

7.23

< 0.33

108

81.3

< 0.08

145

< 0.17

0.421

2.29

0.593

< 0.002

7.20

< 0.03

0.202

0.272

0.0418

16600

1.33

0.005

103000

28.9

< 0.33

248

1.35

0.200

60.8

< 0.17

0.486

0.02

0.012

0.0009

0.01

0.007

0.005

0.002

0.003

0.08

0.020

0.0009

0.02

0.13

0.07

0.0003

0.04

0.07

0.02

Semi-quantitative metals by ICP-MS ( ±30-50 %)

Bi, bismuth

Ce, cerium

Ga, gallium

I, iodine

La, lanthanum

Li, lithium

Mo,molybdenum

Nb, niobium

Rb, rubidium

Sn, tin

Ti, titanium

W, tungsten

Zr, zirconium

(mg/L)

0.009

< 0.001

0.48

9.9

0.007

0.95

0.011

1.4

2.2

0.40

0.031

0.045

< 0.001

0.011

0.53

7.4

0.002

120

0.79

0.003

3.1

< 0.001

0.53

0.011

0.066

0.017

0.022

0.13

< 0.001

1.3

0.003

2.2

3.1

0.069

0.052

0.018

Calculated Alkalinity

Hydroxide

Carbonate

Bicarbonate

(pH)

(mM)

12.8

2.7

0.0

7.3

0.0

< 0.6

10.0

0.1

6.8

0.0

Anions by ion chromatography ( ±10%)

Inorganic

Bromide

Chloride

Chromate

Fluoride

Nitrate

Nitrite

Phosphate

Sulphate

Organic

Acetate

Citrate

Formate

Oxalate

Phthalate

(mg/L)

(M)

(mg/L)

(mg/L) (mg/L)

(mg/L)

3160

< 20

< 5

340000

5.48

2070

< 10

1510

145

< 10

119

< 10

5820

< 20

< 5

506000

8.16

1430

< 10

2070

596

< 10

208

10.3

< 10

4200

56.2

17.9

391000

6.31

4430

< 10

1850

350

< 10

249

165

< 10

0.05

0.01

0.05

0.10

0.20

0.10

Beta/gamma emitters ( ±10%)

Gross beta

⁶⁰Co

⁹⁰Sr/⁹⁰Y

⁹⁹Tc

¹²⁹I

¹³⁴Cs

¹³⁷Cs

¹⁵²Eu

¹⁵⁴Eu

¹⁵⁵Eu

(Bq/mL)

4.4e+05

3.2e+02

9.5e+04

2.2e+02

1.4e -02

6.3e+02

2.8e+05

< 8.0e+01

< 9.0e+01

< 5.0e+02

9.8e+05

3.7e+03

1.5e+05

4.1e+02

1.9e -02

2.4e+03

5.7e+05

< 2.0e+02

< 6.0e+02

5.4e+05

2.7e+02

1.5e+04

5.8e+02

6.5e -02

8.0e+03

4.3e+05

< 2.0e+02

< 6.0e+02

Alpha emitters ( ±10%)

Gross alpha

²⁴⁴Cm

²³⁹Pu/²⁴⁰Pu

²³⁸Pu/²⁴¹Am

Total Pu alpha

²³⁸Pu

²³⁹Pu/²⁴⁰Pu

²⁴²Pu

(Bq/mL)

4.4

< 1

140

< 1

6.2

3.7

2.5

< 0.1

Uranium isotopics by TIMS ( ±0.5%)

²³³U

²³⁴U

²³⁵U

²³⁶U

²³⁸U

²³³U/MS

²³⁵U/MS

²³⁸U/²³⁵U FEM

(atom %)

(ng/mL)

0.10

< 0.01

0.26

< 0.01

99.63

0.7

1.8

256

0.12

< 0.01

0.24

< 0.01

99.63

170

344

252

0.11

< 0.01

0.30

0.01

99.58

65.5

180

226

0.01

U activity

²³³U

²³⁴U

²³⁵U

²³⁶U

²³⁸U

(Bq/mL)

0.2

< 0.1

60.8

< 0.1

1.8

23.4

< 0.1

0.8

Table 5 Analytical Data for Sludge in Tanks W-24, W-25, and W-26

Characteristic

(Analysis)

W-24 S

W-25 S

W-26 S

IDL^j

Physical properties and miscellaneous data

Request number

Sample number

Water^a

TS^b

Bulk density

TC^c

TIC^d

TOC^e

(%)

(mg/g)

(g/mL)

(mg/Kg)

7749C

960806-006

12.8

51.2

488

1.37

13700

< 15

7749D

960822-036

12.6

50.9

491

1.36

15700

< 15

7749E

960830-044

9.7

50.9

491

1.38

13500

11600

1900

RCRA Metals ( ±10%)

Ag^f (100)^g

As (100)

Ba (2000)

Cd (20)

Cr (100)

Hg (4)

Ni (1000)

Pb (100)

Se (20)

Tl (18)

(mg/Kg)

< 1.9

< 5.3

75.5

13.9

61.6

38.0

45.2

303

< 5.3

< 1.8

< 1.3

105

11.9

92.1

73.2

56.8

442

< 1.3

< 1.9

< 1.4

63.1

19.8

74.4

12.7

42.8

212

< 1.4

0.005

0.001

0.006

0.004

0.0002

0.009

0.005

Process metals ( ±10%)

Cs^h

Si ⁱ

(mg/Kg)

3330

4.35

4.45

51200

2.42

28.5

0.900

1250

13400

9280

84.7

48800

1240

< 19

3820

283

3270

6780

2.23

479

5810

3.76

6.91

50800

5.86

37.0

0.857

1810

8850

7650

140

52100

1850

114

8890

325

9250

7660

3.85

285

1980

11.3

1.85

45900

2.69

29.0

1.53

1010

25300

14700

102

48900

1070

52.8

2100

254

3280

19400

2.32

405

0.02

0.012

0.0009

0.01

0.007

0.002

0.005

0.003

0.08

0.020

0.0009

0.02

0.13

0.013

0.0003

0.04

0.07

0.02

Semi-quantitative metals by ICP-MS ( ±30-50 %, * indicates data from water leach)

Au, gold

Bi, bismuth

Ce, cerium

Er, erbium

Eu, europium

Ga, gallium

Gd, gadolinium

Ho, holmium

I, iodine

La, lanthanum

Li, lithium

Mo,molybdenum

Nb, niobium

Rb, rubidium

Sn, tin

Ti, titanium

W, tungsten

Zr, zirconium

(mg/Kg)

1.5

170

6.5

0.25

1.1

5.3

1.2

1.0

* 13

9.1

* 170

* 2.1

0.93

* 1.4

1.0

8.4

0.28

250

9.4

0.02

2.1

8.1

1.7

2.0

* 12

* 33

* 2.0

0.72

* 1.0

0.61

0.92

5.5

0.24

2.3

4.0

6.4

1.0

* 12

4.8

* 76

* 2.2

0.22

* 2.5

7.3

3.2

1.5

5.4

Anions by ion chromatography in water wash of sludge ( ±10%)

Inorganic

Bromide

Chloride

Chromate

Fluoride

Nitrate

Nitrite

Phosphate

Sulphate

Organic

Acetate

Citrate

Formate

Oxalate

Phthalate

(mg/Kg)

(mg/Kg) (mg/Kg)

(mg/Kg)

< 50

2770

< 20

103

165000

2250

< 20

1370

242

< 20

175

690

< 20

< 50

2110

95.5

118

162000

4967

< 20

1750

318

< 20

247

521

< 20

< 50

3070

< 20

< 50

214000

1652

< 20

2120

336

< 20

243

44.2

< 20

0.05

0.01

0.05

0.10

0.20

0.10

Beta/gamma emitters ( ±10%)

Gross beta

⁵⁹Ni

⁶³Ni

⁶⁰Co

⁹⁰Sr/⁹⁰Y

⁹⁹Tc

¹²⁹I

¹³⁴Cs

¹³⁷Cs

¹⁵¹Sm

¹⁵²Eu

¹⁵⁴Eu

¹⁵⁵Eu

²²⁷Ac

²⁴¹Pu

(Bq/g)

4.6e+06

< 2.5e+01

3.3e+03

2.8e+04

1.4e+06

4.5e+02

1.3e+04

5.3e+05

< 6.0e+02

8.9e+04

3.8e+04

1.0e+04

< 4.7e+03

1.4e+04

8.3e+06

< 2.5e+01

3.4e+03

2.5e+04

3.2e+06

1.0e+02

6.0e+03

4.7e+05

< 5.5e+02

7.1e+04

3.7e+04

8.4e+03

< 5.3e+03

2.6e+04

3.5e+06

< 3.0e+01

4.0e+03

5.8e+04

7.1e+05

1.2e+03

1.2e+04

8.9e+05

< 5.8e+02

6.4e+05

2.9e+05

6.3e+04

< 9.3e+03

1.5e+04

Alpha emitters ( ±10%)

Gross alpha

²³²Th

²³³U

²³⁴U

²³⁵U

²³⁸U

²³⁷Np

²⁴¹Am

²⁴⁴Cm

²⁵⁰Cf

²⁵²Cf

Total Pu alpha

²³⁸Pu

²³⁹Pu/²⁴⁰Pu

²⁴²Pu

TRU activity

Pu+Am (3700)

(Bq/g)

34000

1600

2.6

1.0

3900

22000

< 100

6600

4000

2600

10500

83000

2800

100

3.2

1.1

9300

58000

< 100

13000

7700

4900

22300

52000

10000

180

4.0

2.8

3900

28000

< 100

7600

5300

2300

11500

Uranium isotopics by TIMS ( ±0.5%)

²³³U

²³⁴U

²³⁵U

²³⁶U

²³⁸U

²³³U/MS

²³⁵U/MS

²³⁸U/²³⁵U FEM

(atom %)

(mg/Kg)

0.054

0.003

0.496

0.005

99.442

3.58

33.2

177

0.088

0.006

0.542

0.006

99.358

6.60

45.2

153

0.132

0.003

0.268

0.005

99.592

25.1

51.3

227

0.001

Uranium isotopics by ICP-MS ( ±2%)

²³³U

²³⁴U

²³⁵U

²³⁶U

²³⁸U

²³³U/MS

²³⁵U/MS

²³⁸U/²³⁵U FEM

(atom %)

(mg/Kg)

0.067

0.005

0.543

0.006

99.379

4.45

36.4

159

0.103

0.006

0.597

0.006

99.289

7.72

45.2

137

0.152

0.004

0.296

0.006

99.543

28.9

56.7

202

0.001

Plutonium isotopics by TIMS ( ±1%)

²³⁸Pu

²³⁹Pu

²⁴⁰Pu

²⁴¹Pu

²⁴²Pu

²⁴⁴Pu

(atom %)

0.63

87.14

10.81

0.37

1.05

< 0.01

0.72

84.95

12.42

0.40

1.51

< 0.01

1.23

82.27

15.11

0.57

0.81

< 0.01

Pu activity

²³⁸Pu

²³⁹Pu

²⁴⁰Pu

²⁴¹Pu

²⁴²Pu

²⁴⁴Pu

(²³⁹Pu)

²³²Th/²³⁹Pu

(Bq/g)

(ng/g)

3800

1900

870

14000

1.5

< 0.1

960

3920

7800

3400

1800

26000

3.8

< 0.1

1700

6320

5400

1300

890

15000

0.8

< 0.1

700

5730

(a) Free water content of sludge, (b) Total solids, (c) Total carbon, (d) Total inorganic carbon, (e) Total organic carbon, (f) nitric-hydrochloric acid prep., (g) RCRA regulatory limits, (h) measured by ICP-MS or GFAA, (i) nitric-hydrofluoric acid prep., (j) Instrument detection limits.

Table 6 Analytical Data for Sludge in Tanks W-27, W-28, and W-31

Characteristic
(Analysis)

W-27 S

W-28 S

W-31 S

IDLⁱ

Physical properties and miscellaneous data

Request number
Sample number

pH

Water^a
TS^b
Bulk density
TC^c
TIC^d
TOC^e

(%)
(mg/g)
(g/mL)
(mg/Kg)
(mg/Kg)
(mg/Kg)
7749F
960904-248

12.3

54.9
451
1.44
12400
10000
2400
7749B
960724-060

12.3

47.3
527
1.37
12800
10200
2600
7749A
960717-023

9.9

51.4
486
1.44
10200
5300
4900
-
-

-

-
-
-
15
15
15

RCRA Metals ( ±10%)

Ag^f (100)^g
As (100)
Ba (2000)
Cd (20)
Cr (100)
Hg (4)
Ni (1000)
Pb (100)
Se (20)
Tl (18)
(mg/Kg)
(mg/Kg)
(mg/Kg)
(mg/Kg)
(mg/Kg)
(mg/Kg)
(mg/Kg)
(mg/Kg)
(mg/Kg)
(mg/Kg)
< 1.8
< 1.4
41.8
14.8
55.3
29.0
48.9
157
< 1.4
< 1.4
< 1.8
< 5.0
43.3
24.9
54.8
6.55
53.6
195
< 5.0
5.97
< 1.9
< 5.0
124
9.03
130
70.7
104
764
< 5.0
< 5.0
0.005
0.005
0.001
0.006
0.004
0.0002
0.009
0.005
0.005
0.005

Process metals ( ±10%)

