S WHC-SA-3085-FP

Management of Data Quality for High-Level Waste Characterization W. I. Winters A. G. King T. C. Trible Westinghouse Hanford Company, Richland, Washington, USA

K. J. Kuhl-Klinger Pacific Northwest National Laboratory

Date Published June 1996

To Be Presented at American Chemical Society 51st Northwest Regional Meeting June 19-22, 1996 Cowallis, Oregon

Prepared for the U.S. Department of Energy Assistant Secretary for Environmental Management

Westinghouse P.O BOX 1970 Hanford Company filchland, Washington

Management and Operations ContractOT far the U.6. Department of Energy under Contract DE-AC06-87RL10930

b-ht Limr By rsmncs of thi d d s . the pubhha d l o r d e n t &owkdos the U.S. Govmmt'm k h t to r h i n nonudusivs, roydlyhoa h md to m y Sopwbht s0v-o thi p 9 r .

Approved for public release; distribution is unlimited

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MANAGEMENT OF DATA QUALITY FOR HIGH-LEVEL WASTE CHARACTERIZATION

ABSTRACT

Over the past IO years, the Hanford Site has been transitioning j b m nuclear materials

production to Site cleanup operations. High-level waste characterization at the Hanford Site

provides data to support present waste processing operations, tank safety programs, and

future waste disposal programs. Quality elements in the high-level waste characterization

program will be presented by following a sample through the data quality objective,

sampling, laboratory analysis and data review processes.

Tramition from production to cleanup has resulted in changes in quality systems and

programs; the changes, as well as other issues in these quality programs, will be hcribed.

Laboratory assessment through quality control and per$onnance evalm'on programs will be

described, and abta assessments in the laboratory and fhal reporting in the tank

characterim'on reports will be discussed.

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CONTENTS

INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7

THE HANFORD SITE’S PRODUCTION MISSION ...................... 7 FuelRepmcessing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 ProductRefining . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 WasteRecovery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

HIGH-LEVEL WASTE PROGRAMS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

Q U A L m ASSURANCE FOR PRODUCTION AND MEASUREMENT PROCESSES . 12

QUALITY ASSURANCE SYSTEMS AND PLANS . . . . . . . . . . . . . . . . . . . . . . . 16

SYSTEMATIC APPROACH TO CHARACTERIZATION . . . . . . . . . . . . . . . . . . . 16

DATA QUALITY OBJECTIVE PROCESS . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17

TANK SAMPLING AND ANALYSIS PLANS . . . . . . . . . . . . . . . . . . . . . . . . . . 23

FIELD SAMPLING QUALITY ELEMENTS . . . . . . . . . . . . . . . . . . . . . . . . . . . 24

SUBSAMPLING QUALITY ELEMENTS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26

QUALITY ELEMENTS IN THE MEASUREMENT PROCESS . . . . . . . . . . . . . . . 26

PERFORMANCE EVALUATION PROGRAMS . . . . . . . . . . . . . . . . . . . . . . . . . 28

DATA EVALUATION AND REPORTING . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29

AUDITS AND ASSESSMENTS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31

CONCLUSION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33

REFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34

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LIST OF FIGURES

1 . 2 . 3 . 4 . 5 .

1 . 2 . 3 . 4 . 5 . 6 . 7 . 8 . 9 . 10 . 11 . 12 . 13 . 14 . 15 . 16 . 17 . 18 .

19 .

Relationship of Hanford Site High-Level Waste Activities . . . . . . . . . . . . . . . . 11 Production Process Quality Assurance . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13 Measurement Process Quality Assurance . . . . . . . . . . . . . . . . . . . . . . . . . . . 15 Systematic Approach to Characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . 18 Continuous Quality Improvement Process . . . . . . . . . . . . . . . . . . . . . . . . . . 32

LIST OF TABLES

. . . . . . . . . . . . . . . . . . . . . . . . . . Origin of Hanford Site High-Level Waste 7

14 High-Level Waste Programs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10 Differences in Production and High-Level Waste Characterization Processes . . . . . Quality Assurance System Transitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17 Elements of Various Quality Assurance Systems and Plans . . . . . . . . . . . . . . . . 19 DQO Process Steps . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20 Tank Waste Characterization Data Quality Objectives . . . . . . . . . . . . . . . . . . . 20

Safety Screening of Waste Tanks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21 Issues Associated with Developing DQOs . . . . . . . . . . . . . . . . . . . . . . . . . . 23 Tank Sampling and Analyses Plan Contents . . . . . . . . . . . . . . . . . . . . . . . . . 23 Field Sampling Quality Elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24 Subsampling (Hot Cell) Quality Elements . . . . . . . . . . . . . . . . . . . . . . . . . . 26 High-Level Waste Measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27 Quality Elements In the Measurement Process . . . . . . . . . . . . . . . . . . . . . . . 27 Performance Evaluation Programs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28 Phase Development of the SEE Program 30 . . . . . . . . . . . . . . . . . . . . . . . . . 29 Data Evaluation for High-Level Waste Characterization . . . . . . . . . . . . . . . . . 30 Key Criteria for QA Review of High-Level Waste Characterization Data Package . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33 Audits and Assessments 33

Example of DQO Process Results for

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

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LIST OF TERMS

Pgk AES ANSI ASME ASTM CLP CQIP DOE DOWRL DQO DSC DST EDTA EMSL EPA

HASQAP HDEHPA HEDTA HHF HLW ICP in. Jk LERF LFL mL MST NPH PUREX QA QAP QC REDOX SAP SEE SST TAP TBP TGA TWRS

micrograms per gram atomic emission spectrometry American National Standards Institute American Society of Mechanical Engineers American Society for Testing and Materials Contract Laboratory Program continuous quality improvement process U.S. Department of Energy U.S. Department of EnergylRichland Operations Office data quality objective differential scanning calorimetry double-shell tank ethylenediinetetraacetic acid Environmental Monitoring Systems Laboratory Environmental Protection Agency

