NUREG-1576
EPA402-B-04-001A
NTIS PB2004-105421
Multi-Agency Radiological
Laboratory Analytical Protocols Manual
(MARLAP)
Part I: Chapters 1 - 9
Appendices A - E
(Volume I)
United States Environmental Protection Agency
United States Department of Defense
United States Department of Energy
United States Department of Homeland Security
United States Nuclear Regulatory Commission
United States Food and Drug Administration
United States Geological Survey
National Institute of Standards and Technology
July 2004
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Disclaimer
References within this manual to any specific commercial product, process, or service by trade
name, trademark, manufacturer, or otherwise does not necessarily imply its endorsement or
recommendation by the United States Government. Neither the United States Government nor
any agency or branch thereof, nor any of their employees, makes any warranty, expressed or
implied, nor assumes any legal liability of responsibility for any third party's use, or the results
of such use, of any information, apparatus, product, or process disclosed in this manual, nor
represents that its use by such third party would not infringe on privately owned rights.
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ABSTRACT
The Multi-Agency Radiological Laboratory Analytical Protocols (MARLAP) manual provides
guidance for the planning, implementation, and assessment of projects that require the laboratory
analysis of radionuclides. MARLAP's basic goal is to provide guidance for project planners,
managers, and laboratory personnel to ensure that radioanalytical laboratory data will meet a
project's or program's data requirements. To attain this goal, the manual offers a framework for
national consistency in the form of a performance-based approach for meeting data requirements
that is scientifically rigorous and flexible enough to be applied to a diversity of projects and
programs. The guidance in MARLAP is designed to help ensure the generation of radioanalytical
data of known quality, appropriate for its intended use. Examples of data collection activities that
MARLAP supports include site characterization, site cleanup and compliance demonstration,
decommissioning of nuclear facilities, emergency response, remedial and removal actions,
effluent monitoring of licensed facilities, environmental site monitoring, background studies, and
waste management activities.
MARLAP is organized into two parts. Part I, intended primarily for project planners and
managers, provides the basic framework of the directed planning process as it applies to projects
requiring radioanalytical data for decision making. The nine chapters in Part I offer
recommendations and guidance on project planning, key issues to be considered during the
development of analytical protocol specifications, developing measurement quality objectives,
project planning documents and their significance, obtaining laboratory services, selecting and
applying analytical methods, evaluating methods and laboratories, verifying and validating
radiochemical data, and assessing data quality. Part II is intended primarily for laboratory
personnel. Its eleven chapters provide detailed guidance on field sampling issues that affect
laboratory measurements, sample receipt and tracking, sample preparation in the laboratory,
sample dissolution, chemical separation techniques, instrumentation for measuring radionuclides,
data acquisition, reduction, and reporting, waste management, laboratory quality control,
measurement uncertainty, and detection and quantification capability. Seven appendices provide
complementary information and additional details on specific topics.
MARLAP was developed by a workgroup that included representatives from the U.S. Environ-
mental Protection Agency (EPA), Department of Energy (DOE), Department of Defense (DOD),
Department of Homeland Security (DHS), Nuclear Regulatory Commission (NRC), National
Institute of Standards and Technology (NIST), U.S. Geological Survey (USGS), and Food and
Drug Administration (FDA), and from the Commonwealth of Kentucky and the State of
California.
JULY 2004 III MARLAP
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FOREWORD
MARLAP is organized into two parts. Part I, consisting of Chapters 1 through 9, is intended
primarily for project planners and managers. Part I introduces the directed planning process
central to MARLAP and provides guidance on project planning with emphasis on radioanalytical
planning issues and radioanalytical data requirements. Part n, consisting of Chapters 10 through
20, is intended primarily for laboratory personnel and provides guidance in the relevant areas of
radioanalytical laboratory work. In addition, MARLAP contains seven appendices—labeled A
through G—that provide complementary information, detail background information, or concepts
pertinent to more than one chapter. Six chapters and one appendix are immediately followed by
one or more attachments that the authors believe will provide additional or more detailed
explanations of concepts discussed within the chapter. Attachments to chapters have letter
designators (e.g, Attachment "6A" or "3B"), while attachments to appendices are numbered (e.g.,
"Bl"). Thus, "Section B.I.I" refers to section 1.1 of appendix B, while "Section B 1.1" refers to
section 1 of attachment 1 to appendix B. Cross-references within the text are explicit in order to
avoid confusion.