Al
B
Be
Ca
Co
Cu
Cs^h
Fe
K
Mg
Mn
Na
P
Sb
Siⁱ
Sr
Th
U
V
Zn
(mg/Kg)
(mg/Kg)
(mg/Kg)
(mg/Kg)
(mg/Kg)
(mg/Kg)
(mg/Kg)
(mg/Kg)
(mg/Kg)
(mg/Kg)
(mg/Kg)
(mg/Kg)
(mg/Kg)
(mg/Kg)
(mg/Kg)
(mg/Kg)
(mg/Kg)
(mg/Kg)
(mg/Kg)
(mg/Kg)
2250
5.98
1.10
43700
2.57
14.2
0.892
935
6970
7820
65.4
58200
1000
37.4
3860
107
1290
11700
3.31
360
571
7.33
1.36
45800
3.53
28.0
0.480
599
14600
14500
91.0
61000
907
< 18
1080
151
1360
18500
1.54
278
12700
11.6
21.0
24100
4.76
80.2
0.543
2820
8320
2170
247
60600
4240
< 19
10200
174
20700
19800
7.18
125
0.02
0.012
0.0009
0.01
0.007
0.002
0.005
0.003
0.08
0.020
0.0009
0.02
0.02
0.13
0.013
0.0003
0.04
0.07
0.02
0.02

Semi-quantitative metals by ICP-MS ( ±30-50 %, * indicates data from water leach)

Au, gold
Bi, bismuth
Ce, cerium
Er, erbium
Eu, europium
Ga, gallium
Gd, gadolinium
Ho, holmium
I, iodine
La, lanthanum
Li, lithium
Mo,molybdenum
Nb, niobium
Rb, rubidium
Sn, tin
Ti, titanium
W, tungsten
Zr, zirconium
(mg/Kg)
(mg/Kg)
(mg/Kg)
(mg/Kg)
(mg/Kg)
(mg/Kg)
(mg/Kg)
(mg/Kg)
(mg/Kg)
(mg/Kg)
(mg/Kg)
(mg/Kg)
(mg/Kg)
(mg/Kg)
(mg/Kg)
(mg/Kg)
(mg/Kg)
(mg/Kg)
0.62
130
7.2
0.12
0.80
4.2
1.9
1.6
* 6.8
7.3
* 53
* 2.0
0.56
* 1.2
4.0
99
1.3
4.0
1.9
12
7.9
0.07
1.5
3.1
6.0
0.97
* 9.1
2.0
* 170
* 2.3
0.30
* 1.9
5.9
4.1
1.4
1.8
2.6
1200
20
0.85
0.54
12
0.75
0.22
* 20
54
* 81
* 1.4
2.0
* 1.3
40
34
1.3
51
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-

Anions by ion chromatography in water wash of sludge ( ±10%)

Inorganic
Bromide
Chloride
Chromate
Fluoride
Nitrate
Nitrite
Phosphate
Sulphate
Organic
Acetate
Citrate
Formate
Oxalate
Phthalate

(mg/Kg)
(mg/Kg)
(mg/Kg)
(mg/Kg)
(mg/Kg)
(mg/Kg)
(mg/Kg)
(mg/Kg)

(mg/Kg)
(mg/Kg)
(mg/Kg) (mg/Kg)
(mg/Kg)

< 50
2280
< 20
< 50
210000
2283
< 20
549

196
< 20
200
16.0
< 20

< 50
3460
< 20
< 50
248000
1120
< 20
1773

325
< 20
271
19.1
< 20

< 50
2570
51.5
125
197000
3470
< 50
1090

237
< 50
251
89.8
< 50

0.05
0.05
0.01
0.05
0.10
0.10
0.20
0.10

-
-
-
-
-

Beta/gamma emitters ( ±10%)

Gross beta
⁵⁹Ni
⁶³Ni
⁶⁰Co
⁹⁰Sr/⁹⁰Y
⁹⁹Tc
¹²⁹I
¹³⁴Cs
¹³⁷Cs
¹⁵¹Sm
¹⁵²Eu
¹⁵⁴Eu
¹⁵⁵Eu
²²⁷Ac
²⁴¹Pu
(Bq/g)
(Bq/g)
(Bq/g)
(Bq/g)
(Bq/g)
(Bq/g)
(Bq/g)
(Bq/g)
(Bq/g)
(Bq/g)
(Bq/g)
(Bq/g)
(Bq/g)
(Bq/g)
(Bq/g)
1.6e+06
< 2.0e+01
1.7e+03
1.2e+04
4.5e+05
8.7e+01
-
< 8.1e+02
3.9e+05
< 5.7e+02
4.1e+04
1.7e+04
< 2.7e+03
< 6.2e+03
6.5e+03
3.1e+06
<2.5e+01
3.3e+03
4.2e+04
7.0e+05
1.2e+02
4.1e - 02
< 1.2e+03
3.1e+05
< 5.6e+02
8.0e+05
2.7e+05
7.0e+04
< 6.7e+03
1.2e+04
2.4e+07
< 3.3e+01
4.4e+03
2.2e+04
1.1e+07
1.4e+02
4.5e - 02
2.5e+03
4.3e+05
< 6.0e+02
3.0e+04
2.0e+04
< 3.4e+03
< 5.8e+03
2.4e+04
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-

Alpha emitters ( ±10%)

Gross alpha
²³²Th
²³³U
²³⁴U
²³⁵U
²³⁸U
²³⁷Np
²⁴¹Am
²⁴⁴Cm
²⁵⁰Cf
²⁵²Cf

Total Pu alpha
²³⁸Pu
²³⁹Pu/²⁴⁰Pu
²⁴²Pu

TRU activity
Pu+Am (3700)
(Bq/g)
(Bq/g)
(Bq/g)
(Bq/g)
(Bq/g)
(Bq/g)
(Bq/g)
(Bq/g)
(Bq/g)
(Bq/g)
(Bq/g)

(Bq/g)
(Bq/g)
(Bq/g)
(Bq/g)

(Bq/g)
26000
5.2
1000
53
2.5
1.7
12
2800
17000
< 100
< 100

3400
2200
1200
-

6200
44000
5.5
5200
130
3.8
3.1
16
4600
25000
< 100
< 100

4400
2700
1700
-

9000
160000
84
5200
310
10
1.9
21
14000
110000
< 100
< 100

19000
13000
6200
-

33000
-
-
-
-
-
-
-
-
-
-
-

-
-
-
-

-

Uranium isotopics by TIMS ( ±0.5%)

²³³U
²³⁴U
²³⁵U
²³⁶U
²³⁸U

²³³U/MS
²³⁵U/MS
²³⁸U/²³⁵U FEM
(atom %)
(atom %)
(atom %)
(atom %)
(atom %)

(mg/Kg)
(mg/Kg)
-
0.022
0.002
0.309
0.005
99.662

2.52
35.7
298
0.066
0.003
0.253
0.007
99.671

12.0
46.2
296
0.056
0.004
0.621
0.002
99.316

10.9
121
145
0.01
0.01
0.01
0.01
0.01

-
-
-

Uranium isotopics by ICP-MS ( ±2%)

²³³U
²³⁴U
²³⁵U
²³⁶U
²³⁸U

²³³U/MS
²³⁵U/MS
²³⁸U/²³⁵U FEM
(atom %)
(atom %)
(atom %)
(atom %)
(atom %)

(mg/Kg)
(mg/Kg)
-
0.025
0.002
0.308
0.006
99.660

2.86
35.6
296
0.081
0.003
0.296
0.007
99.613

14.7
54.1
249
0.075
0.007
0.750
0.004
99.165

14.5
150
118
0.01
0.01
0.01
0.01
0.01

-
-
-

Plutonium isotopics by TIMS ( ±1%)

²³⁸Pu
²³⁹Pu
²⁴⁰Pu
²⁴¹Pu
²⁴²Pu
²⁴⁴Pu
(atom %)
(atom %)
(atom %)
(atom %)
(atom %)
(atom %)
1.08
84.88
12.64
0.49
0.91
< 0.01
< 1.06
81.54
15.93
0.70
0.76
0.01
< 1.16
81.94
14.55
0.34
1.9
0.11
-
-
-
-
-
-

Pu activity
²³⁸Pu
²³⁹Pu
²⁴⁰Pu
²⁴¹Pu
²⁴²Pu
²⁴⁴Pu

(²³⁹Pu)
²³²Th/²³⁹Pu

(Bq/g)
(Bq/g)
(Bq/g)
(Bq/g)
(Bq/g)
(Bq/g)

(ng/g)

2400
670
370
6500
0.5
< 0.1

350
4390

3000
830
600
12000
0.5
< 0.1

440
3750

13000
3400
2200
24000
5.1
< 0.1

1820
13800

-
-
-
-
-
-

-
-

(a) Free water content of sludge, (b) Total solids, (c) Total carbon, (d) Total inorganic carbon, (e) Total organic carbon, (f) nitric-hydrochloric acid prep., (g) RCRA regulatory limits, (h) measured by ICP-MS or GFAA, (i) nitric-hydrofluoric acid prep., (j) Instrument detection limits.

5.2 Discussion of MVST Supernatant Characteristics

The analytical data for the MVST supernatant samples are presented in Tables 3 and 4. This data is based on samples that were first clarified by centrifugation and then stabilized with nitric acid. Extra care was taken to remove suspended particles from the liquid samples because the particulate material was an artifact of the sampling technique and could bias the liquid phase data. If the pH is above 12, most compounds of thorium, uranium and other actinide elements in the ORNL waste tanks form an insoluble precipitate. This chemical behavior is apparent with the supernatant data when the pH is compared to the uranium concentration and the alpha activity. For example, with tanks W-28 at pH=7.3 and W-31 at pH=10, the uranium increases to 145 mg/L and 60.8 mg/L, respectively. With tanks W-24, W-25, and W-27, where the pH>12, the uranium concentration is less than 10 mg/L. If higher levels of uranium are observed at pH>12, it usually indicates that there are suspended particles of insoluble uranium present.

The Group IA elements, sodium and potassium, are very soluble in the supernatant at any pH. In general, the concentration of Group IIA metals, calcium and strontium, increases in the supernatant as the pH decreases. These Group IIA metals remain somewhat soluble in the liquid phase, even at high pH, unless the supernatant has absorbed some carbon dioxide from the air, which forms insoluble carbonate compounds with both calcium and strontium. The general distribution of radioactivity in the MVST tanks is a function of the pH, where at higher pH the ¹³⁷Cs dominates the beta activity in the liquid phase and the ⁹⁰Sr/⁹⁰Y is the predominate source of the beta activity in the sludge phase. At high pH, the actinide elements are mostly insoluble which corresponds to most of the alpha activity being concentrated in the sludge phase.

As expected, the concentration of silicon compounds increases in the supernatant as the pH increases. Many of the other common metals found in the waste, such as iron and magnesium, are less soluble as the pH increases. In general, as the pH decreases, the total dissolved solids in the supernatant increases. Figure 1 and Fig. 2, illustrate the distribution of major cations and anions in the MVST liquid samples. Figure 2 is similar to Fig. 1, but with the sodium and nitrate removed to show more detail for species present at lower concentrations.

Figure 1 Distribution of Major Cations and Anions in Liquid Phase

Figure 2 Distribution of Selected Ionic Species in Liquid Phase

The sludge layers in the ORNL waste tanks are typically high in several RCRA metals, including chromium, mercury, and lead. At high pH these RCRA metals are below the hazard limits in the supernatant, but as the pH decreases the concentration of these RCRA metals can increase to the point where the regulatory limits are exceeded in the liquid phase.

A good check for data completeness is the mass and charge balance, which are summarized in Table 7 for the MVST supernatant samples. The mass balance check is based on the summation of cation and anion concentrations divided by the total solids concentration. The total solids concentration is measured directly by weighing a known volume of sample that has been dried to a constant weight. The mass balance data shows a high bias of 12-20% for the MVST supernatant samples. The charge balance checks are less accurate than the mass balance check because one must make an assumption about the chemical form and oxidation state for each species present in solution. The charge balance data is based on the summation of the molar cation charge divided by the summation of the molar anion charge. The charge balance data shows fair agreement but with a positive bias ranging from 22-34% for the MVST liquid samples. The charge balance data is acceptable considering the assumptions required for the calculation. The loss of nitrate as volatile oxides of nitrogen is one possible explanation for the high bias observed for both the total solids and the charge balance. For both the mass and charge balance checks on the supernatant samples, the calculations were dominated by the sodium, potassium, and nitrate concentration.

Table 7 Summary of Quality Checks for MVST Supernatant Data

Tank	Mass Balance (TS_calc./TS_meas.)	Charge Balance (M⁺/A^-)	pH	¹³⁴Cs+¹³⁷Cs (%)	⁹⁰Sr/⁹⁰Y (%)	Beta Recovery (%)
W-24	1.12	1.22	12.3	99.06	0.87	111
W-25	1.13	1.28	12.6	99.69	0.24	103
W-26	1.15	1.31	8.4	96.83	2.93	101
W-27	1.15	1.34	12.8	63.21	36.68	118
W-28	1.17	1.29	7.3	68.70	30.87	99
W-31	1.19	1.34	10.0	92.79	5.55	100

The beta recovery listed in Table 7 is based on the summation of the activity for the known beta emitters divided by the gross beta activity. Considering the typical analytical errors associated which radiochemical measurements, the beta recoveries listed in Table 7 are excellent. The gross beta data reported is based on a total activity measurement by liquid scintillation counting which includes contributions from the conversion and Auger electrons. To determine the beta recovery, the total activity measurement minus the alpha activity is the gross beta value that is compared to the summation of the individual radionuclides identified. Also, one must take into account the large effect that analytical error for the radioactive strontium activity can have on the value of the beta recovery. Since the ⁹⁰Sr is in secular equilibrium with the⁹⁰Y, any error on the ⁹⁰Sr activity would be doubled when calculating the beta recovery.

Another point of interest in Table 7 is that the distribution of ¹³⁷Cs is independent of pH, and that the ⁹⁰Sr activity is a function of both pH and carbonate concentration. At the most basic pH observed, almost all of the ⁹⁰Sr is precipitated into the sludge. As the basic environment becomes more acidic, the ⁹⁰Sr activity slowly increases in the supernatant. There was a significant jump in the relative ⁹⁰Sr activity observed in the supernatant when the pH dropped below pH=9.