Hanford Analytical Services Quality Assurance Plan di-2ethylhexylphosphoric acid hydroxyethylethylenediaminetriacetic acid (HEDTA) hydrostatic head fluid high-level waste inductively coupled plasma inch joules per gram Liquid Effluent Retention Facility lower flammability limit milliliter National Institute of Standards and Technology normal paraffin hydrocarbon plutonium-uranium extraction

grams per liter

quality assurance quality assurance plan quality control reduction-oxidation sampling and analysis plan Sample Evaluation and Exchange Program single-shell tank Technical Advisory Panel tributyl phosphate thermogravimetric analysis Tank Waste Remediation System

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REDOX Plant Hexone Solvent Extraction

INTRODUCTION

Plutonium Finishing Plant B Plant Fission Product Recovery HDEHPA Solvent Extraction and Ion Exchange

During the last ten years, the work scope at the Hanford Site has changed significantly. Emphasis has shifted from operation of nuclear material production facilities to management and cleanup of nuclear facilities, waste, and Hanford Site lands. This change in work scope has required increased interaction with Federal and State environmental regulatory agencies, and has led to significant changes in the systems and programs used to ensure quality. Quality wntrol programs associated with high-level waste (HLW) measurements present unique problems. This paper discusses the changes in the Hanford Site mission, how the changes impact the direction of quality assurance programs, and how these quality elements are being implemented in the present Tank Waste Remediation System (TWR!5) HLW characterization program.

THE HANFoRD SITE’S PRODUCTION MISSION

Understanding the Hanford Site’s production processes is important in understanding the origin of the waste and some of the complexities in its characterization. The major chemical processing operations are identified in Table 1. For discussion purposes, the operations have been classified as fuel reprocessing, product refining, and waste recovery operations.

Table 1. Origin of Hanford Site High-Level Waste.

IBismuth Phosphate Process Uranium Recovery TBP Solvent Extraction

PUREX Plant Waste Encapsulation Plant I TBP Solvent Extraction

Fuel Reprocessing

The first fuel reprocessing at the Hanford Site was performed at B Plant in the 200 East Area using the bismuth phosphate precipitation process. The aluminum cladding on the reactor fuel was removed with sodium hydroxide and the uranium metal fuel dissolved in nitric acid. Plutonium was removed from the dissolved fuel by co-precipitation with bismuth phosphate.

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The plutonium was purified by multiple precipitations with bismuth phosphate and lanthanum fluoride. The uranium was not recovered in this process, but was sent to the waste tanks with fission products and other neutralized waste. The bismuth phosphate process was also used at the T Plant facility in the 200 West Area. Large waste volumes generated in the bismuth phosphate process are responsible for much of the waste presently found in the single-shell tanks at the Hanford Site.

The next fuel repromsing process, known as the reduction-oxidation (REDOX) process, used hexone to extract and recover both uranium and plutonium from the dissolved fuel. The nitric-acid-dissolved fuel was highly salted with aluminum nitrate to increase the extraction efficiency of uranium and plutonium. The plutonium was partitioned and purified from the uranium and fission products by adjustment of its valence state with different oxidants and reductants. The waste volumes produced by the REDOX process were significantly less than those. produced by the bismuth phosphate process. Neutralized REDOX waste contained significant quantities of aluminum from the salting agent and chromium used for plutonium oxidation.

The last fuel reprocessing method at the Hanford Site, plutonium-uranium extraction 0, used a process based on the solvent extraction of uranium and plutonium from the dissolved fuel using tributyl phosphate (TBP) in normal paraffm hydrocarbon (NPH). Like the REDOX process, the PUREX process controlled the plutonium valence state to separate plutonium from uranium and fission products. However, it did not require the large quantities of aluminum nitrate used in the REDOX process to achieve good extraction efficiencies, and therefore the waste volumes from the PUREX process were reduced further. The PUREX facility was also used to reprocess zirconium-clad fuels from the Hanford Site N Reactor. Decladding of zkwloy fuel was done with an ammonium nitrate and ammonium fluoride solution. PUREX waste contained significant quantities of iron from ferrous sulfamate reductant used in the process. All of the reprocessing facilities generated large quantities of sodium salts, particularly nitrates, from the sodium hydroxide neutralization of the nitric acid waste streams generated in the process before they were transferred to the waste tanks.

Product Refining

Three product refining operations were used at the Hanford Site. These operations produced significantly smaller quantities of waste than fuel reprocessing operations. The U Q Plant was used to convert purified uranyl nitrate from the reprocessing facilities to uranium oxide. This process involved further uranium purification and conversion by precipitation and calcination. The Plutonium Finishing Plant used several different processes in the recovery, purification and conversion of plutonium from reprocessing facilities and scrap to plutonium oxide and metal. The Waste Encapsulation and Storage Facility used precipitation and calcination to produce '"Cs chloride and %.r fluoride product capsules from isotopes separated in the fission product recovery process.

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Waste Recovery

The first waste recovery activity was the uranium recovery process initiated in the early 1950s. This process was introduced to recover the uranium discarded to the waste tanks from the bismuth phosphate process. Sludge in the waste tanks was sluiced and sent to the U Plant facility where the uranium was separated by solvent extraction using TBP. During this period, the cesium nickel ferrocyanide process was used to remove I"Cs from the large volumes of supemate waste in the waste tanks.