Because of its length, the printed version of MARLAP is bound in three volumes. Volume I
(Chapters 1 through 9 and Appendices A through E) contains Part I. Because of its length, Part II
is split between Volumes II and III. Volume II (Chapters 10 through 17 and Appendix F) covers
most of the activities performed at radioanalytical laboratories, from field and sampling issues
that affect laboratory measurements through waste management. Volume III (Chapters 18
through 20 and Appendix G) covers laboratory quality control, measurement uncertainty and
detection and quantification capability. Each volume includes a table of contents, list of
acronyms and abbreviations, and a complete glossary of terms.
MARLAP and its periodic revisions are available online at www.epa.gov/radiation/marlap and
www.nrc.gov/reading-rm/doc-collections/nuregs/staff/srl576/. The online version is updated
periodically and may differ from the last printed version. Although references to material found
on a web site bear the date the material was accessed, the material available on the date cited may
subsequently be removed from the site. Printed and CD-ROM versions of MARLAP are
available through the National Technical Information Service (NTIS). NTIS may be accessed
online at www.ntis.gov. The NTIS Sales Desk can be reached between 8:30 a.m. and 6:00 p.m.
Eastern Time, Monday through Friday at 1-800-553-6847; TDD (hearing impaired only) at 703-
487-4639 between 8:30 a.m. and 5:00 p.m Eastern Time, Monday through Friday; or fax at 703-
605-6900.
MARLAP is a living document, and future editions are already under consideration. Users are
urged to provide feedback on how MARLAP can be improved. While suggestions may not
always be acknowledged or adopted, commentors may be assured that they will be considered
carefully. Comments may be submitted electronically through a link on EPA's MARLAP web
site (www.epa.gov/radiation/marlap).
JULY 2004 V MARLAP
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ACKNOWLEDGMENTS
The origin of the Multi-Agency Radiological Laboratory Analytical Protocols (MARLAP)
manual can be traced to the recognition by a number of agencies for the need to have a nationally
consistent approach to producing radioanalytical data that meet a program's or project's needs. A
workgroup was formed with representatives from the U.S. Environmental Protection Agency
(EPA), Department of Energy (DOE), Department of Homeland Security (DHS), Nuclear
Regulatory Commission (NRC), Department of Defense (DOD), U.S. Geological Survey
(USGS), National Institute of Standards and Technology (NIST), and Food and Drug Adminis-
tration (FDA) to develop guidance for the planning, implementation, and assessment of projects
that require the laboratory analysis of radionuclides. Representatives from the Commonwealth of
Kentucky and the State of California also contributed to the development of the manual.
Contractors and consultants of EPA, DOE, and NRC—and members of the public—have been
present during open meetings of the MARLAP workgroup.
MARLAP would not have been possible without the workgroup members who contributed their
time, talent, and efforts to develop this guidance document:
John Griggs*, EPA, Chair
EPA: H.Benjamin Hull DOD: Andrew Scott (Army)
Marianne Lynch* Ronald Swatski* (Army)
Keith McCroan* Jan Dunker (Army Corps of Engineers)
Eric Reynolds William J. Adams (Navy)
Jon Richards Troy Blanton (Navy)
David Farrand (Navy)
FDA: Edmond Baratta Dale Thomas (Air Force)
DOE: EmileBoulos* DHST: Carl Gogolak*
Stan Morton* Pamela Greenlaw*
Stephanie Woolf* Catherine Klusek*
Colin Sanderson*
NRC: Rateb (Boby) Abu Eid NIST: Kenneth GW. Inn*
Tin Mo
George Powers USGS: Ann Mullin*
* These workgroup members also served as chapter chairs.
t All with the Environmental Measurements Laboratory, which was part of DOE prior to the establishment of DHS
on March 1,2003.