Tank W-27 appears to be an exception to this behavior, however, the elevated levels of radioactive strontium observed in the highly basic environment was due to the recent history with the tank chemistry. Tank W-27 had a pH in the same range as tank W-28 (pH=7.3) until one month prior to the sample being collected. Sodium hydroxide was added to tank W-27 until the pH was greater than pH=12 and the supernatant was allowed to set undisturbed until the samples were taken for this project. The solubility of the strontium is dependent upon the concentration of carbonate, which was very low prior to the addition of the sodium hydroxide. There was insufficient time for the basic liquid to absorb carbon dioxide from the air and increase the carbonate concentration to a level that would precipitate the strontium (the calcium is also higher than expected at the high pH for the same reason).

Under conditions where the pH was high and the carbonate concentration was low, it is possible for the ⁹⁰Sr to remain soluble and the ⁹⁰Y to precipitate as the hydroxide and disrupt the secular equilibrium. It is important to understand any conditions that could disrupt this equilibrium because some radiochemical screening techniques and the interpretation of beta dose assume that the ⁹⁰Y activity is equal to the ⁹⁰Sr activity. The separation of the strontium from the yttrium is frequently observed with ⁹⁰Sr contaminated water moving through soil. The soluble ⁹⁰Sr moves with the water and the ⁹⁰Y is absorbed to the soil by an ion exchange process. Past practices used clay based materials as a mobilizing agent for pumping sludge. Therefore, the sludge may have an ion exchange affinity for yttrium or other radionuclides, which could interfere with the expected behavior for some radionuclides or other chemical species.

In general, the beta/gamma emitters found in the supernatant represent what would be expected for fission product waste that had been aged for several years. The relative distribution of the beta activity in the MVST supernatant is summarized in Table 8. The distribution of the activity in these MVST supernatant samples is typical of ORNL liquid waste. The ORNL liquid waste is normally stored at a caustic pH and the radioactive cesium dominates the activity. The pH in tank W-28 is lower than normal and there is a corresponding increase in the strontium and uranium in the liquid phase.

Table 8 Distribution of Beta Activity in Supernatant

Tank	pH	Percent of Total Beta Activity				Uranium (mg/L)
Tank	pH	⁹⁰Sr/⁹⁰Y (%)	⁹⁹Tc (%)	¹³⁴Cs (%)	¹³⁷Cs (%)	Uranium (mg/L)
W-24	12.3	0.87	0.06	3.04	96.02	7.1
W-25	12.6	0.24	0.06	3.43	96.26	3.3
W-26	8.4	2.93	0.11	1.19	95.64	7.8
W-27	12.8	36.68^a	0.04	0.12	63.09	0.71
W-28	7.3	30.87	0.04	0.25	68.45	150
W-31	10.0	5.55	0.11	1.50	92.79	61

^a See previous discussion on tank W-27 concerning high strontium activity.

The alpha activity in the supernatant is low, as would be expected with a caustic pH. The small amount of alpha activity that is observed in the liquid phase can not be accounted for with the uranium present, however, the mass of the uranium present is much higher than the other actinide elements. Below pH = 12, the uranium forms a complex with the carbonate present and becomes more soluble as the pH decreases. As can be seen in Table 8, at the higher pH the uranium concentration is generally below 10 mg/L, but in tank W-28 where the pH drops to 7.3, the uranium concentration increases significantly.

The alpha content in the MVST supernatant is usually very low at higher pH, but can increase if the pH is allowed to decrease too low. The alpha activity for the supernatant samples varies from <1 to 140 Bq/mL. Based on past experience, the alpha activity is likely due to suspended particles which are usually dominated by the ²⁴⁴Cm alpha activity present. The uranium contribution to the total alpha activity is typically minor relative to the ²⁴⁴Cm activity present in ORNL waste.

5.3 Discussion of MVST Sludge Characteristics

Determination of the mass and charge balance for the sludge samples are more difficult than for the supernatant samples. Not only are there assumptions required about the chemical form and the oxidation state of the species present in the sludge, but many of the compounds in the sludge are mixed oxides which are not directly measured. Also, the sludge is actually a slurry with a high water content. The interstitial liquid is in close contact with the sludge, and there are many ionic solubility equilibriums. The anion data for the sludge samples are based on the water soluble anions that would be available to a water wash. The water wash would not account for the insoluble hydroxides, carbonates, and mixed oxides present. The insoluble species do not contribute to the charge balance, and the cation charge is not used in the calculation, as indicated in Table 9. Most of the nitrate reported for the sludge is due to the interstitial liquid. Considering these limitations, the compounds listed in Table 9 were used to estimate the mass and charge balance.

Table 9 Assumption Used for Major Compounds in MVST Sludge

Cation	Chemical Form	Cation Charge Used	Gravimetric Factors
Al³⁺	Al₂O₃	0	1.890
Ca²⁺	CaCO₃	0	2.497
Fe³⁺	Fe₂O₃	0	1.430
K⁺	K⁺NO₃^-	+1	2.586
Mg²⁺	Mg(OH)₂	0	2.399
Mn²⁺	Mn(OH)₂	0	1.619
Na⁺	Na⁺NO₃^-	+1	3.697
Th⁴⁺	Th(OH)₄	0	1.293
UO₂²⁺	UO₂((OH)₂-H₂O	0	1.353

Table 10 summarizes the mass and charge balance for the MVST tank sludge samples. Considering the limitations of these calculations, the mass balance is within the analytical error (±20%) for these sludge samples. The charge balance is more influenced by the chemical form assumptions, and the results have a larger corresponding error range.

Table 10 Summary of Quality Checks for MVST Sludge Data

Tank	Mass Balance (TS_calc./TS_meas.)	Charge Balance (M⁺/A^-)	pH	¹³⁴Cs+¹³⁷Cs (%)	⁹⁰Sr/⁹⁰Y (%)	Beta Recovery (%)
W-24	0.831	0.752	12.8	17.4	77.3	79.4
W-25	0.879	0.745	12.6	7.8	89.6	87.0
W-26	0.908	0.693	9.7	29.3	39.6	104.0
W-27	0.889	0.705	12.3	31.7	62.7	91.2
W-28	0.857	0.673	12.3	12.2	47.3	96.8
W-31	0.928	0.807	9.9	2.2	97.2	94.9

The beta recovery results are listed in Table 10, and most of the discussion for the supernatant samples also applies to the sludge samples. As discussed before, the variability for the beta recovery is probably due to the analytical error on the ⁹⁰Sr measurement. Any measurement error for the ⁹⁰Sr activity would be doubled when considering the beta recovery calculation.

The distribution, by weight percent, of the major compounds from Table 9 are illustrated in Fig. 3 for each MVST sludge sample. The distribution of the total uranium and thorium concentration for each MVST sludge sample are shown in Fig. 4.

Figure 3 Distribution of Major Compounds in MVST Sludge

Figure 4 Distribution of Uranium and Thorium in MVST Sludge

The distribution of the beta emitters found in the MVST sludge samples are summarized in Table 11. The distributions of the beta activity are shown to be dependent upon the radionuclides present, which is a function of the age of the radioactive waste, and the pH of the supernatant found over the sludge. Under the typical basic conditions for ORNL waste tanks, the major difference in the beta distribution between the supernatant and the sludge is that the distribution of the longer lived fission products (⁹⁰Sr and ¹³⁷Cs) are reversed due to the differences in solubility. The Group IA metals (¹³⁴Cs and ¹³⁷Cs) and the radionuclides that form anionic species (⁹⁹TcO₄^-, ¹²⁹I^-, and ¹²⁹IO₃^-) are more soluble in the supernatant. The solubility of the Group IIA metals (⁹⁰Sr) in the supernatant are a function of both pH and carbonate concentration. At high pH most of the other metals, lanthanides, and actinide elements form insoluble hydroxides and mixed oxides, which are found in the sludge. The ⁹⁹Tc activity is higher in the supernatant than the sludge. The source of most of the ⁹⁹Tc found in the sludge samples was the interstitial liquid, and not insoluble forms of technetium. The shorter lived radionuclides observed include the europium (¹⁵²Eu, ¹⁵⁴Eu, and ¹⁵⁵Eu) isotopes and to some extent ¹³⁴Cs.

Table 11 Distribution of Beta Activity in MVST Sludge

Tank	pH	Percent of Total Beta Activity
Tank	pH	⁹⁰Sr/⁹⁰Y (%)	¹³⁴Cs+¹³⁷Cs (%)	⁶⁰Co (%)	⁹⁹Tc (%)	^152,154,155Eu (%)	²⁴¹Pu (%)
W-24	12.8	77.3	17.4	0.8	< 0.1	3.9	0.4
W-25	12.6	89.6	7.8	0.4	< 0.1	1.7	0.4
W-26	9.7	39.6	29.3	1.6	< 0.1	28.8	0.4
W-27	12.3	62.7	31.7	0.8	< 0.1	3.9	0.5
W-28	12.3	47.3	12.2	1.4	< 0.1	38.3	0.4
W-31	9.9	97.2	2.2	0.1	< 0.1	0.2	0.1

Table 12 Summary of Actinide Elements in MVST Sludge

Actinide	W-24	W-25	W-26	W-27	W-28	W-31
Actinide	(% )	(% )	(% )	(% )	(% )	(% )
²³²Th	0.04	0.05	0.03	0.02	0.01	0.06
²³³U	4.68	3.36	20.12	4.11	13.20	3.51
²³⁴U	0.23	0.12	0.36	0.22	0.33	0.21
²³⁵U	< 0.01	< 0.01	< 0.01	0.01	0.01	< 0.01
²³⁸U	< 0.01	< 0.01	< 0.01	< 0.01	< 0.01	< 0.01
²³⁷Np	0.03	0.01	< 0.01	0.05	0.04	0.01
²³⁸Pu	11.12	9.37	10.87	9.87	7.62	8.77
²³⁹Pu	5.56	4.08	2.62	2.76	2.11	2.29
²⁴⁰Pu	2.55	2.16	1.79	1.52	1.52	1.48
²⁴¹Am^a	11.41	11.17	7.85	11.52	11.68	9.45
²⁴⁴Cm	64.38	69.67	56.35	69.92	63.47	74.21
Gross (Bq/g)	34000	83000	52000	26000	44000	160000

^a The ²⁴¹Am data is based on subtracting the ²³⁸Pu by TIMS from the alpha peak measured at 5.15 MeV (²³⁸Pu +²⁴¹Am) in the alpha spectrum.

The distribution of the alpha activity is summarized in Table 12, which includes the percent alpha for each MVST sludge sample. In general, the alpha activity in the MVST system is strongly weighted by the ²⁴⁴Cm, which has a high specific activity. The list of actinides in Table 12 required several radiochemical and inorganic analytical measurements to generate the best estimates for each of the alpha activities. The ²³²Th activity is calculated from the total thorium measured by ICP-AES. The other thorium isotopes (²²⁸Th, ²²⁹Th, and ²³⁰Th) are present in the ORNL sludge waste at such low mass, their presence would not effect the ICP-AES measurement. The uranium isotopes are measured by TIMS. The atom % results are converted to weight %, which is used to calculate the concentration of each uranium isotope from the total uranium results obtained by ICP-AES. The activity for each uranium radionuclide is then calculated from the specific activity for each isotope. The plutonium isotopes are first measured by TIMS, and the total plutonium alpha activity, measured after a chemical separation, is used to calculate the activity for each isotope. The ²⁴⁴Cm was measured directly by alpha spectrometry without any chemical separation. The ²⁴¹Am activity is determined by subtracting the ²³⁸Pu activity from the sum of the ²³⁸Pu + ²⁴¹Am measured by alpha spectrometry. Both ²³⁸Pu and ²⁴¹Am have an alpha energy of about 5.50 MeV and can not be resolved by alpha spectrometry. There was no chemical separation of the plutonium and americium for this project because of cost concerns.

5.4 RCRA Characteristics for the MVST System

The RCRA regulatory limits are listed in Table 13, which also includes the limits for the EPA Toxicity Characteristic Leaching Protocol (TCLP) extract and the functional total metal limits for a solid or sludge waste. The total metal limits are a factor of twenty times higher than the TCLP extraction limits and are based on the 1:20 dilution used for the TCLP extraction procedure.

Table 13 Summary of RCRA Regulatory Limits

Metals	TCLP Extract and Liquids (mg/L)	Solid/Sludge Total Metal (mg/Kg)
Silver (Ag)	5	100
Arsenic (As)	5	100
Barium (Ba)	100	2000
Cadmium (Cd)	1	20
Chromium (Cr)	5	100
Mercury (Hg)	0.2	4
Nickel (Ni)	50	1000
Lead (Pb)	5	100
Selenium (Se)	1	20
Thallium (Tl)	0.9	18

If the RCRA metal concentrations are found to be below the total metal limits, the solid waste can not fail the TCLP leach test. If the RCRA metal concentrations exceed the total metal limits, the TCLP leach test must be done to determine if the solid waste is hazardous. For solid samples, the TCLP leach test is only valid for the final waste form ready for disposal. The total metal concentration data can be used as acceptable process knowledge if the final waste form only results in a dilution of the RCRA metal concentrations. Examples of waste forms that result in a dilution of a solid waste includes grouting (2 fold dilution) and vitrification (3 fold dilution). If the total metal limit is exceeded after stabilizing the waste, the TCLP leach test would be required for only the metals that had the potential to exceed the regulatory limits.

Several of the supernatant samples from the MVST tanks exceed the RCRA regulatory limits. Waste tanks W-26, W-27, W-28, and W-31 slightly exceed the limit for mercury. Waste tanks W-24, W-25, W-26, and W-31 come close to exceeding the limits for cadmium and could be considered over the limit depending on the confidence limits used. The current technology used for long term storage of the liquid waste is a solidification process that results in a final waste form that passes the TCLP leach test. The nickel and thallium are proposed RCRA metals and are included in the data for future waste management decisions.