The second waste recovery activity, fission product recovery, was initiated in the late 1960s. This p m s used solvent extraction with a mixture of di-2-ethylhexylphosphoric acid and TBP (HDE€PA/TJ3P/NpH) to separate %r, '"Ce and 147Pm and ion exchange to separate InCs from different sources of PUREX and REDOX wastes. The relatively large quantities of water soluble organics found in some waste tanks were introduced in this process. Complexants (hydrox yethyleth ylenediminetriamtic acid W T A ] , ethylenediamine- tetraacetic acid [EDTA], glycolate, tartrate, and citrate) were used to inhibit the extraction of iron and other metal impurities that would contaminate the WSr product. The fission product recovery process was complex and used other separation procedures on a smaller scale, such as lead sulphate precipitation and phosphotungstic acid, to separate and purify ?3r and '"Cs, respectively.

The combining and mixing of the waste from these processes has created waste tanks with supemates, saltcakes and sludges of widely varying compositions. Achieving reliable information from sampling and measurements on this complex composition of waste is a difficult task.

HIGH-LEVEL WASTE PROGRAMS

As shown in Table 2, HLW activities fall into three primary areas: present waste processing operations, tank safety programs, and future waste disposal programs. One of the present HLW activities is the operation of the 242-A Evaporator. The Evaporator is used to concentrate dilute waste from the double-shell tanks @STs). Liquid condensate from the Evaporator is transferred to the Liquid Effluent Retention Facility (LERF) for storage before being treated by the Effluent Treatment Facility and disposed of to the ground.

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P

I I I ~ E A I I

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Figure 1. Relationship of Hanford Site High-Level Waste Activities. - f

PI d

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QUALITY ASSURANCE FOR PRODUCTION AND MEASUREMENT PROCESSES

The focus of quality assurance at the Hanford Site has shifted from control of producing a material product to control of measurements used to make decisions on site cleanup and waste disposal. The quality assurance procedures for typical production and measurement processes have been summarized in Taylor (1987). The production quality assurance approach is outlined in Figure 2. In this approach, quality control is applied to the production proms and the product is tested for acceptability against a specification. Experience and knowledge of the process determines the level of control that is needed to obtain products of desired quality.

This type of quality process was used at the production facilities at the Hanford Site and also applies to operational control of the 242-A Evaprator. These processes normally involved well-characterid process streams that, if maintained withiin a specified range, would result in acceptable products. Most of the samples were liquid and homogeneous. Solid product materials were very pure and homogenous. Because the wastes from these processes were being stored and were not regulated, they were normally tested only against criticality and corrosion requirements. For the most part, these facilities were based on continuous, not batch, operations. Therefore, the samples and analyses were performed primarily to confirm that the process was operating within the desired ranges, not to make process decisions. Some of the differences in production and HLW clean-up processes are summarized in Table 3.

Because of production’s objectives and characteristics, many of the quality control elements found in today’s HLW characterization program were not used during production. Duplicate samples were not routinely taken for analysis. No field or preparation blanks, other than analytical method blanks, were performed. Analytical spikes were not used to evaluate matrix interferences because most of the methods had been developed and thoroughly tested for the process streams for which they were applied. Quality control was performed on a periodic basis (a prescribed number of standards per quarter) rather than on a batch basis as presently implemented in the characterization program. In this respect, the standards were used more as performance base indicators rather than as a tool for evaluating and controlling the measurement. An exception to this quality approach was the analysis of the product, which required more rigorous control procedures for sampling and analysis, such as replicate analyses and external National Institute of Standards and Technology (NIST) performance evaluation standards.

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Figure 2. Production Process Quality Assurance.

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QUALITY ASSURANCE SYSTEMS AND PLANS

During the last 10 years, the Hanford Site has seen numerous changes in quality assurance requirements. Some of these changes are outlined in Table 4. The primary applicable quality assurance program in the 1980s was NQA-1 (ASME 1986). This standard was developed by the American National Standards Institute (ANSI) and the American Society of Mechanical Engineers (ASME), and set the requirements for establishment and execution of quality assurance programs for siting, design, construction, operation and decommissioning of nuclear facilities. A laboratory interpretation (C-1009-83) of the NQA-1 requirements was developed by the American Society of Testing Materials (ASTM 1983) and used for guidance in quality assurance for nuclear analytical chemistry laboratories.

Recently, the quality assurance for U. S. Department of Energy (DOE) facilities and operations has been defined in DOE Order 5700.6C (DOE 1991). These requirements are also the basis for 10 CFR 830.120. Table 5 summarizes the major quality areas addressed for NQA-1 (ASME 1986), 10 CFR 830.120, and QAMS-005 @PA 1980b). In the late 1980s, the Hanford Federal Facility Agreement and Consent Order (Ecology et al. 1996) was signed introducing environmental quality assurance requirements. These requirements are defined in Environmental Protection Agency (EPA) guidance documents QAMS-004 (EPA 198Oa) and QAMS-005 (EPA 1980b) for development of quality assurance program and project plans. QAMS-004 and QAMS-005 are in the process of being revised by the EPA (EPA 1994a and 1994b). The elements for the QAMS-005 guideline for project plans are more specific for directing sampling and analysis systems for environmental cleanup operations than NQA-1 or DOE orders, which address broader quality assurance programs.

The Department of Energy, Richland Operations Office (DOWRL) has developed the Hanford Analytical Services Quality Assurance Plan (HASQAF') (DOE 1995) in response to the DOE and EPA requirements. This plan is designed to maintain a consistent level of quality for analytical services in support of Hanford Site operations. Laboratories performing measurements for Hanford Site operations have incorporated these HASQAP requirements into their laboratory-specific quality assurance plans. These requirements are implemented through laboratory standard operating procedures used in sample analysis.