JULY 2004 VII MARLAP
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Acknowledgments
Special recognition is given to John Volpe, Commonwealth of Kentucky, and Penny Leinwander,
State of California, for their contributions to the development of the MARLAP manual. The
following federal agency contractors provided assistance in developing the MARLAP manual:
EPA: N. Jay Bassin (Environmental Management Support, Inc.)
U. Hans Behling ( S. Cohen & Associates, Inc.)
Richard Blanchard (S. Cohen & Associates, Inc.)
Leca Buchan (Environmental Management Support, Inc.)
Jessica Burns (Environmental Management Support, Inc.)
Harry Chmelynski
Diane Dopkin (Environmental Management Support, Inc.)
Scott Hay (S. Cohen & Associates, Inc.)
Patrick Kelly (S. Cohen & Associates, Inc.)
Robert Litman
David McCurdy
Charles (Chick) Phillips (S. Cohen & Associates, Inc.)
William Richardson in (S. Cohen & Associates, Inc.)
Steven Schaffer (S. Cohen & Associates, Inc.)
Michael Schultz
Robert Shannon (Time Solutions Corp.)
DOE: Stan Blacker (MACTEC, Inc.)
Pat Harrington (MACTEC, Inc.)
David McCurdy
John Maney (Environmental Measurements Assessments)
Mike Miller (MACTEC, Inc.)
Lisa Smith (Argonne National Laboratory)
NRC: Eric W. Abelquist (ORISE)
Dale Condra (ORISE)
The MARLAP workgroup was greatly aided in the development of the manual by the
contributions and support provided by the individuals listed below.
John Arnold (USGS) David Friedman (EPA) Jim Mitchell (EPA)
David Bottrell (DOE) Lino Fragoso (Navy) Colleen Petullo (EPA)
Lloyd Currie (NIST) Richard Graham (EPA) Steve Pia (EPA)
Mike Carter (EPA) Patricia Gowland (EPA) Phil Reed (NRC)
Mary Clark (EPA) Larry Jensen (EPA) Cheryl Trottier (NRC)
Ron Colle (NIST) K. Jack Kooyoomjian (EPA) Mary C. Verwolf (DOE)
Mark Doehnert (EPA) Jim Kottan (NRC) John Warren (EPA)
Steve Domotor (DOE) Ed Messer (EPA) Mary L. Winston (EPA)
Joan Fisk (EPA) Kevin Miller (DOE) Tony Wolbarst (EPA)
MARLAP VIII JULY 2004
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Acknowledgments
EPA's Science Advisory Board (SAB) Radiation Advisory Committee's Review Subcommittee
that conducted an extensive peer review of the MARLAP includes:
Chair
Dr. Janet A. Johnson, Shepherd Miller, Inc.
SAB Members
Dr. Lynn R. Anspaugh, University of Utah
Dr. Bruce B. Boecker, (Scientist Emeritus), Lovelace Respiratory Research Institute
Dr. Gilles Y. Bussod, Science Network International
Dr. Thomas F. Gesell, Idaho State University
Dr. Helen Ann Grogan, Cascade Scientific, Inc.