All of the MVST tank sludge samples exceed the total metal limits for lead and mercury, and two tanks are over or near the limit for chromium. Most of the ORNL radioactive waste sludge samples, characterized to date, have exceeded the total metal limits for these three RCRA metals. Based on past experience, it is expected that solidification of the ORNL MVST sludge would fix these RCRA metals such that the final waste form would pass the TCLP leach test.

5.5 TRU Classifications for LLLW System

The DOE definition for Transuranic (TRU) Waste includes the following conditions,

TRU activity 3700 Bq/g (100 nCi/g),

TRU isotopes must be alpha emitting actinide with Z > 92 (uranium),

TRU isotopes must have a half life 20 years.

This definition excludes all thorium and uranium isotopes. The short lived actinide ²⁴⁴Cm (t_1/2 = 18.1 years), which is common to ORNL waste, falls outside the TRU definition. Also, the plutonium isotope, ²⁴¹Pu, would be excluded from calculation of the TRU activity because it is a pure beta emitter. The primary actinide elements common to ORNL waste, that are present at sufficient levels to meet the TRU definition, include ²³⁸Pu, ²³⁹Pu,²⁴⁰Pu, and ²⁴¹Am. There is some current work at the Radiochemical Engineering Development Center (Mark-42 fuel assembly processing) that could generate enough ²⁴³Am to make a significant contribution to TRU alpha content of the waste. The remaining actinide elements present in ORNL waste are generally not available at high enough activity, and/or do not have a long enough half-life to meet the TRU definition.

None of the MVST supernatant samples discussed in this report had enough alpha activity to be considered as TRU waste. All of the MVST sludge that has been characterized to date has been classified as TRU waste based on only the plutonium and americium activity. The alpha activity reported is based on wet weight, if adjusted for dry weight the activity would almost double. The MVST sludge samples contained enough plutonium and americium activity to easily satisfy the WIPP waste acceptance criteria¹² for transuranic waste. Based on the TRU activity, any dilution of the sludge that would result from a solidification process such as grouting or vitrification would most likely not effect the TRU classification.

5.6 Distribution of Fissile Material in LLLW System

As discussed in section 3.5, the ORNL LLLW waste acceptance criteria (WAC) requires the fissile isotopes of uranium and plutonium to be diluted with ²³⁸U and ²³²Th, respectively. Table 14 summarizes the dilution or "denature" ratios for the MVST supernatant samples. All the dilution ratios for the MVST liquid phase exceed the required dilution factors. Only one of the supernatant samples, W-31, had enough thorium and plutonium to allow estimates for the plutonium dilution ratios. A summary of the dilution ratios for fissile material in the sludge samples is provided in Table 15. All the dilution ratios for the MVST sludge samples exceed the required dilution factors for the fissile isotopes of uranium and plutonium. All the dilution ratios listed in Table 14 and 15 are based on equations discussed in section 3.5 of this report.

Table 14 Summary of Denature Ratios for MVST Supernatant

Tank	²³⁸U/²³⁵U f₃₅ (eq. 1)	²³⁸U/²³⁵U (eq. 3)	²³⁸U/²³³U (eq. 4)	²³²Th/²³⁹Pu (eq. 2)	pH
W-24	231	273	632	na^a	12.3
W-25	203	226	571	na	12.6
W-26	225	281	521	na	8.4
W-27	256	312	729	na	12.8
W-28	252	321	626	na	7.3
W-31	226	263	622	184	10.0

^a Concentration of thorium and plutonium to low to calculate ratio.

Table 15 Summary of Denature Ratios for MVST Sludge

Tank	²³⁸U/²³⁵U f₃₅ (eq. 1)	²³⁸U/²³⁵U (eq. 3)	²³⁸U/²³³U (eq. 4)	²³²Th/²³⁹Pu (eq. 2)	pH
W-24	177	181	862	3920	12.8
W-25	153	153	470	6320	12.6
W-26	227	279	545	5730	9.7
W-27	298	313	3070	4390	12.3
W-28	296	347	1120	3750	12.3
W-31	145	144	581	13900	9.9

The dilution ratios listed in Tables 14 and 15 are base on the ratio of weight %, not the ratio of atom % given in the data tables. There is a small difference between atom %, reported for the uranium and plutonium, and weight %, which is needed for many calculations performed with the analytical data. To convert from atom % to weight %, we used the following equation,

To be inserted...

where, W_i = weight %,

M_i = nuclidic mass

a_i = atom %.

An example of this calculation is provided in Table 16, which shows there is not much difference between the atom % and the weight %.

Table 16 Example of Converting Atom % to Weight % for W-31 Sludge

Isotope

Nuclidic mass

(g/mol)

atom %

(a_i M_i)

weight %

²³³U

²³⁴U

²³⁵U

²³⁶U

²³⁸U

Total

233.039629

234.040947

235.043924

236.045563

238.050785

0.056

0.004

0.621

0.002

99.316

99.999

13.0502

0.9362

145.9623

0.4721

23642.2518

23802.6726

0.0548

0.0039

0.6132

0.0020

99.3260

99.9999

The distribution of plutonium isotopes by alpha activity are illustrated in Fig. 5 for each of the MVST samples. For comparison, Fig. 6 shows the distribution of the plutonium isotopes by concentration for each of the MVST sludge samples. One should note that the ²³⁸Pu dominates the alpha activity and the ²³⁹Pu is the major isotope by weight or concentration.

Figure 5 Distribution of Plutonium by Alpha Activity in MVST Sludge

Figure 6 Distribution of Plutonium by Concentration in MVST Sludge

5.7 Discussion of the Total Anion Content in the Sludge

As discussed in section 3.3, there were three sample preparation methods used to investigate the total anion content of the sludge samples, which included (1) water leach, (2) oxygen bomb combustion, and (3) sodium peroxide/sodium hydroxide fusion. A summary and comparison of these sludge preparation methods are given in Table 17.

Table 17 Summary of Total Anion Data for MVST Sludge

Anion Method (mg/Kg)

W-24 W-25 W-26 W-27 W-28 W-31

Bromide Water Leach¹
Bomb
Fusion
< 47
213
320
< 49
158
236
< 50
322
420
< 48
117
290
< 48
133
287
< 45
118
240

Chloride Water Leach
Bomb
Fusion
2770
2740
nd²
2110
2170
nd²
3070
2800
nd²
2280
1850
nd²
3460
3210
nd²
2570
2150
nd²

Fluoride Water Leach
Bomb
Fusion
103
41
nd²
118
71
nd²
< 50
81
nd²
< 48
44
nd²
< 48
64
nd²
125
218
nd²

Nitrate Water Leach
Bomb
Fusion
165000
111000
90400
162000
101000
71800
214000
148000
113000
210000
120000
143000
248000
167000
204000
197000
119000
157000

Nitrite Water Leach
Bomb
Fusion
2250
7310
32400
4970
8090
39000
1650
5820
38000
2280
6090
38400
1120
8090
11600
3470
6190
10300

Phosphate Water Leach
Bomb
Fusion
ICP-AES
ICP-MS
< 19
114
277
3800
-
< 20
< 51
340
5670
4350
< 20
89
211
3280
-
< 19
< 36
< 190
3070
-
< 19
117
< 190
2780
-
< 45
253
1540
13000
9430

Sulfate Water Leach
Bomb
Fusion
ICP-MS
1370
1520
2540
-
1750
2070
2950
29300
2120
2460
4600
-
549
752
4270
-
1770
1810
3260
-
1090
1030
1650
9500

¹ Unable to resolve bromide peak from nitrate on ion chromatography column used for this sample.

² Unable to quantify by ion chromatography due to interference from fusion matrix.

5.7.1 Nitrate/Nitrite

It is difficult to compare the yield for these two anions between the three preparation methods. The majority of the compounds present in the MVST waste system that contain nitrate and nitrite readily dissolve in water and are accounted for in the water leaches. This can be argued by looking at the cation/anion charge balance calculations for the sludge analysis. These calculations show acceptable agreement between the anionic species and the cationic species (which are accurately determined by conventional methods) present in the sludges. The majority of the anion contribution is by far due to the nitrate ion with the other anions contributing just a fraction of the total negative molar charge. Based on this calculated charge balance it is believed that the majority of the nitrates are accounted for in the water leaches. When the sludge is prepared using either the bomb or fusion method the sample is subject to an oxidizing environment which will not only change the nitrate/nitrite ratio in the sample but will also oxidize any nitrogen present in the sample to nitrate or nitrite. The ratio of the nitrate/nitrite measured after the bomb or fusion methods does not represent the ratio in the original sample. The mole percent of nitrite relative to the sum of the nitrate and nitrite ranged from 0.6 % to 4 % in the water leach samples and represents the nitrite content of the samples as recieved. The mole percent of nitrite observed after the bomb combustion ranged from 5 % to 9.7 %, and after the fusion preparation ranged from 7.1 % to 42 %. The change in the mole percent of nitrite is a function of the oxidizing environment from each preparation method.

5.7.2 Halides (fluoride, chloride, bromide)

The data in Table 17 shows that there is no benefit for using a bomb combustion over a water leach of the MVST sludges for fluoride and chloride. For the bromide results the water leach was analyzed using a Dionex AS4A ion exchange column while the bomb combustion and fusion results were analyzed using a new Dionex AS14 ion exchange column. The older AS4A column separation of the bromide and nitrate peaks is not as good as the AS14 and due to the high levels of nitrate present in the sludges the bromide peak could not be resolved from the nitrate peak using the AS4A column. Therefore, a comparison could not be made between the water leaches and the other methods for bromide. It does appear that the fusion method yields slightly higher bromide values than the bomb.

Due to the extremely high levels of sodium in the sample matrix after the fusion it was impossible to determine fluoride or chloride concentrations using ion chromatography. The matrix caused large interfering peaks to elute off of the column at the beginning of the analysis run where fluoride is detected; then a large negative dip occurred in the chromatogram where chloride is eluted. It may be possible to measure fluoride and chloride in the fusion matrix after using a clean-up procedure prior to analysis. Possible solutions are being investigated.

5.7.3 Phosphate

It is believed that a large fraction of the phosphate in the MVST sludge is present as tributyl phosphate and degradation products dibutyl- and monobutyl phosphate. The tributyl phosphate has low solubility in water and would not be seen in the water leach. This is illustrated in the table showing phosphate values below the detection limit of the instrument. When the sludges were prepared using the Parr bomb some phosphate was detected but still at low levels. The explanation for this could be due to poor combustion of the sludge. In order to obtain an adequate combustion 5000 calories of heat must be produced in the bomb. Since the MVST sludges are not comprised of combustible material all of the heat must be generated by the combustion aid (mineral oil). Using the heat of combustion for mineral oil, 0.5 mL was determined to be able to produce greater than 5000 calories and therefore provide for an adequate combustion. After a material undergoes complete combustion it should have an ash like appearance. By visual observation after the sludge was combusted it appears to be just dried out sludge with a crusty appearance. Based on this and the fact that only low levels of phosphates were detected it is felt that the bomb is a poor choice for preparation of the sludge for anion determination. A good sample for bomb combustion would have some combustibility with the combustion aid acting as a catalyst to start the reaction. The MVST sludges have no combustible properties.

When phosphate was determined using the fusion method slightly higher values were obtain. However, four matrix spiked samples were analyzed with the fusion batches and all spike recoveries were zero percent. This indicates that phosphate is lost during the fusion preparation and therefore the method used as is, is not adequate for the analysis of phosphate in the sludges.

Also shown in the Table 17 are the phosphate results by ICP-AES for each MVST sludge sample and two results by ICP-MS for W-25 and W-31. These phosphate values are calculated results based on the analysis of total phosphorus by the ICP methods after a closed vessel microwave acid digestion of the sludge. The ICP-AES values are currently considered to be the best results for the total phosphorus in the sludge. The ICP-MS measurements are estimates done to confirm the high levels of phosphorus observed in the MVST sample. The water leach, bomb combustion, and fusion methods all yielded phosphate results much lower than the ICP measurements after an acid digestion.

5.7.4 Sulfate

The analysis of sulfate between the water leaches and the bomb combustion show good agreement but there may be sulfate compounds present in the sludge that are not water soluble and would not be accounted for using the bomb procedure due to the problems discussed earlier. The fusion results show an appreciable increase in the measured sulfate concentration. But one needs to keep in mind that this is a total sulfur determination and the sulfate measured does not necessarily have to come from a sulfate compounds. Similar to the phosphate, sulfate is lost during the fusion preparation phase. Four matrix spikes analyzed with the fusion batch averaged out to only a thirty percent spike recovery. Two cursory measurements for sulfur by ICP-MS on the W-25 and W-31 sludge samples produced much higher sulfate equivalent values than the other sample preparation methods. The ICP-MS technique for sulfur needs additional investigation to ensure molecular mass interference problems are properly accounted for with the sludge samples. This investigation would have been out of scope for this project.

5.7.5 Summary

There is no ideal method to obtain a total anion content on the MVST sludges. The water leaches are considered to be adequate for nitrate, nitrite, and the halides. The total phosphate and sulfate content however will not be obtained by a water leach and any method used that oxidizes the sample would be considered to be a total phosphorus or sulfur. The best preparation method for total phosphorus or sulfur appears to be closed vessel microwave digestion followed by analysis by ICP-AES or ICP-MS. Other DOE sites that have experience with caustic high nitrate sludge samples and have worked with the bomb and fusion procedures, have related similar observations which include poor yields and heavy matrix interferences associated with these preparation methods.

5.8 Solubility of MVST Sludge in Water

The MVST sludge samples were taken through a water wash to determine the water soluble anions and measure the effect of the sludge on pH. Since this water leach solution was available, several of the lower cost analytical measurements, including the metals by ICP-AES, gross alpha/beta, and gamma emitters, were measured on the wash solution to evaluate the relative solubility of the sludge in water. The water wash experiment consisted of taking 5 grams of wet sludge and diluting the sample to 50 mL with deionized water. The sludge was leached with the water on a vortex mixer for several minutes and the clarified liquid was then removed for analysis. Results from the water leaching experiment are summarized in Table 18.