SYSTEMATIC APPROACH TO CHARACTERIZATION

A chemical measurement is more than a single process; it is actually a series of processes that may be categorized as a system (Taylor 1987). These processes are outlined in Figure 4. Chemical measurements are made to answer questions necessary to solve a problem. The problem is represented in a model that defines the questions that need to be answered and the data requirements and their use. Based on the model, a measurement plan can be developed that addresses the sampling, analysis and quality control steps to be followed. These processes are dependent on each other and information from each process must be fed back to strengthen the overall measurement system. During the last few years this type of systematic approach has been applied to characterization of Hanford Site HLW.

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DOE Order

Federal Code EPA

EPA

DO=

Contractor

Table 4. Quality Assurance System Transitions.

5700.C (DOE 1991)

lOCFR830.120

QAMS-004/005 (EPA 198Oa, 1980b)

(EPA 1994a, 1994b)

HASQAP (DOE 1995)

Lab-Specific QAP

QA/R-2 and R-5

ANWASME NOA-1 (ASTM C-10091 I - (ASTM 1983) '

DATA QUALITY OBJECTIVE PROCESS

The EPA has used the data quality objective (DQO) process to minimize its sampling and analysis requirements in superfund remedial response activities @PA 1987). The DQO process has been explained further by Neptune (Neptune 1990). The seven general steps in the DQO process shown in Table 6 encompass the f is t three processes identified in the systematic approach discussed previously and shown in Figure 4. The tank waste characterization program has been using this process (Dove 1995) over the last several years in an effort to obtain data that can be used to address multiple problems associated with tank WaSte.

The DQO process has been used to develop characterization plans to provide data for the problems identified in Table 7. These problems have been categorized into three areas: safety, operations and waste treatment. The safety DQOs address the data requirements for specific safety concerns for the tanks. The safety screening DQO identifies the data requirements to determine if a tank has a potential safety issue and which specific safety concern is applicable. The ferrocyanide DQO is applicable to those tanks known or believed to contain significant quantities of ferrocyanide that could potentially react exothermally with the nitrates or other oxidants in the waste. The organic DQO applies to tanks that contain significant quantities of organic compounds that may react with the nitrates in the tanks. Tanks that are known or expected to generate flammable gases such as hydrogen from chemical or radiological reactions will be analyzed using the requirements identified in the flammable gas DQO. The vapor DQO applies to tanks that potentially contain toxic vapors. Many tanks have more than one applicable DQO.

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Development of the Model

Development of the Plan f

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b ? = . $

I

" L a

Sampling - Measurement + Data Assessment

Quality Control Quality Assessment

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Table 5. Elements of Various Quality Assurance Systems and Plans.

Control

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2

3

Table 6. DQO Process Steps.

Identify Decision(s) That Addresses the Problem

Identify Inputs Affecting Decision

4

5 6 7

Specify Domain of Decision Develop Logic Statement

Establish Constraints on Uncertainty

Optimize Design for Obtaining Data

Table 7. Tank Waste Characterization Data Quality Objectives.

Ferrocyanide

organic

EvaporatorILERF Pretreatment/Vitrification

Historical

Flammable Gas

Vapor

The compatibility DQO was developed to define the requirements for transferring waste. from one tank to another. It is applied during SST stabilization efforts when residual liquid is pumped to a DST for storage. It is also applied when waste is transferred between DSTs. Issues for the compatibility DQO include chemical compatibility, criticality, pumpability, and tank corrosion control. The DQO process was also used to develop sampling and analysis plans for the 242-A Evaporator.

The first step in the waste treatment process will be the retrieval of the material from the tanks. The DQO for retrieval addresses data needs for the development of retrieval systems. Retrieval decisions will be dependent on many of the physical properties of the waste. The pretreatment DQO focuses on the data requirements to develop processes for: 1) segregating the waste into high- and low-level components; 2) isolating specific radionuclides from the waste; and 3) producing the final waste disposal form. The historical DQO defines the data requirements to evaluate tank composition models based on historical processing records and previous analyses and verifies if tanks can be accurately sorted based on historical waste types. This DQO may also be useful to other tank characterization problems

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Wt% Water (TGA)

Fissile/Isotopes (Total Alpha)

by allowing information from a small set of tanks of one type to be used in evaluation of other tanks of this type. The data required for the historical model are similar to those required by the pretreatment DQO.

< 17wt% TOC > 30,000 I.rglg*

> 1 glL Cyanide > 39,000 Pglg

An example of the results from the DQO process for safety screening is summarized in Table 8. This DQO identifies four primary tests that should be performed in duplicate on homogenized half segments and on any drainable liquid. If the differential scanning calorimetry @SC) data shows an exotherm for the half segment greater than 480 J/g based on the dry weight of the sample, additional secondary tests are required to verify the reactivity and help identify the fuel source in the sample so that the waste can be properly classified. The weight percent water analyses are performed to calculate results for a dry sample and to further evaluate the potential of a propagating reaction. If the weight percent water is greater than 1746, an exothermic reaction cannot propagate through the waste. The potential for criticality is not a concern unless the total fissile concentration of the waste is > 1 glL. A total alpha analysis is used to make a conservative estimate of fissile content. If the total alpha analysis is exceeded, additional secondary measurements are needed. Before sampling from a tank, the potential for the flammability of its vapor must be established. This is accomplished using a flammability or explosivity meter that provides an estimate of the lower flammability limit (LFL) of the vapor gases. This vapor measurement must be less than 25% of the LFL before the tank can be sampled.

Vapor (LFL)

Sampling Requirement

Table 8. Example of DQO Process Results for Safety Screening of Wkte Tanks.