Dr. Richard W. Hornung, University of Cincinnati
Dr. Jill Lipoti, New Jersey Department of Environmental Protection
Dr. Genevieve S. Roessler, Radiation Consultant
SAB Consultants
Dr. Vicki M. Bier, University of Wisconsin
Dr. Stephen L. Brown, R2C2 (Risks of Radiation and Chemical Compounds)
Dr. Michael E. Ginevan, M.E. Ginevan & Associates
Dr. Shawki Ibrahim, Colorado State University
Dr. Bernd Kahn, Georgia Institute of Technology
Dr. June Fabryka-Martin, Los Alamos National Laboratory
Dr. Bobby R. Scott, Lovelace Respiratory Research Institute
Science Advisory Board Staff
Dr. K. Jack Kooyoomjian, Designated Federal Officer, EPA
Ms. Mary L. Winston, Management Assistant, EPA
Dozens of individuals and organizations offered hundreds of valuable comments in response to
the Call for Public Comments on the draft MARLAP between August 2001 and January 2002,
and their suggestions contributed greatly to the quality and consistency of the final document.
While they are too numerous to mention individually, Jay A. MacLellan, Pacific Northwest
National Laboratory; Daniel J. Strom, Pacific Northwest National Laboratory; and James H.
Stapleton, Department of Statistics and Probability of Michigan State University are especially
acknowledged for their comments and suggestions.
JULY 2004 IX MARLAP
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CONTENTS
Page
Abstract in
Foreword v
Acknowledgments VII
Contents of Appendices xxxvi
List of Figures XLI
List of Tables XLV
Acronyms and Abbreviations XLIX
Unit Conversion Factors LVII
1 Introduction to MARLAP 1-1
1.1 Overview 1-1
1.2 Purpose of the Manual 1-2
1.3 Use and Scope of the Manual 1-3
1.4 Key MARLAP Concepts and Terminology 1-4
1.4.1 DataLife Cycle 1-4
1.4.2 Directed Planning Process 1-5
1.4.3 Performance-Based Approach 1-5
1.4.4 Analytical Process 1-6
1.4.5 Analytical Protocol 1-7
1.4.6 Analytical Method 1-7
1.4.7 Uncertainty and Error 1-7
1.4.8 Precision, Bias, and Accuracy 1-9
1.4.9 Performance Objectives: Data Quality Objectives and Measurement Quality
Objectives 1-10
1.4.10 Analytical Protocol Specifications 1-11
1.4.11 The Assessment Phase 1-11
1.5 The MARLAP Process 1-12
1.6 Structure of the Manual 1-13
1.6.1 Overview of Part I 1-16
1.6.2 Overview of Part II 1-17
1.6.3 Overview of the Appendices 1-18
1.7 References 1-19
JULY 2004 XI MARLAP
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2 Project Planning Process 2-1
2.1 Introduction 2-1
2.2 The Importance of Directed Project Planning 2-2
2.3 Directed Project Planning Processes 2-3
2.3.1 A Graded Approach to Project Planning 2-4
2.3.2 Guidance on Directed Planning Processes 2-4
2.3.3 Elements of Directed Planning Processes 2-5
2.4 The Project Planning Team 2-6
2.4.1 Team Representation 2-7
2.4.2 The Radioanalytical Specialists 2-7
2.5 Directed Planning Process and Role of the Radioanalytical Specialists 2-8
2.5.1 State the Problem 2-11
2.5.2 Identify the Decision 2-12
2.5.2.1 Define the Action Level 2-12
2.5.2.2 Identify Inputs to the Decision 2-13
2.5.2.3 Define the Decision Boundaries 2-13
2.5.2.4 Define the Scale of the Decision 2-14
2.5.3 Specify the Decision Rule and the Tolerable Decision Error Rates 2-14
2.5.4 Optimize the Strategy for Obtaining Data 2-15
2.5.4.1 Analytical Protocol Specifications 2-16
2.5.4.2 Measurement Quality Objectives 2-16
2.6 Results of the Directed Planning Process 2-17