Table 18 Recovery of Selected Species in Water Leach

Analytical Measurement	% Recovery in Water Leach of Sludge
Analytical Measurement	W-24	W-25	W-26	W-27	W-28	W-31
Selected metals
pH of water wash	12.8	12.6	9.7	12.3	12.3	9.9
Al	14.75	2.82	< 0.01	0.80	< 0.01	0.06
Ca	1.06	0.95	3.07	14.49	32.75	2.29
Cr	7.47	33.55	1.53	8.3	0.91	12.46
Fe	< 0.01	< 0.01	< 0.01	< 0.01	< 0.01	< 0.01
K	102.99	108.59	103.56	114.78	105.48	103.49
Mg	0.01	0.01	5.51	< 0.01	< 0.01	0.38
Na	105.94	102.69	110.02	107.22	111.80	106.44
Th	< 0.01	< 0.01	0.02	< 0.01	< 0.01	< 0.01
U	0.04	0.04	0.03	< 0.01	< 0.01	1.15
Selected radionuclides
Gross alpha	0.38	0.13	0.18	0.12	0.07	< 0.01
Gross beta	10.44	2.29	28.57	30.63	16.77	1.33
⁶⁰Co	0.27	0.24	2.07	1.00	0.95	0.50
¹³⁷Cs	71.70	31.92	96.63	84.62	93.55	48.84
¹⁵²Eu	< 0.01	< 0.01	0.09	< 0.01	0.14	< 0.01

The water leach appears to remove more of the sodium and potassium than the total digestion with nitric acid, however, the high recovery is more likely due to the difference in sample size used for each sample preparation. Only 0.5 g of sample was used for the nitric acid digestion as compared to the 5 g used for the water leach. The larger sample size would be more representative of the overall sludge and introduces less sampling error. The water wash does not remove many of the metals (i.e. uranium) that cause spectral interference problems. Therefore, both analytical and sampling errors most likely contribute to the high bias for the sodium and potassium recovery. In general, the lighter alkali metals are quantitatively removed from the sludge along with the nitrate. Some of the cesium (see ¹³⁷Cs recovery) appears to be bound to the sludge, which could be due to differences in ion exchange properties between the cesium and the lighter alkali metals. The incomplete removal of ¹³⁷Cs from the sludge with water, caustic, and low acid washing has been observed in past experiments with the MVST sludge.

As expected, the actinide and lanthanide elements are not significantly removed by the water wash and this behavior is illustrated by the uranium, thorium, ¹⁵²Eu, and gross alpha recovery listed in Table 18. The water solubility of the alkaline earth elements, represented by calcium in Table 18, are a function of both the pH and the carbonate concentration. The recovery of the calcium ranges from < 1% to about 33 % for the MVST sludge samples, and this behavior would also be expected for the ⁹⁰Sr activity. Most of the other major metals are usually insoluble in a water wash except for the chromium which is probably present as an the anion chromate, and many anionic species tend to be soluble in water.

5.9 Estimates for Compliance with WIPP WAC, Rev. 5 for MVST Sludge

The purpose of this section is to establish upper boundary estimates, based upon a 55-gal. drum shipping container, for several of the nuclear properties criteria and requirements for RH-TRU waste as specified in the WIPP WAC, Revision 5. Specifically, this section will develop estimates for the ²³⁹Pu Fissile Gram Equivalent (FGE), ²³⁹Pu Equivalent Activity, and Thermal Power or decay heat limits per RH-TRU canister. The RH-TRU limits per waste canister for each of these nuclear criteria are listed as follows,

²³⁹Pu FGE < 325 g

²³⁹Pu Equivalent Activity < 1000 Ci

Thermal Power < 300 watts.

For the MVST sludge, the ²³⁹Pu FGE can be estimated by the summation of the gram-equivalents for ²³³U, ²³⁵U, and ²³⁹Pu. As shown in Table 19, the ²³⁵U dominates the total ²³⁹Pu FGE for the MVST sludge samples and the ²³⁹Pu is less than 5% of the total fissile gram equivalent. Based on packaging the wet sludge in 55-gal. drums, none of the MVST sludge would approach the RH-TRU limit of 325 g per canister for the ²³⁹Pu FGE. Estimates for the total weight (Kg) of sludge in a 55 gal. drum, for each MVST sludge sample, are listed in Table 22.

Table 19 Estimates for ²³⁹Pu FGE with the MVST Sludge

Isotope ²³⁹Pu FGE
factor
W-24
(mg/Kg)
W-25
(mg/Kg)
W-26
(mg/Kg)
W-27
(mg/Kg)
W-28
(mg/Kg)
W-31
(mg/Kg)

²³³U 0.865 3.58 6.6 25.1 2.52 12.0 10.9

²³⁵U 0.641 33.2 41.0 51.3 35.7 46.2 121

²³⁹Pu 1.000 0.84 1.46 0.57 0.29 0.36 1.49

²³⁹Pu FGE (mg/Kg) 25.22 33.45 55.16 25.35 40.35 88.48

²³⁹Pu FGE in 55 gal. (g) 7.2 9.5 15.8 7.6 11.5 26.5

Estimates for the total ²³⁹Pu equivalent activity (Ci) in a 55-gal. drum for each of the MVST sludge samples are listed in Table 20. The ²³⁹Pu equivalent activity is based on following calculation,

To be inserted...

where A_i is the activity of radionuclide i, and F_i is the ²³⁹Pu equivalent activity weighting factor for radionuclide i. The weighting factors for the major radionuclides found in the MVST sludge are listed in Table 20. As shown in the last row of Table 20, all of the MVST sludge estimates for ²³⁹Pu Equivalent activity would be less than 1 Ci for a 55 gal. drum, which is well below the RH-TRU limits. The MVST sludge is well below the CH-TRU limit of 80 Ci of plutonium equivalent activity for untreated waste in a 55-gal. drum and will not approach the 1000 Ci WAC limit for a RH-TRU canister, which holds three 55-gal. drums.

Table 20 Estimates for ²³⁹Pu Equivalent Activity with the MVST Sludge

Isotope ²³⁹Pu
wt. factor^a
W-24
(Bq/g)
W-25
(Bq/g)
W-26
(Bq/g)
W-27
(Bq/g)
W-28
(Bq/g)
W-31
(Bq/g)

²³³U 3.9 1600 2800 10000 1000 5200 5200

²³⁸Pu 1.1 3800 7800 5400 2400 3000 13000

²³⁹Pu 1.0 1900 3400 1300 670 830 3400

²⁴⁰Pu 1.0 870 1800 890 370 600 2200

²⁴¹Pu 52.0 14000 26000 15000 6500 12000 24000

²⁴¹Am 1.0 3900 9300 3900 2800 4600 14000

²⁴⁴Cm 1.9 22000 58000 28000 17000 25000 110000

²³⁹Pu Eqv. (Bq/g) 22382.98 53335.17 28588.50 15350.60 23479.27 91107.79

²³⁹Pu Eqv. in 55 gal. (Ci) 0.17 0.41 0.22 0.12 0.18 0.74

^a Radionuclide-specific weighting factors for the ²³⁹Pu equivalent activity taken from Appendix A of DOE/WIPP-069, Rev.5

There is concern about the thermal power from the decay heat of the radionuclides present in waste packages prepared for WIPP disposal. These concerns are addressed in Revision 5 of the WIPP WAC, with limits of 40 watts for a TRUPACT-II container for CH-TRU waste and a limit of 300 watts for a RH-TRU canister. High decay heat is also an indicator for potential problems with hydrogen gas generation. The major radionuclides found in the MVST sludge are listed in Table 21 along with the "Q" values needed to calculate the decay heat for each isotope.

An estimate of the decay heat distribution by radionuclide for the MVST sludge samples are listed in Table 22 along with an estimate for an upper boundary for total decay heat that would be in a 55 gal. drum full of wet sludge. These estimates indicate that the decay heat from MVST sludge is far below any of the WIPP WAC limits for thermal power and should have no impact on packaging requirements. For general interest, the relative percent distributions of the decay heat by radionuclide, beta activity, and alpha activity are listed in Table 23. The distribution of decay heat as a function of MVST tank and radionuclide is illustrated in Fig. 7 for beta decay, and in Fig. 8 for alpha decay. Although ²⁴¹Pu is a pure beta emitter, it is included with the other actinides for illustration. It is interesting to note that the beta activity dominates the decay heat output and that the heat from alpha decay is generally less than 10% of the total thermal power.

Table 21 Isotopes that Contribute to the Decay Heat in the MVST Sludge
Isotope	"Q" value	"Q" value	W-24	W-25	W-26	W-27	W-28	W-31
	(W/Ci)	(W/Bq)	(Bq/g)	(Bq/g)	(Bq/g)	(Bq/g)	(Bq/g)	(Bq/g)
⁶⁰Co	1.54E-02	4.16E-13	2.80E+04	2.50E+04	5.80E+04	1.20E+04	4.20E+04	2.20E+04
⁹⁰Sr	1.16E-03	3.14E-14	1.40E+06	3.20E+06	7.10E+05	4.50E+05	7.00E+05	1.10E+07
⁹⁰Y	5.54E-03	1.50E-13	1.40E+06	3.20E+06	7.10E+05	4.50E+05	7.00E+05	1.10E+07
¹³⁷Cs	1.01E-03	2.73E-14	5.30E+05	4.70E+05	8.90E+05	3.90E+05	3.10E+05	4.30E+05
^137mBa	3.94E-03	1.06E-13	5.01E+05	4.45E+05	8.42E+05	3.69E+05	2.93E+05	4.07E+05
¹⁵²Eu	7.65E-03	2.07E-13	8.90E+04	7.10E+04	6.40E+05	4.10E+04	8.00E+05	3.00E+04
¹⁵⁴Eu	9.08E-03	2.45E-13	3.80E+04	3.70E+04	2.90E+04	1.70E+04	2.70E+05	2.00E+04
¹⁵⁵Eu	7.59E-04	2.05E-14	1.00E+04	8.40E+03	6.30E+04	0.00E+00	7.00E+04	0.00E+00
Total beta (Ci/Kg)			1.08E-01	2.02E-01	1.07E-01	4.69E-02	8.64E-02	6.20E-01
²³³U	2.86E-02	7.72E-13	1.60E+03	2.80E+03	1.00E+04	1.00E+03	5.20E+03	5.20E+03
²³⁸Pu	3.26E-02	8.81E-13	3.80E+03	7.80E+03	5.40E+03	2.40E+03	3.00E+03	1.30E+04
²³⁹Pu	3.02E-02	8.17E-13	1.90E+03	3.40E+03	1.30E+03	6.70E+02	8.30E+02	3.40E+03
²⁴⁰Pu	3.06E-02	8.26E-13	8.70E+02	1.80E+03	8.90E+02	3.70E+02	6.00E+02	2.20E+03
²⁴¹Am	3.28E-02	8.87E-13	3.90E+03	9.30E+03	3.90E+03	2.80E+03	4.60E+03	1.40E+04
²⁴¹Pu b^-	3.20E-05	8.65E-16	1.40E+04	2.60E+04	1.50E+04	6.50E+03	1.20E+04	2.40E+04
²⁴⁴Cm	3.44E-02	9.29E-13	2.20E+04	5.80E+04	2.80E+04	1.70E+04	2.50E+04	1.10E+05
Total alpha (Ci/Kg)			9.21E-04	2.25E-03	1.34E-03	6.55E-04	1.06E-03	3.99E-03
Total beta in 55 gal. drum (Ci):			30.80	57.05	30.61	14.01	24.55	185.61
Total alpha in 55 gal. drum (Ci):			0.37	0.83	0.50	0.25	0.39	1.39

Table 22 Distribution of Decay Heat in MVST Sludge
Isotope	"Q" value	"Q" value	W-24	W-25	W-26	W-27	W-28	W-31
	(W/Ci)	(W/Bq)	(W/Kg)	(W/Kg)	(W/Kg)	(W/Kg)	(W/Kg)	(W/Kg)
⁶⁰Co	1.54E-02	4.16E-13	1.17E-05	1.04E-05	2.42E-05	5.00E-06	1.75E-05	9.16E-06
⁹⁰Sr	1.16E-03	3.14E-14	4.39E-05	1.00E-04	2.23E-05	1.41E-05	2.19E-05	3.45E-04
⁹⁰Y	5.54E-03	1.50E-13	2.10E-04	4.79E-04	1.06E-04	6.74E-05	1.05E-04	1.65E-03
¹³⁷Cs	1.01E-03	2.73E-14	1.45E-05	1.28E-05	2.43E-05	1.06E-05	8.46E-06	1.17E-05
^137mBa	3.94E-03	1.06E-13	5.34E-05	4.73E-05	8.97E-05	3.93E-05	3.12E-05	4.33E-05
¹⁵²Eu	7.65E-03	2.07E-13	1.84E-05	1.47E-05	1.32E-04	8.47E-06	1.65E-04	6.20E-06
¹⁵⁴Eu	9.08E-03	2.45E-13	9.33E-06	9.08E-06	7.12E-06	4.17E-06	6.63E-05	4.91E-06
¹⁵⁵Eu	7.59E-04	2.05E-14	2.05E-07	1.72E-07	1.29E-06	0.00E+00	1.44E-06	0.00E+00