> 25% of LFL Pu-2391240 > 1 glL

Two cores from two locations as widely spaced as possible

Analyses Requirements Duplicate analyses on homogenized half segments and on drainable liquids

Note: *Bad on the dry weight for the sample

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If the DSC limit is exceeded, a reactive systems screening tool measurement may be performed to verify the DSC results and to obtain a better understanding of the reactivity of the sample. Total organic carbon (TOC) and cyanide analyses are performed to establish if the fuel causing the exotherm is organic or cyanide, thus permitting the proper identification of the hazard and appropriate safety issue for the waste. If the total alpha exceeds its limits, then specific isotope analysis for the major fissile isotopes, Pu-239/240, is performed. In addition, inductively coupled plasma (ICP) analyses for metals will be performed to identify neutron absorbers in the waste.

When data from primary testing exceeds the action levels, the tank operation groups are immediately notified of the potential safety issue. Analyses from the safety screening DQO may trigger additional testing identified in another DQO. For example, high TOC found in the safety screening DQO may require the sample to be tested for analytes identified in the organic or flammable gas DQOs.

Development of DQOs for waste characterization has not been a simple process. The type and number of problems associated with tank waste characterization are more complex than those addressed in normal environmental remediation projects. Some of the issues associated with the development of the DQos are summarized in Table 9. In general, applying the first four qualitative steps of the DQO process to tank characterization problems is relatively straightforward; however, defining the quantitative requirements beginning with the logic statement are difficult to achieve. For some of the tank problems, such as those for pretreatment and vitrification, the final processes to be used have not been determined. Therefore, there is considerable uncertainty in the data requirements. Accurately defining the safety problem also depends on the status of the models used to perform the safety analysis.

Another problem in developing DQOs is defining the acceptable risk for making an incorrect decision and obtaining concurrence from al l the stakeholders. Data users also experience difficulty in establishing the accuracy of and precision requirements for the data. DQO developers often inappropriately use analytical accuracy and precision estimates rather than defining statistically what data quality is needed to make a decision and what confidence level is adequate. DQOs are normally developed with all the data stakeholders involved. With multiple users of data, this can be a lengthy, labor-intensive process with numerous meetings that require good facilitation to achieve the desired result. Experience in the HLW characterization program showed that DQO development could be expedited by developing a draft DQO using a limited number of participants and then modifying the DQO by reviews and a limited number of meetings with data users and data generators. Even though the DQOs for waste characterization do not incorporate all the DQO process steps, the process has been valuable in: 1) generating more thought about final data use; 2) more accurately defining the problem; and 3) helping to develop more applicable sample and analysis plans.

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Table 9. Issues Associated with Developing DQOs. . -

Planners, Regulators, and Operations Personnel

TANK SAMPLING AND ANALYSIS PLANS

Based on historical knowledge and previous sampling and analysis events, the most applicable DQOs for a tank can be identified (Brown 1995). The appropriate DQOs for the tank are integrated into a sampling and analysis plan (SAP). This plan contains most of the details for the sampling and measurement processes needed to meet the DQO data requirements. The contents of the plan are summarized in Table 10. The S A P identifies the type of sampler to be used (core, grab or auger), the number of samples and the sample points (tank risers). The plan will also identify the need for field blanks and duplicates. If it is necessary to use a hydrostatic head fluid (HHF) to keep waste from rising into the core sample drill string, the plan will identify the needed analyses (lithium and bromide) and criteria to indicate when excessive HHF may be present. The analytical procedures and quality control protocols for spikes, duplicates and blanks are summarized in the SAP. The S A P also describes the notification limits for safety analytes based on the DQO and the reporting requirements. Reporting levels include: 1) early notification; 2) process control; 3) safety screening; 4) waste management; 5) Resource Conservation and Recovery Act of 1976 compliance; and 6) custom. The reporting requirements vary with the turnaround time and level of documentation required by the data user.

Table 10. Tank Sampling and Analyses Plan Contents. Integrates Applicable DQO Requirements

0

0

Identifies Sampling Procedure (Core, Grab or Auger) Identifies Number of SamDles and SamDle Points

0

0

0

Identifies Sampling Quality Control (QC) (Blanks, Duplicates and Hydrostatic Head Fluid) Describes Sample Treatment and Subsampling Requirements Identifies Measurement Methods and Controls Describes Reporting Requirements and Notification Limits

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Sample Size

FIELD SAMPLING QUALITY ELEMENTS

Some of the quality elements in sampling high-level tank waste are summarized in Table 11. For SSTs and DSTs that are heterogenous and contain large amounts of solids, at least two core or auger samples from two widely s p a d risers are normally obtained. Sampling of the waste tanks is constrained by the risers that are available for sampling. Therefore, a statistidy based random sampling plan is not normally possible. However, for some DSTs containing mostly supernate, statistically based sampling from several risers and depths has been used.

Problems have also been encountered in obtaining complete cores or augers of samples because of the variability in the sample consistency (hardnesdsoftness). If the waste is too dry or too fluid, it may fall off the auger during sampling. If a core sampler hits a hard layer before a soft layer, the sampler may become plugged with the harder material, which then pushes the softer material below it out of the way. These problems may affect the representativeness of the samples. In the worst cases, these problems prevent the data from being used for making tank waste decisions. However by taking multiple samples from different risers at different depths, it is normally possible to obtain profiles of the waste variability in the tank and estimate mors associated with the sampling process.

Table 11. Field Sampling Quality Elements.

Limited by radiological constraints

- 300 mL for core segments

- 100 mL for grab samples

Sampling Procedures

Samplers

Holding Times

Blanks

Samule Control

- 200 mL for 10-in. auger

Hydrostatic Head Fluid Tracer

X-ray verification of full sampler

Stainless steel disposable

Minimized

Combined: field/equipment/hot cell

Chain of custody and shipping controls

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The size of the samples is limited by radiological constraints such as the radiological shielding on the sampling equipment. The core samplers typically contain a 2.5-cm (1-in.)dmeter, 48-cm (19-in.)-long segment that contains about 300 mL of sample. R p t e d segments are taken until the entire depth of the waste is sampled. The average depth of the waste in the SSTs results in 5 segments; however, some tanks may have up to 22 segments of waste.

Grab samples are taken using the "bottle on the string" method. The bottles used collect about 100 mL of sample. The stoppered bottles are lowered to the desired depth in the liquid waste and the stopper removed to allow the bottle to fdl with waste from that level. Because the liquid wastes are more homogeneous, samples from multiple risers may not be required.

Auger samplers were developed to sample either hard crust on the top of the waste or to sample tanks that contain only small quantities (depth of < 51 cm DO in.]) of hard sludge wastes. The auger is inserted into the waste by manually turning the auger to the desired depth. It is then pulled back up into a sleeve and removed from the tank. The auger is not effective at removing any liquids in the waste and works best for thick cohesive sludges. The 10-in. auger will remove about 170 mL of waste and the 20-in. auger will remove about 450 mL.

When sampling sofi waste that is greater than one or two segments deep, it is necessary to use a hydrostatic head fluid to prevent deeper waste from rising into the drill string. For the push more core sampler, a lithium bromide solution is used as the hydrostatic head fluid. The rotary sample truck has the capability of using nitrogen gas for the hydrostatic head.

Analyses are performed for Li and Br in the waste to assess the level of contamination from the HHF in the sample. If the contamination level is too large (> - 20%), the data are corrected for the dilution effects of the HHF liquid. If the contamination level is very large (> -5096), the data may be classified as unusable because accurate corrections to the weight percent water and associated analyses are not possible.

Recently, sampling operations have added the ability to determine if the core sampler has been sufficiently filled by using an X-ray examination technique. This technique increases the reliability of the sampling process by permitting a resampling effort before the sample truck is moved to another riser or tank. The core samplers are made of stainless steel and are disposed of after each sampling. Therefore, the level of contamination from corrosion, cleaning and reuse is minimal. Efforts are made to minimize the time samples remain in the field and in the laboratory. Field blanks are taken to evaluate contamination in the sampling and subsampling process. A sampler is filled with water in the field, transported to the laboratory and extruded in the hot cell as if it were a sample. This blank measures contamination from several sources: the sampler, the extrusion system and other hot cell operations. If high blanks are observed, more specific blanks for each operation are used to identify the source of the contamination. The samples are labeled and transported to the laboratory under a chain of custody procedure.

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SUBSAMPLING QUALITY ELEMENTS

Chain of custody and sample hacking are maintained in the laboratory by the sample custodian. These and other QC elements for hot cell and subsampling are summarized in Table 12. The samples are loaded into the hot cell and extruded using standard operating procedures. Hot cell blanks may be requested so that the potential for contamination of the sample in the hot cell may be evaluated. Because of the high variability of the tank waste, the sample obtained may be significantly different from what was expected. This may require changes in the hot cell breakdown procedure and the sampling and analysis plan. These changes are captured in the hot cell worksheets and documented in report narratives.

After homogenization, a homogenization test may be performed based on the SAP or the direction of the project coordinator or hot cell chemist. In the homogenization test, duplicate subsamples are removed from two locations in the sample and are analyzed in duplicate for specified analytes. This test is used to evaluate the effectiveness of the homogenization procedure and provide estimates of subsampling reproducibility. Samples are stored in preclmed glass jars to minimize contamination. A small portion of sample is archived for additional tests that may be required after the data have been completely reviewed.

Table 12. Subsampling (Hot Cell) Quality Elements.

Hot CellBlanks

Sample Load-In and Extrusion Procedures

Sample Homogenization and Homogenization Testing

In-Lab Chain of Custody Procedures

Sample Archives '

Sample Packaging - Preclmed Glass Jars

QUALITY ELEMENTS IN THE MEASUREMENT PROCESS

A large variety of measurements is performed on Hanford Site HLWs (Table 13), including several types of sample preparation, analyte determinations, and physical property tests. Most of the quality elements outlined in Table 14 are based on standard environmental regulatory procedures and good laboratory practices. These. quality elements may be different for different methodologies; this is particularly true for radiochemical and physical property measurements.

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Samse Exchange i d Evzuation Program -Internal

Blind Standards - Internal

PERFORMANCE EVALUATION PROGRAMS

Actual tank waste - metals, anions, radionuclides and physical properties

Soils and waters Varies

4 per year

The performance evaluation programs being used at the Hanford Site have been described by Markel (1996). These performance evaluation programs are summarized in Table 15. One of the problems with DOE and EPA performance evaluation reference materials is that they are designed to evaluate performance on environmental samples in which concentrations of the analytes and radionuclides are much lower than those found in Hanford Site HLW. Many times the procedures used for HLW must be modified to accommodate the low levels of analytes found in these standards. Even though the results on these standards do not represent the performance that can be expected on the HLW, they have been valuable in helping the laboratories develop and refine the skills needed to analyze complex samples to exacting standards. These national programs have also helped to demonstrate that DOE high-level laboratories have the technical capability to perform on the same quality level as other environmental laboratories.

Mixed Analyte PE Program - DOE

Radiological Measurement Assurance Program - NIST

Table 15. Performance Evaluation Programs.