²³³U	2.86E-02	7.72E-13	1.24E-06	2.16E-06	7.72E-06	7.72E-07	4.02E-06	4.02E-06
²³⁸Pu	3.26E-02	8.81E-13	3.35E-06	6.87E-06	4.76E-06	2.11E-06	2.64E-06	1.15E-05
²³⁹Pu	3.02E-02	8.17E-13	1.55E-06	2.78E-06	1.06E-06	5.48E-07	6.78E-07	2.78E-06
²⁴⁰Pu	3.06E-02	8.26E-13	7.19E-07	1.49E-06	7.35E-07	3.06E-07	4.96E-07	1.82E-06
²⁴¹Am	3.28E-02	8.87E-13	3.46E-06	8.25E-06	3.46E-06	2.48E-06	4.08E-06	1.24E-05
²⁴¹Pu b^-	3.20E-05	8.65E-16	1.21E-08	2.25E-08	1.30E-08	5.62E-09	1.04E-08	2.08E-08
²⁴⁴Cm	3.44E-02	9.29E-13	2.04E-05	5.39E-05	2.60E-05	1.58E-05	2.32E-05	1.02E-04
Total (W/Kg)			3.92E-04	7.49E-04	4.51E-04	1.71E-04	4.52E-04	2.20E-03
Density	(Kg/L):		1.37	1.36	1.38	1.44	1.37	1.44
Total in 55 gal drum (Kg):			285	283	287	300	285	300
Total in 55 gal drum (Watt):			0.112	0.212	0.130	0.051	0.129	0.660

Table 23 Summary of Relative Decay Heat in MVST Sludge
Isotope	"Q" value	"Q" value	W-24	W-25	W-26	W-27	W-28	W-31
	(W/Ci)	(W/Bq)	(% Watt)	(% Watt)	(% Watt)	(% Watt)	(% Watt)	(% Watt)
⁶⁰Co	1.54E-02	4.16E-13	2.98%	1.39%	5.35%	2.92%	3.87%	0.42%
⁹⁰Sr	1.16E-03	3.14E-14	11.20%	13.39%	4.93%	8.25%	4.85%	15.66%
⁹⁰Y	5.54E-03	1.50E-13	53.51%	63.93%	23.57%	39.38%	23.18%	74.80%
¹³⁷Cs	1.01E-03	2.73E-14	3.69%	1.71%	5.39%	6.22%	1.87%	0.53%
^137mBa	3.94E-03	1.06E-13	13.63%	6.32%	19.87%	22.96%	6.91%	1.97%
¹⁵²Eu	7.65E-03	2.07E-13	4.70%	1.96%	29.32%	4.95%	36.57%	0.28%
¹⁵⁴Eu	9.08E-03	2.45E-13	2.38%	1.21%	1.58%	2.44%	14.66%	0.22%
¹⁵⁵Eu	7.59E-04	2.05E-14	0.05%	0.02%	0.29%	0.00%	0.32%	0.00%
Total beta heat (%):			92.15%	89.93%	90.30%	87.13%	92.23%	93.88%
²³³U	2.86E-02	7.72E-13	0.32%	0.29%	1.71%	0.45%	0.89%	0.18%
²³⁸Pu	3.26E-02	8.81E-13	0.85%	0.92%	1.05%	1.24%	0.58%	0.52%
²³⁹Pu	3.02E-02	8.17E-13	0.40%	0.37%	0.24%	0.32%	0.15%	0.13%
²⁴⁰Pu	3.06E-02	8.26E-13	0.18%	0.20%	0.16%	0.18%	0.11%	0.08%
²⁴¹Am	3.28E-02	8.87E-13	0.88%	1.10%	0.77%	1.45%	0.90%	0.56%
²⁴¹Pu b^-	3.20E-05	8.65E-16	0.00%	0.00%	0.00%	0.00%	0.00%	0.00%
²⁴⁴Cm	3.44E-02	9.29E-13	5.22%	7.19%	5.77%	9.23%	5.14%	4.64%
Total alpha heat (%):			7.85%	10.07%	9.70%	12.87%	7.77%	6.12%

Figure 7 Distribution of Beta Decay Heat in MVST Sludge

Figure 8 Distribution of Alpha Decay Heat in MVST Sludge

6.0 Summary of Organic Analytical Results

The organic content of the MVST samples was very low, with almost nothing above the detection limits observed in the supernatant and only trace amounts observed in the sludge samples. The few organic compounds observed consisted of products from the Purex and other actinide separation processes used by past chemical processing plants within the Laboratory. The target compound list (TCL) hits and the tentatively identified compounds (TIC) from the GC-MS analyses are listed in Table 24 for the supernatant samples and Table 25 for the sludge samples. For the organic chemical characterization results the following reporting conventions are used:

Reporting limits The reporting limits are the concentrations above which the response of the instrument for the calibrated range of concentrations is linear.

B Data qualifier meaning that the compound was also found in the accompanying laboratory blank sample.

D Data qualifier meaning sample dilution was required.

E Data qualifier indicating that the reported concentration of the compound exceeded the calibration range of the instrument.

J Data qualifier meaning that the compound was estimated at a concentration below the reporting limit; also used to indicate that the concentrations for tentatively identified compounds (TICs) are estimates.

U Data qualifier meaning compound was not detected and method detection limits was reported.

TIC Tentatively identified compound. The identification is based upon mass spectral data only, and the quantitation is based upon the response factor of the nearest eluting internal standard. All TIC values are estimates and are flagged with the "J" qualifier.

Table 24 Analytical Organic Data for MVST Liquid Samples

Target Compound	Concentration in Liquid, mg/L
Target Compound	W-24	W-25	W-26	W-27	W-28	W-31
Non-halogenated Volatile Organic Compounds (NH-VOA)
Methanol	2 U	2 U	2 U	2 U	2 U	2 U
Acetone	2 U	2 U	2 U	2 U	2 U	2 U
Methyl Ethyl Ketone	2 U	2 U	2 U	2 U	2 U	2 U
Isobutanol	2 U	2 U	2 U	2 U	2 U	2 U
Butanol	2 U	2 U	2 U	2 U	2 U	2 U
Pyridine	2 U	2 U	2 U	2 U	2 U	2 U
Volatile Organic Compounds (VOA)
Vinyl Chloride	1 U	1 U	1 U	1 U	1 U	1 U
Trichlorofluoromethane	1 U	1 U	1 U	1 U	1 U	1 U
Ethyl Ether	1 U	1 U	1 U	1 U	1 U	1 U
1,1,2-Trichloro-1,2,2-trifluoroethane	1 U	1 U	1 U	1 U	1 U	1 U
1,2-Dichloroethylene	1 U	1 U	1 U	1 U	1 U	1 U
Methylene Chloride	1 U	1 U	1 U	1 U	1 U	1 U
Chloroform	1 U	1 U	1 U	1 U	1 U	1 U
1,2-Dichloroethane	1 U	1 U	1 U	1 U	1 U	1 U
1,1,1-Trichloroethane	1 U	1 U	1 U	1 U	1 U	1 U
Carbon Tetrachloride	1 U	1 U	1 U	1 U	1 U	1 U
Benzene	1 U	1 U	1 U	1 U	1 U	1 U
Trichloroethylene	1 U	1 U	1 U	1 U	1 U	1 U
1,1,2-Trichloroethane	1 U	1 U	1 U	1 U	1 U	1 U
Bromoform	1 U	1 U	1 U	1 U	1 U	1 U
Toluene	1 U	1 U	1 U	1 U	1 U	1 U
Tetrachloroethylene	1 U	1 U	1 U	1 U	1 U	1 U
Chlorobenzene	1 U	1 U	1 U	1 U	1 U	1 U
Ethylbenzene	1 U	1 U	1 U	1 U	1 U	1 U
m&p-Xylenes	1 U	1 U	1 U	1 U	1 U	1 U
o-Xylene	1 U	1 U	1 U	1 U	1 U	1 U
1,1,2,2-	1 U	1 U	1 U	1 U	1 U	1 U
1,4-Dichlorobenzene	1 U	1 U	1 U	1 U	1 U	1 U
Ortho-Dichlorobenzene	1 U	1 U	1 U	1 U	1 U	1 U
Tentatively Identified Volatile Organic Compounds
Tetrahydrofuran	-	-	-	-	-	0.01 J
3-Heptanone	-	-	-	-	-	0.02 J
Unknown	0.04 J (3)^a	0.06 J (3)^a	0.11 J (5)^a	0.24 J (9)^a	0.22 J (8)^a	0.3 J (11)^a
Unknown Hydrocarbon	-	-	-	-	-	0.03 J (2)^a
Semivolatile Organic Compounds (SVOA)
2-Methyl Phenol	0.05 U	0.05 U	0.05 U	0.05 U	0.05 U	0.05 U
Hexachloroethane	0.05 U	0.05 U	0.05 U	0.05 U	0.05 U	0.05 U
4-Methyl Phenol	0.05 U	0.05 U	0.05 U	0.05 U	0.05 U	0.05 U
Nitrobenzene	0.05 U	0.05 U	0.05 U	0.05 U	0.05 U	0.05 U
2,4-Dinitrotoluene	0.05 U	0.05 U	0.05 U	0.05 U	0.05 U	0.05 U
2,4-Dinitrophenol	0.05 J	0.05 U	0.05 U	0.30 J	0.09 J	0.41 J
Hexachlorobenzene	0.05 U	0.05 U	0.05 U	0.05 U	0.05 U	0.05 U
Pentachlorophenol	0.05 U	0.05 U	0.05 U	0.05 U	0.05 J	0.05 U
Tentatively Identified Semivolatile Organic Compounds
Benzenesulfonamide, N-butyl	-	0.47 J	-	-	0.37 J	-
Benzoic acid	-	-	-	-	-	0.56 J
2-Butanamine	-	-	0.03 J	-	-	-
Dimethyl sulfone	-	-	0.06 J	-	-	-
Di-n-octyl phthalate	-	0.40 J	0.03 J	-	-	-
Heptanal	0.07 J	-	-	-	-	-
Tributylphosphate (TBP)	0.66 J	1.1 J	-	0.94 J	0.14 J	0.72 JD
Unknown	2.0 J (19)^a	4.6 J (16)^a	0.7 J (19)^a	4.9 J (19)^a	5.8 J (19)^a	10 J (20)^a

^a Number of compounds grouped together listed in parenthesis.

Table 25 Analytical Organic Data for MVST Sludge Samples

Target Compound	Concentration in Sludge, mg/Kg
Target Compound	W-24	W-25	W-26	W-27	W-28	W-31
Semivolatile Organic Compounds (SVOA)
2-Methyl Phenol	5 U	10 UD	5 U	5 U	5 U	5 U
Hexachloroethane	5 U	10 UD	5 U	5 U	5 U	5 U
4-Methyl Phenol	5 U	10 UD	5 U	5 U	5 U	5 U
Nitrobenzene	5 U	10 UD	5 U	5 U	5 U	5 U
2,4-Dinitrotoluene	0.3 U	0.6 UD	0.3 U	0.3 U	0.3 U	0.3 U
2,4-Dinitrophenol	5 U	10 UD	5 U	5 U	5 U	5 U
Hexachlorobenzene	0.3 U	0.6 UD	0.3 U	0.3 U	0.3 U	0.3 U
Pentachlorophenol	5 U	10 UD	5 U	5 U	5 U	5 U
Tentatively Identified Semivolatile Organic Compounds
Benzene, diethyl-	7.4 J (2)^a	21 JD	-	-	-	-
Benzene, 1,3-bis(1-	3.0 J	9.0 JD	-	-	-	-
Benzophenone	-	-	0.99 J	1.0 J	1.1 J	2.8 J
Dibutyl phthalate	-	-	1.4 J	1.2 J	1.2 J	-
1-Docosene	-	-	1.2 J	-	-	-
Dodecane	3.5 J	7.3 JD	1.0 J	1.9 J	0.7 J	3.5 J
1-Dotriacontanol	-	-	-	1.2 J	-	-
Ethanone, 1-(4-ethylphenyl)-	-	-	1.3 J	-	-	-
Heptadecane	-	-	-	0.9 J	-	-
Heptane, 4-ethyl-2,2,6,6-tetramethyl	3.6 J	-	-	-	-	5.3 J
1-Hexanol, 2-ethyl	-	-	-	-	0.54 J	-
Hexadecanoic acid	-	-	1.8 J	-	-	-
Nonadecane	-	-	-	1.1 J	-	-
1- Nonadecanol	-	-	3.1 J	-	-	-
Octadecane	-	-	-	1.6 J	-	-
1-Octanamine, N-nitroso-n-octyl-	1.4 J	-	-	-	-	-
Pentadecane	-	-	-	1.1 J	-	-
Tetradecane	8.7 J	11 JD	2.3 J	3.7 J	1.5 J	2.3 J
Tributylphosphate	2.5 J	14 JD	-	-	2.1 J	15 J
Tridecane	11 J	13 JD	2.2 J	4.5 J	1.4 J	3.6 J
Undecane	3.3 J	6.8 J	-	1.7 J	-	5.1 J
Unknown	4 J (2)^a	56 JD	-	-	-	28 J (8)^a
Polychlorinated Biphenyls (PCB) Analysis
Aroclor-1016	0.048 U	0.050 U	nd^b	nd	0.050 U	0.050 U
Aroclor-1221	0.048 U	0.050 U	nd	nd	0.050 U	0.050 U
Aroclor-1232	0.048 U	0.050 U	nd	nd	0.050 U	0.050 U
Aroclor-1242	0.049 J	0.050 U	0.050 U	0.050 U	0.050 U	0.050 U
Aroclor-1248	0.048 U	0.050 U	nd	nd	0.050 U	0.050 U
Aroclor-1254	0.048 U	0.050 U	0.050 U	0.050 U	0.050 U	0.050 U
Aroclor-1260	0.048 U	0.050 U	nd	nd	0.050 U	0.050 U

^a Number of compounds grouped together listed in parenthesis.

^b Compounds not detected and calibration was not available to calculate detection limit.

6.1 Discussion of Organic Analysis

Some difficulties were encountered during the extraction preparation for samples W-26 and W-28 supernatant samples. These problems appear to have impacted the semivolatile and PCB analysis for W-26 as explained below. Although the hold time requirements from the sample collection to the sample extraction were satisfied, the hold time from extraction to analysis for PCB analysis was exceeded by thirteen days for sludge samples from tanks W-28 and W-31 because of instrument downtime. The surrogate recoveries for these samples were within control limits and thus there is considered to be no impact to data quality due to the missed holding time.