Soils and waters for inorganics, 2 per Year

Radiological 6 Per year

organics and radionuclides

National Exposure Research

Laboratory - DOE biota

Evaluation (CLP) - EPA and soils

1 2 p e r y e a r I Clean water act, waters - inorganic I (EMSL) - EPA I and organics Water Pollution Program

In 1993 the Sample Evaluation and Exchange Program (SEE) was initiated between the Westinghouse Hanford Company’s 2224 Laboratory and the Pacific Northwest National Laboratory’s Analytical Chemistry Laboratory to evaluate differences in radiochemical methods. This program has evolved through several phases described in Table 16. Overall,

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Phase III

Phase IV

the program is transitioning from a methods evaluation program to a routine sample split or external laboratory exchange program. The program has been implemented in phases to obtain a better understanding of the differences in results and their causes. The SEE program started with the exchange of common aqueous samples from digestions and fusions to eliminate differences that might be introduced from sample heterogeneity and subsampling procedures. This provided a more direct evaluation of methods. Phases 111 and IV have used exchanges of homogenized solids so that differences between the labs also represent differences in solids subsampling and sample preparation methods. In general, the laboratory results have been very comparable when analytes in the samples are far enough above their detection limits to be measured with reasonable accuracy and precision. Occasional differences have been observed whose causes could not be identified with the limited amount of data available. Phase IV is designed to increase the data base on these methods by analyzing a larger number of sample types to improve the overall evaluation.

Radionuclide, anion, and metal analyses on split solid samples for sample preparation and analytical method evaluation

Routine split of solid waste samples for selected analytes for evaluation of laboratory performane

Table 16. Phase Development of the SEE Program.

method evaluation

DATA EVALUATION AND REPORTING

Evaluation of the HLW characterization data is done in three stages: 1) analytical batch evaluation; 2) sample evaluation; and 3) tank evaluation. Data areas reviewed for these stages are summarized in Table 17. Batch evaluation is done by technologists and chemists at the working level where the analyses are performed. It is the technologist and chemists responsibility to review each batch of data for an analyte or test to ensure that it meets the quality requirements of the procedure, HASQAP, and/or the customer’s specifications as ,summarized in the SAP. The method controls (calibration, standards and blanks ) should all meet the data quality requirements before the data is reported. Control charts are used to monitor the analytical systems. Sample quality tests (duplicates and spikes) are evaluated against the SAP requirements with consideration for factors such as detection limits, spike levels and sample heterogeneity. Failure to meet the desired requirements may result in reruns or other corrective actions. When quality factors can not be achieved for the batch, they are identified and addressed in the narrative for the data.

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The chemists performing batch evaluation are normally looking at data for one method and analyte for several samples. When the batch data for all the analyses on a sample are compiled and evaluated, additional evaluations of the data quality and suitability are possible. These reviews and reports are prepared by the Project Coordinator. Data are again checked against the project limits and data quality requirements. By comparing the precision for different analytes, it is sometimes possible to c o n f m sample heterogeneity problems. For example, if both the total beta and "Sr results showed large RPDs it is a good indication that the differences are due to errors in subsampling rather than errors in t h e 3 r separation procedure. It is also possible at this stage to do comparisons of data between methods. When available, the ICP and ion chromatography (IC) data for phosphorus and sulfur on water digestions can be compared, If they agree, it is a good indication that both methods performed properly. A similar comparison can be done between total alpha or be& and the sum of the primary isotopes emitting this type of radiation. When the data are compiled for the preliminary 45-day report or final laboratory report, it is reviewed for overall consistency by comparing analyte concentrations across the segment level to ensure that none of the values appear to be outside the normal concentration. This helps to identify calculation and transcription errors that may have occurred in the data.

Table 17. Data Evaluation for High-Level Waste Characterization. (2 Sheets)

between methods sampling & analysis events

between methods - total beta vs Sr and Cs

furnace oxidation

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Table 17. Data Evaluation for High-Level Waste Characterization. (2 Sheets)

criteria and objectives

The final stage of data evaluation is done for the tank in the development of the tank characterization report by Tank Coordinators. The data from the sampling and analysis event are compared to the historical contents of the tank (Brevick et al. 1994a, 1994b, 1994c, 1994d). The data are also compared to data from previous sampling and analysis events. If sufficient data are available, mass and charge balance calculations are performed to evaluate the data consistency and to identify possible major components that may not be accounted for. Comparison of results from different methods are performed. The quality of the data from field and laboratory is reviewed to identify areas that may impact the use of the data for key decisions. The vertical and horizontal distribution of the components in the waste is also evaluated for trends and identification of layers. These evaluations may also identify data anomalies that have escaped previous reviews. Finally, the data are evaluated against the applicable DQO criteria, and conclusions or recommendations on data use or future characterization efforts are made.

AUDITS AND ASSESSMENTS

An important part of the laboratory’s quality assurance plan that supports the quality of the HLW characterization project are the technical and managerial self assessments that they perform. The key criteria for the Analytical Services QA review of the data package are summarized in Table 18. A continuous quality improvement process (CQIP), illustrated in Figure 5 , is used by the laboratory for self assessment of problems and to direct the improvement in measurement operations. In this process, data from sample analyses and reports are evaluated in specific areas where improvements are needed. This data is evaluated by QA and technical staff to establish an action plan. Performance indicators are identified to evaluate the changes and statistical process control tools are utilized to evaluate and maintain the improved status. The data reviews and CQIP have resulted in improved data quality while at the same time laboratory production has increased significantly.

25

N m

Understand Current Process

~

+ Opportunityfor Improvement

Possible Cause

4

Collect Data

5

Closure

8

Hold the Gain

Unacceptable

I b Take Action - W

WHC-SA-3085-FP

~

Results meet the requirements of QC protocol for project

Results can be verified for traceability and supported by defensibility

Table 18. Key Criteria for QA Review of High-Level waste charactenza ’ tion Data Package.

I use of proper reporting format 1 0

0

Meet analysis requirements defined in DQOs and S A P

Assure narrative adequately describes anomalies, deficiencies, and limitations in the sampling and analyses

Meet instrument calibration and performance criteria

In addition to these internal reviews of the data, reviews are also made by other groups as shown in Table 19. The Analytical Services organization has a QA group, which is independent of the laboratory, that performs quality assurance audits and reviews the data. The TWRS customer also has a quality assurance group that reviews the laboratory and characterization operations. Finally the DOE assesses the contractors performance through its local quality assurance organization and by outside consultants and government oversight groups.

Table 19. Audits and Assessments.

Analytical Services Internal QA

TWRSProgramQA

DOEQA - RLOperations QA - -

-

Tank Characterization Advisory Panel Consultants to DOWRL Defense Nuclear Facilities Safety Board Congressional Oversight Committee TAP and Sub TAPS Technical Advisory Panels

CONCLUSION

The quality assurance applied to measurement data has changed significantly with the Hanford Site’s transition from production to cleanup. Greater attention and requirements are being placed on HLW measurements because of the decisions that are being made with the data and because of the regulatory implications and greater oversite and interaction from outside groups. The result is that more systematic processes for defining, attaining and assessing data quality have been implemented to meet Hanford’s new mission. This systematic process uses DQOs to define the problem, SAPS based on the DQOs to define the

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sampling and analysis requirements and several levels of data assessment and reporting to ensure that data of known quality is produced to support the HLW characterization program at the Hanford Site.

REFERENCES

10 CFR 830.120, 1994, "Quality Assurance Requirements," U.S. Code of Federal Regulatiom, as amended.

ASME, 1986, Quality Assurance Program Requirements for Nuclear Facilities, ANSYASME NQA-1, The American Society of Mechanical Engineers, New York, New York.

ASTM, 1983, Btablishing a Quality Assurance Program for Amlyrical Chemisny Laboratories within the Nuclear Industry, C 1009-83, 1983, American Society for Testing and Materials, Philadelphia, Pennsylvania.

Brevick , C. H., L A . Gaddis, and W. W. Pickett, 1994a, Historical Tank Content &timate for the Northeast Quadrant of the Hanford 200 East Areas, WHC-SD-WM-ER-349, Rev. 0, Westinghouse Hanford Company, Richland Washington.

Brevick , C. H., L A . Gaddis, and W. W. Pickett, 1994b, Historical Tank Content Estimate for the Northwest Quadrant of the Hmford 200 East Areas, WHC-SD-WM-ER-351, Rev. 0, Westinghouse Hanford Company, Richland Washington.

Brevick , C. H., L.A. Gaddis, and W. W. Pickett, 1994c, Historical Tank Content Errimare for the Southwest Quadrant of the Hanford 200 West Areas, WHC-SD-WM-ER-352, Rev. 0, Westinghouse Hanford Company, Richland Washington.

Brevick , C. H., L.A. Gaddis, and W. W. Pickett, 1994d, Historical Tank Content Estimate for the Southeast Quadrant of the Hmford 200 East Areas, WHC-SD-WM-ER-350, Rev. 0, Westinghouse Hanford Company, Richland Washington.

Brown T. M., 1995, Tank Waste Characterization Basis, WHC-SD-WM-TA-164, Rev. 1, August 1995, Westinghouse Hanford Company, Richland Washington.

DOE, 1991, "Qualify Assurance", DOE Order 5700.6C, U.S. Department of Energy Washington, D.C.

DOE, 1995, Hanford Analyrical Sem'ces Qualify Assurance Plan, DOEIRL-94-55, Rev. 2, U.S. Department of Energy Washington, D.C.

Dove T. H. , 1995, Tank Waste Characterization Process, WHC-SD-WM-TA-163, Rev. 0, June 1995, Westinghouse Hanford Company, Richland Washington.

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Ecology, EPA, and DOE, 1996, Hanford Federal Facility Agreement and Consent Onier, Washington State Department of Ecology, U.S. Environmental Protection Agency, and the U.S. Department of Energy, Olympia Washington.

EPA, 198Oa, Guidelines and Spec@cm.ons for Preparing QA Program Plans, QAMS-004180, U.S. Environmental Protection Agency, Washington, D.C.

EPA, 1980b, Interim Guidelines and Specificatons for Preparing Quality Assurance Prqjea Plans, EPA QAMS-005180, U.S. Environmental Protection Agency, Washington, D.C.

EPA, 1992, USEPA Methods for EvalUnring Solid Waste, Physical/C%emical Methods, SW-846, 3rd Edition, as revised with Update 1, July 1992, U.S. Environmental Protection Agency, Office of Solid Waste and Emergency Response, Washington, D.C.

EPA, 1987, Data Quality Objectives for Remedial Response Activities, EPA1540lG-871004, March 1987, U.S. Environmental Protection Agency, Washington, D.C.

EPA 1991a, USEPA Contract Laboratory Program Statement of Work for Organics Analysis, OLMo2.1, U.S. Environmental Protection Agency, Washington, D.C.

EPA 1991b, USEPA Contract Laboratory Program Statement of Work for Inorganics Analysis, ILMO1.0, U.S. Environmental Protection Agency, Washington, D.C.

EPA, 1994a, Draft Interim Final, EPA Requirements for Quality Management Plans, EPA QAIR-2, August 1994, U.S. Environmental Protection Agency, Washington, D.C.

EPA, 1994b, Draft Interim Final, EPA Requirements for Quality Assurance Project Plans for Environmental Data Operan'ons, EPA QAIR-5, August 1994, U S . Environmental Protection Agency, Washington, D.C.

Markel L. P. , 1996, Hanford Performance Evaludon Program, WHC-SD-QA-QAPP-002, Rev. 1, Westinghouse Hanford Company, Richland Washington.

Neptune, D., 1970, E. P. Brantly, M. J. Messner, and D. I. Michael, "Quantitative Decision Making in Superfund: A Data Quality Objectives Case Study," Hazardous Material Control, V O ~ . 3(3), pp. 18-27.

Taylor J. K., 1987, Qualily Assurance of Chemical Measurements, Lewis Publishers, Chelsea, Michigan.

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