During the extraction of the W-26 liquid sample the extraction mixture formed three layers. The bottom and middle layers appeared to be emulsions and the top layer was clear. The top layer was determined to be methylene chloride, which was not expected because methylene chloride is more dense than water. Additional methylene chloride extractions were performed on the emulsions to try to recovery any organic compounds which may have been trapped in the emulsified layers. Including all attempts to recover the methylene chloride, only 50% of the total volume used in the extraction was actually recovered. The PCB surrogate recoveries were below the control limits for this sample. The semivolatile surrogate recoveries were comparable to the other MVST supernatant samples but still were low.

During the W-28 extraction there was no layer formation after the addition of methylene chloride even after centrifuging the extraction. It is interesting to note that the sample density was determined to be 1.34 g/mL for the W-28 liquid sample which is the same density of methylene chloride at 20 ^oC. This similarity in density explains the absence of any separation of the organic and aqueous phase. The sample was acidified using sulfuric acid which increased the density of the aqueous phase and an organic phase separated out on top of the aqueous. After acidification the added methylene chloride volume was fully recovered and the subsequent extractions were successfully performed on the acidified sample portion. The PCB and semivolatile surrogate recoveries for this sample were comparable to other MVST supernatant samples.

REFERENCES

T. D. Hylton, Sampling and Analysis Plan for the Bethel Valley Evaporator Service Tanks and the Melton Valley Storage Tanks, ORNL/M-5224, July 1996.

2. F. J. Peretz, B. R. Clark, C. B. Scott, and J. B. Berry, Characterization of Low-Level Liquid Wastes at the Oak Ridge National Laboratory, ORNL/TM-10218, December 1986.

3. M. B. Sears, J. L. Botts, R. N. Ceo, J.J. Ferrada, W. H. Griest, J. M. Keller, and R. L. Schenley, Sampling and Analysis of Radioactive Liquid Wastes and Sludges in the Melton Valley and Evaporator Facility Storage Tanks at ORNL, ORNL/TM-11652, September 1990.

4. J. M. Keller, J. M. Giaquinto, and W. H. Griest, Characterization of Selected Waste Tanks from the Active LLLW System, ORNL/TM-13248, August 1996.

5. M. B. Sears, Results of Sampling the Contents of the Liquid Low-Level Waste Evaporator Feed Tank W-22, ORNL/TM-13234, September 1996.

6. S. M. DePaoli, Oak Ridge National Laboratory, personal communication to J. M Keller, December 12, 1996.

7. U. S. Environmental Protection Agency, Test Methods for Evaluating Solid Waste, SW-846, 3rd ed, Office of Solid Waste and Emergency Response, Washington, D.C., November 1986; Update I, July 1992; and Final Update II, September 1994.

8. J. M. Giaquinto, A. M. Essling, and J. M. Keller, Comparison of SW-846 Method 3051 and SW-846 Method 7471A for the Preparation of Solid Waste Samples for Mercury Determination, ORNL/TM-13236, July 1996.

9. Transuranic Waste Characterization Quality Assurance Program Plan, Rev. 0, CAO-94-1010, April 30, 1995

10. Radioactive Materials Analysis Laboratory - Oak Ridge National Laboratory (RMAL-ORNL) Quality Assurance Project Plan (QAPjP) for the Transuranic Waste Characterization Program (TWCP), Rev. 1, QAP-X-CASD/RML-002, January 1996.

11. Radioactive Materials Analysis Laboratory Quality Assurance Plan for the Characterization of Radioactive Waste, QAP-X-CASD/RML-001, Rev. 1, June 1996

12. Waste Acceptance Criteria for the Waste Isolation Pilot Plant, WIPP-DOE-069, Rev. 5.0, April 1996.

APPENDIX A

Radioactive Materials Analytical Laboratory

QC Acceptance Criteria for Radioactive Liquid/Solid Waste Samples

Analysis

Method (s)

CASD-AM-

Quality Control

Check

(per batch)

SW-846

Acceptance

Criteria

(%D, %R, RPD)^e

RMAL

Acceptance

Criteria

(%D, %R, RPD)^e

Metals by ICP-AES (inductively coupled plasma atomic emission spectroscopy)

SW846-6010A

high standard

calibration verifications (ICV & CCV)^a

calibration blank & checks (ICB & CCB)^b

method blank (sample prep)^c

matrix spike

matrix spike duplicate or sample duplicate

laboratory control sample (sample prep)^c

serial dilution (if interference suspected)

post digestion spike^d

±5%D

±10%D

<3 x IDL

±20%D

±20 RPD

none specified

±10%R

±20%D

±5%D

±10%D

<3 x IDL

±25%D (liq.), ±30%D (solid)

±20 RPD (liq.), ±30 RPD (solid)

±20%D

±10%R

±25%D (liq.), ±30%D (solid)

Metals by ICP-MS (inductively coupled plasma-mass spectrometry)

SW846-6020

calibration verifications (ICV & CCV)^a

calibration blank & blank checks (CCB)^b

method blank (sample prep)^c

matrix spike

matrix spike duplicate or sample duplicate

laboratory control sample (sample prep)^c

internal standard

post digestion spike^d

±10%D

<3 x IDL

none specified

±20 RPD

none specified

30-120% R

±10%D

<3 x IDL

<10 x IDL

±25%D (liq.), ±30%D (solid)

±20 RPD (liq.), ±30 RPD (solid)

±20%D

±30%D

±20%D

Metals by GFAA (graphite furnace atomic absorption)

SW846-7000A

high standard

calibration verifications (ICV & CCV)^a

method blank (sample prep)^c

matrix spike

matrix spike duplicate

laboratory control sample (sample prep)^c

serial dilution (if interference suspected)

post digestion spike^d

not required

±10%D (ICV), ±20%D (CCV)

none specified

±10%R

±15%D

±5%D

±10%D (ICV), ±20%D (CCV)

<3 x IDL

±25%D (liq.), ±30%D (solid)

±20 RPD (liq.), ±30 RPD (solid)

±25%D

±10%R

±25%D (liq.), ±30%D (solid)

Mercury by CVAA (cold vapor atomic absorption)

SW846-7471A

SW846-7470

instrument blank

calibration verification (ICV & CCV)^a

method blank (sample prep)^c

laboratory control sample (sample prep)^c

matrix spike

matrix spike duplicate or sample duplicate

post digestion spike^d

none specified

<5 x IDL

±10%D

<5 x IDL

±25%D

±25%D (liq.), ±30%D (solid)

±20 RPD (liq.), ±30 RPD (solid)

±25%D (liq.), ±30%D (solid)

Carbon (total organic carbon, total carbon, total inorganic carbon)

SW846-9060

instrument blank

calibration verification (ICV & CCV)^a

matrix spike

matrix spike duplicate

none specified

<3 x IDL

±10%D (ICV.), ±20%D (CCV)

±25%D (liq.), ±30%D (solid)

±20 RPD (liq.), ±30 RPD (solid)

Anions by Ion Chromatography

(IC)

SW846-9056

calibration verification (ICV & CCV)^a

matrix spike

sample duplicate

±10%D (ICV), ±5%D (CCV)

none specified

±10%D (ICV), ±15%D (CCV)

±25%D

±20 RPD

pH measurement

SW846-9040A

SW846-9045B

check standard

sample duplicate

none specified

±10%D

±20%D

Total and dissolved solids (TS & TDS)

EPA600-160.2

EPA600-160.3

sample duplicate

check standard

none specified

±10 mg/ 10mL sample

±10%D

Carbonate and bicarbonate titration

AC-MM-1 003105

sample duplicate

check standard

none specified

±20 RPD

±20%D

Gross alpha/beta

EPA-900.0

RML-RA02

RML-RA12

background check

calibration verification

method blank (optional)^f

sample duplicate

matrix spike

none specified

< 3sigma daily change

±10%D

evaluated for contamination

±25 RPD (liq.), ±30 RPD (solid)

±25%D (liq.) & ±30%D (solid)

Nuclides by gamma spectrometry

EPA-901.1

background check

calibration verification

sample duplicate

none specified

< 3sigma daily change

± 10%D

±25%D (liq.) & ±30%D (solid)

Sr-90 determination

RML-RA13

EPA-905.0

method blank (optional)^f

laboratory control sample

matrix spike

matrix spike duplicate or sample duplicate

associated instrument QC

none specified

evaluated for contamination^g

20%D

±25%D (liq.) & ±30%D (solid)

±25 RPD (liq.), ±30 RPD (solid)

see gross alpha/beta criteria

Tc-99 determination

DOE Compendium RP550

RML-RA05

method blank (optional)^f

laboratory control sample

matrix spike

matrix spike or sample duplicate

associated instrument QC

none specified

< 3 x IDL

20%D

±25%D (liq.) & ±30%D (solid)

±25 RPD (liq.), ±30 RPD (solid)

see ICP-MS criteria

H-3 determination

EPA-906.0

method blank (optional)^f

laboratory control sample

matrix spike

matrix spike duplicate or sample duplicate

associated instrument QC

none specified

evaluated for contamination^g

20%D

±25%D (liq.) & ±30%D (solid)

±25 RPD (liq.), ±30 RPD (solid)

see gross alpha/beta criteria

Cm-244

RML-RA06

method blank (optional)^f

laboratory control sample

matrix spike

matrix spike duplicate or sample duplicate

associated instrument QC

none specified

evaluated for contamination^g

20%D

±25%D (liq.) & ±30%D (solid)

±25 RPD (liq.), ±30 RPD (solid)

see gross alpha/beta criteria

Pu-238,239/240

RML-RA11

RML-RA08

method blank (optional)^f

laboratory control sample

matrix spike

matrix spike duplicate or sample duplicate

associated instrument QC

none specified

evaluated for contamination^g

20%D

±25%D (liq.) & ±30%D (solid)

±25 RPD (liq.), ±30 RPD (solid)

see gross alpha/beta criteria

U-233/234

RML-RA10

method blank (optional)^f

laboratory control sample

matrix spike

matrix spike duplicate or sample duplicate

associated instrument QC

none specified

evaluated for ^{contaminating}

20%D

±25%D (liq.) & ±30%D (solid)

±25 RPD (liq.), ±30 RPD (solid)

see gross alpha/beta criteria

Th Determination

EPA-901.1

RML-RA09

method blank (optional)^f

laboratory control sample

matrix spike

matrix spike duplicate or sample duplicate

associated instrument QC

none specified

evaluated for contamination^g

20%D

±25%D (liq.) & ±30%D (solid)

±25 RPD (liq.), ±30 RPD (solid)

see gamma spectrometry criteria

PCBs

(polychlorinated-biphenyls)

SW846-8080

calibration verification (ICV & CCV)^a

method blank (sample prep)^c

surrogate standard

matrix spike

matrix spike duplicate

sample duplicate

laboratory control sample (sample prep)^c

refer to method 8080

none specified

to be specified^h

< regulatory limit (2ppm)

± 50-150%R

to be specified^h

Volatile organics

SW846-8260

calibration verification (ICV & CCV)^a

method blank (sample prep)^c

surrogate standard

matrix spike

matrix spike duplicate

sample duplicate

laboratory control sample (sample prep)^c

see SW846 8260, Sept. '86

± 20% D

3 X MDL

refer to supplement Table A

Nonhalogenated volatile organics

SW846-8015

calibration verification (ICV & CCV)^a

method blank (sample prep)^c

surrogate standard

matrix spike

matrix spike duplicate

sample duplicate

laboratory control sample (sample prep)^c

see SW846-8015, Sept. '86

± 15% D

3 X MDL

refer to supplement Table B

Semivolatile organics

SW846-8270

calibration verification (ICV & CCV)^a

method blank (sample prep)^c

surrogate standard

matrix spike

matrix spike duplicate

sample duplicate

laboratory control sample (sample prep)^c

see SW846-8270, Sept. '86

± 20% D

3 X MDL

refer to supplement Table C

a Initial calibration verification (ICV) is typically performed at the beginning of a run to check the calibration and must be independent of the calibration standards. The continuing calibration verification (CCV) must also be independent of the calibration standards, but may be the same standard as the ICV. The CCV is typically analyzed every 10 samples and at the end of the run for metals analysis or every 12 samples for organic analysis.

b The calibration blank is an instrument blank used in the calibration to initially determine the blank value and therefore used as blank subtraction. The continuing calibration blank (CCB) is also an instrument blank which is analyzed every 10 samples and at the end of the run, but is not used in blank subtraction, but only to monitor instrument contamination.

c Method blanks and laboratory control samples are only required if a sample preparation is performed before analysis. Sample preparation does not include dilutions or transfers to containers.

d Post digestion spikes are not necessary if the pre-digestion spike is in control. If this control does not meet the QC acceptance criteria, the post digestion spike should be performed.

e Acceptance criteria:

%D = % deviation from true value

%R = % recovery of true value

RPD = relative percent difference between two compared values

f Method blanks for radiochemical analysis are used to monitor cross contamination. However, due to the levels of radioactivity present in samples at the RMAL, the effect of contamination may be insignificant in most cases. Therefore, the requirement to analyze a method blank for radiochemical analysis is optional (i.e. at the discretion of the chemist or supervisor).

g Acceptance criteria for the method blanks performed for radiochemical analysis varies based upon the level of activity in the samples and the amount of background activity. A qualified chemist reviews the data from method blanks to determine if significant contamination is present.

h The acceptance criteria for PCB analyses which are not identified in this table, shall be specified at a later date. Currently, the Analytical Methods Group group leader specifies the QC criteria if different from SW846 and if not specified by the sample generator.

SUPPLEMENT TABLE A

Volatile Organic Analyses QC Limits

CAS # Compound Precision (RPD) Accuracy
(% R)
MDL
(mg/Kg)
PRQL
(mg/Kg)
LCS
(% R)

75-01-4 Vinyl Chloride 200 D-251 1 4 34-100

75-69-4 Trichlorofluoromethane 110 17-181 1 10 47-103

76-13-1 1,1,2-Trichloro-1,2-2-Trifluoroethane 50 60-150 1 10 49-105

75-35-4 1,1-Dichloroethylene 250 D-234 1 10 43-100

75-9-2 Methylene Chloride 50 D-221 1 10 67-108

75-15-0 Carbon Disulfide 50 60-150 1 10 36-100

67-66-3 Chloroform 44 51-138 1 10 72-111

107-6-2 1,2-Dichloroethane 42 49-155 1 10 76-112

71-55-6 1,1,1-Trichloroethane 33 52-162 1 10 71-110

56-23-5 Carbon Tetrachloride 30 70-140 1 10 54-115

71-43-2 Benzene 45 37-151 1 10 70-109

79-1-6 Trichloroethylene 36 71-157 1 10 80-120

79-0-5 1,1,2-Trichloroethane 38 52-150 1 10 80-120

75-25-2 Bromoform 47 45-169 1 10 61-115

108-88-3 Toluene 29 47-150 1 10 80-120

127-18-4 Tetrachloroethylene 29 64-148 1 10 80-120

108-90-7 Chlorobenzene 38 37-160 1 10 80-120

100-41-4 Ethylbenzene 43 37-162 1 10 80-120

1330-20-7 Xylenes 50 60-150 1 10 80-120

79-34-5 1,1,2,2-Tetrachloroethane 55 46-157 1 10 67-117

106-46-7 1,4-Dichlorobenzene 60 18-190 1 10 80-120

95-50-1 ortho-Dichlorobenzene 60 18-190 1 10 80-112

60-29-7 Ethyl Ether 50 60-150 1 10 54-100

Surrogates

1,2-Dichloroethane-d₄ 61-129

Toluene-d₈ 89-118

4-Bromofluorobenzene 93-107

SUPPLEMENT TABLE B

Nonhalogenated Volatile Organic Analyses QC Limits

CAS #	Compound	Precision (RPD)	Accuracy (% R)	MDL (mg/Kg)	PRQL (mg/Kg)	LCS (% R)
67-56-1	Methanol	50	60-150	10	100	49-145
67-64-1	Acetone	50	60-150	10	100	61-136
78-93-3	Methyl Ethyl Ketone	50	60-150	10	100	62-134
78-83-1	Isobutanol	50	60-150	10	100	52-126
71-36-3	Butanol	50	60-150	10	100	50-110
110-86-1	Pyridine	50	60-150	10	100	64-122
Surrogate
71-23-8	n-Propanol		60-150

SUPPLEMENT TABLE C

Semivolatile Organic Analyses

QC Limits

CAS #	Compound	Precision (RPD)	Accuracy (% R)	MDL (mg/Kg)	PRQL (mg/Kg)	LCS (% R)
95-48-7	2-Methylphenol	50	60-150	5	40	46-104
67-72-1	Hexachloroethane	44	40-113	5	40	38-100
106-44-5	4-Methylphenol	50	60-150	5	40	46-114
98-95-3	Nitrobenzene	72	35-180	5	40	46-100
121-14-2	2,4-Dinitrotoluene	46	39-139	0.3	2.6	54-146
118-74-1	Hexachlorobenzene	319	D-152	0.3	2.6	52-115
87-86-5	Pentachlorophenol	128	14-176	5	40	54-130
51-28-5	2,4-Dinitrophenol	119	D-172	5	40	47-100
Surrogates
367-12-4	2-Fluorophenol		D-107
	Phenol-d₅		8-142
	Nitrobenzene-d₅		28-117
321-60-8	2-Fluorobiphenyl		24-144
	2,4,6-Tribromophenol		D-100
	Terphenyl-d₁₄		D-226

APPENDIX B

This section includes three tables of information and measurements that may be of value to the data users. The first Table B1, includes the field measurements taken from the top of the tank to each phase change (air/liquid, liquid/sludge, and bottom of the tank). Table B1 also includes the total mass and/or activity for some of the major species in the sludge of general interest to the data users.

The dose measurement taken in during the field sampling for the liquid and sludge samples are included in Table B2 and Table B3. The dose measurements were taken at contact with the sampling container (250 mL I-Chem jar) for the liquids and at contact with the one inch core sludge sampling device.

Table B1 Total Mass and Activity for Selected Species of Interest in Sludge

Measurement W-24 W-25 W-26 W-27 W-28 W-31

Depth to top of liquid (in.) 192 140 139 184 140 148

Depth to top of sludge (in.) 225 204 214 206 235 218

Depth to top of hard sludge (in.) 258 258 255 249 256 247

Depth to bottom of tank (in.) 258 258 255 257 256 256

Depth of supernatant (in.) 33 64 75 22 95 70

Depth of soft Sludge (in.) 33 54 41 43 21 29

Depth of hard Sludge (in.) 0 0 0 8 0 9

Total depth of Sludge (in.) 33 54 41 51 21 38

Summary of tank volumes and sludge mass Total

Volume of Supernatant (L) 51500 101500 124200 37900 150300 126100 591500

Volume of Sludge (L) 32900 65500 44700 60600 17000 40100 260800

Density of Sludge (Kg/L) 1.37 1.36 1.38 1.44 1.37 1.44

Mass of Sludge (Kg) 45073 89080 61686 87264 23290 57744 364137

Concentration of selected species of interest in sludge

Thorium (mg/Kg) 3270 9250 3280 1290 1360 20700

Uranium (mg/Kg) 6780 7660 19400 11700 18500 19800

Plutonium (mg/Kg) 0.96 1.73 0.70 0.35 0.45 1.82

²³³U (mg/Kg) 3.6 6.6 25.1 2.5 12.0 10.9

²³⁵U (mg/Kg) 33.2 45.2 51.3 35.7 46.2 121.0

²³⁹Pu (mg/Kg) 0.84 1.46 0.57 0.29 0.36 1.49

Activity for selected species of interest in sludge

⁹⁰Sr (Bq/g) 1400000 3200000 710000 450000 700000 11000000

¹³⁷Cs (Bq/g) 530000 470000 890000 390000 310000 430000

²³³U (Bq/g) 1600 2800 10000 1000 5200 5200

²³⁸Pu (Bq/g) 3800 7800 5400 2400 3000 13000

²⁴¹Am (Bq/g) 3900 9300 3900 2800 4600 14000

²⁴⁴Cm (Bq/g) 22000 58000 28000 17000 25000 110000

Total mass for selected species of interest in sludge Total

Thorium (Kg) 147.4 824.0 202.3 112.6 31.7 1195.3 2513.3

Uranium (Kg) 305.6 682.4 1196.7 1021.0 430.9 1143.3 4779.8

Plutonium (Kg) 0.043 0.154 0.043 0.030 0.010 0.105 0.386

²³³U (Kg) 0.162 0.588 1.548 0.220 0.279 0.629 3.427

²³⁵U (Kg) 1.496 4.026 3.164 3.115 1.076 6.987 19.866

²³⁹Pu (Kg) 0.038 0.130 0.035 0.026 0.008 0.086 0.323

Total activity for selected species of interest in sludge Total

⁹⁰Sr (Ci) 1705.46 7704.22 1183.70 1061.32 440.62 17167.14 29262.5

¹³⁷Cs (Ci) 645.64 1131.56 1483.80 919.81 195.13 671.08 5047.0

²³³U (Ci) 1.95 6.74 16.67 2.36 3.27 8.12 39.1

²³⁸Pu (Ci) 4.63 18.78 9.00 5.66 1.89 20.29 60.2

²⁴¹Am (Ci) 4.75 22.39 6.50 6.60 2.90 21.85 65.0

²⁴⁴Cm (Ci) 26.80 139.64 46.68 40.09 15.74 171.67 440.6

Table B2 Dose Measurements on Liquid Samples
	Supernatant
	(mR/hr)
					Date
Tank	L1	L2	L3	Color	sampled
W-24	420	440	none	yellow	08/05/96
W-25	440	450	none		08/05/96
W-26	600	600	none		07/24/96
W-27	130	125	none		07/24/96
W-28	220	240	none	yellow	07/10/96
W-31	180	200	none	yellow	07/10/96





Table B3 Dose Measurements on Sludge Samples
	Sludge
	(mR/hr)
					Date
Tank	S1	S2	S3	Color	sampled
W-24	600	650	none	tan	08/06/96
W-25	350	400	800		08/22/96
W-26	500	700	none		08/30/96
W-27	150	250	250		09/04/96
W-28	1100	2900	none	brown	07/24/96
W-31	1400	1500	none	lt. brown	07/16/96

Note: All dose measurements measured on contact with sampling device.

INTERNAL DISTRIBUTION

J. F. Alexander

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C. A. Bednarz

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D. A. Bostick

7-8. Central Research Library

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14-16. J. M. Giaquinto

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EXTERNAL DISTRIBUTION

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Isotope	²³⁹Pu FGE factor	W-24 (mg/Kg)	W-25 (mg/Kg)	W-26 (mg/Kg)	W-27 (mg/Kg)	W-28 (mg/Kg)	W-31 (mg/Kg)
²³³U	0.865	3.58	6.6	25.1	2.52	12.0	10.9
²³⁵U	0.641	33.2	41.0	51.3	35.7	46.2	121
²³⁹Pu	1.000	0.84	1.46	0.57	0.29	0.36	1.49
²³⁹Pu FGE (mg/Kg)		25.22	33.45	55.16	25.35	40.35	88.48
²³⁹Pu FGE in 55 gal. (g)		7.2	9.5	15.8	7.6	11.5	26.5

Isotope	²³⁹Pu wt. factor^a	W-24 (Bq/g)	W-25 (Bq/g)	W-26 (Bq/g)	W-27 (Bq/g)	W-28 (Bq/g)	W-31 (Bq/g)
²³³U	3.9	1600	2800	10000	1000	5200	5200
²³⁸Pu	1.1	3800	7800	5400	2400	3000	13000
²³⁹Pu	1.0	1900	3400	1300	670	830	3400
²⁴⁰Pu	1.0	870	1800	890	370	600	2200
²⁴¹Pu	52.0	14000	26000	15000	6500	12000	24000
²⁴¹Am	1.0	3900	9300	3900	2800	4600	14000
²⁴⁴Cm	1.9	22000	58000	28000	17000	25000	110000
²³⁹Pu Eqv. (Bq/g)		22382.98	53335.17	28588.50	15350.60	23479.27	91107.79
²³⁹Pu Eqv. in 55 gal. (Ci)		0.17	0.41	0.22	0.12	0.18	0.74

Measurement		W-24	W-25	W-26	W-27	W-28	W-31
Depth to top of liquid	(in.)	192	140	139	184	140	148
Depth to top of sludge	(in.)	225	204	214	206	235	218
Depth to top of hard sludge	(in.)	258	258	255	249	256	247
Depth to bottom of tank	(in.)	258	258	255	257	256	256

Depth of supernatant	(in.)	33	64	75	22	95	70
Depth of soft Sludge	(in.)	33	54	41	43	21	29
Depth of hard Sludge	(in.)	0	0	0	8	0	9
Total depth of Sludge	(in.)	33	54	41	51	21	38
Summary of tank volumes and sludge mass								Total
Volume of Supernatant	(L)	51500	101500	124200	37900	150300	126100	591500
Volume of Sludge	(L)	32900	65500	44700	60600	17000	40100	260800
Density of Sludge	(Kg/L)	1.37	1.36	1.38	1.44	1.37	1.44
Mass of Sludge	(Kg)	45073	89080	61686	87264	23290	57744	364137
Concentration of selected species of interest in sludge
Thorium	(mg/Kg)	3270	9250	3280	1290	1360	20700
Uranium	(mg/Kg)	6780	7660	19400	11700	18500	19800
Plutonium	(mg/Kg)	0.96	1.73	0.70	0.35	0.45	1.82
²³³U	(mg/Kg)	3.6	6.6	25.1	2.5	12.0	10.9
²³⁵U	(mg/Kg)	33.2	45.2	51.3	35.7	46.2	121.0
²³⁹Pu	(mg/Kg)	0.84	1.46	0.57	0.29	0.36	1.49
Activity for selected species of interest in sludge
⁹⁰Sr	(Bq/g)	1400000	3200000	710000	450000	700000	11000000
¹³⁷Cs	(Bq/g)	530000	470000	890000	390000	310000	430000
²³³U	(Bq/g)	1600	2800	10000	1000	5200	5200
²³⁸Pu	(Bq/g)	3800	7800	5400	2400	3000	13000
²⁴¹Am	(Bq/g)	3900	9300	3900	2800	4600	14000
²⁴⁴Cm	(Bq/g)	22000	58000	28000	17000	25000	110000
Total mass for selected species of interest in sludge								Total
Thorium	(Kg)	147.4	824.0	202.3	112.6	31.7	1195.3	2513.3
Uranium	(Kg)	305.6	682.4	1196.7	1021.0	430.9	1143.3	4779.8
Plutonium	(Kg)	0.043	0.154	0.043	0.030	0.010	0.105	0.386
²³³U	(Kg)	0.162	0.588	1.548	0.220	0.279	0.629	3.427
²³⁵U	(Kg)	1.496	4.026	3.164	3.115	1.076	6.987	19.866
²³⁹Pu	(Kg)	0.038	0.130	0.035	0.026	0.008	0.086	0.323
Total activity for selected species of interest in sludge								Total
⁹⁰Sr	(Ci)	1705.46	7704.22	1183.70	1061.32	440.62	17167.14	29262.5
¹³⁷Cs	(Ci)	645.64	1131.56	1483.80	919.81	195.13	671.08	5047.0
²³³U	(Ci)	1.95	6.74	16.67	2.36	3.27	8.12	39.1
²³⁸Pu	(Ci)	4.63	18.78	9.00	5.66	1.89	20.29	60.2
²⁴¹Am	(Ci)	4.75	22.39	6.50	6.60	2.90	21.85	65.0
²⁴⁴Cm	(Ci)	26.80	139.64	46.68	40.09	15.74	171.67	440.6