2.6.1 Output Required by the Radioanalytical Laboratory: The Analytical Protocol
Specifications 2-18
2.6.2 Chain of Custody 2-19
2.7 Project Planning and Project Implementation and Assessment 2-19
2.7.1 Documenting the Planning Process 2-19
2.7.2 Obtaining Analytical Services 2-20
2.7.3 Selecting Analytical Protocols 2-20
2.7.4 Assessment Plans 2-21
2.7.4.1 Data Verification 2-21
2.7.4.2 Data Validation 2-22
2.7.4.3 Data Quality Assessment 2-22
2.8 Summary of Recommendations 2-22
2.9 References 2-23
3 Key Analytical Planning Issues and Developing Analytical Protocol Specifications 3-1
3.1 Introduction 3-1
3.2 Overview of the Analytical Process 3-2
3.3 General Analytical Planning Issues 3-2
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3.3.1 Develop Analyte List 3-3
3.3.2 Identify Concentration Ranges 3-5
3.3.3 Identify and Characterize Matrices of Concern 3-5
3.3.4 Determine Relationships Among the Radionuclides of Concern 3-6
3.3.5 Determine Available Project Resources and Deadlines 3-7
3.3.6 Refine Analyte List and Matrix List 3-7
3.3.7 Method Performance Characteristics and Measurement Quality Objectives . . . 3-7
3.3.7.1 Develop MQOs for Select Method Performance Characteristics 3-9
3.3.7.2 The Role of MQOs in the Protocol Selection and Evaluation Process . . . 3-14
3.3.7.3 The Role of MQOs in the Project's Data Evaluation Process 3-14
3.3.8 Determine Any Limitations on Analytical Options 3-15
3.3.8.1 Gamma Spectrometry 3-16
3.3.8.2 Gross Alpha and Beta Analyses 3-16
3.3.8.3 Radiochemical Nuclide-Specific Analysis 3-17
3.3.9 Determine Method Availability 3-17
3.3.10 Determine the Type and Frequency of, and Evaluation Criteria for, Quality
Control Samples 3-17
3.3.11 Determine Sample Tracking and Custody Requirements 3-18
3.3.12 Determine Data Reporting Requirements 3-19
3.4 Matrix-Specific Analytical Planning Issues 3-20
3.4.1 Solids 3-21
3.4.1.1 Removal of Unwanted Materials 3-21
3.4.1.2 Homogenization and Subsampling 3-21
3.4.1.3 Sample Dissolution 3-22
3.4.2 Liquids 3-22
3.4.3 Filters and Wipes 3-23
3.5 Assembling the Analytical Protocol Specifications 3-23
3.6 Level of Protocol Performance Demonstration 3-24
3.7 Project Plan Documents 3-24
3.8 Summary of Recommendations 3-27
3.9 References 3-27
Attachment 3A: Measurement Uncertainty 3-29
3A.I Introduction 3-29
3A.2 Analogy: Political Polling 3-29
3A.3 Measurement Uncertainty 3-30
3A.4 Sources of Measurement Uncertainty 3-31
3A.5 Uncertainty Propagation 3-32
3A.6 References 3-32
Attachment 3B: Analyte Detection 3-33
3B. 1 Introduction 3-33
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3B.2 The Critical Value 3-34
3B.3 The Minimum Detectable Value 3-35
3B.4 Sources of Confusion 3-36
3B.5 Implementation Difficulties 3-37
4 Project Plan Documents 4-1
4.1 Introduction 4-1
4.2 The Importance of Project Plan Documents 4-2
4.3 A Graded Approach to Project Plan Documents 4-3
4.4 Structure of Project Plan Documents 4-3
4.4.1 Guidance on Project Plan Documents 4-4
4.4.2 Approaches to Project Plan Documents 4-5
4.5 Elements of Project Plan Documents 4-6
4.5.1 Content of Project Plan Documents 4-6
4.5.2 Plan Documents Integration 4-9
4.5.3 Plan Content for Small Projects 4-9
4.6 Linking the Project Plan Documents and the Project Planning Process 4-10
4.6.1 Planning Process Report 4-14
4.6.2 Data Assessment 4-15
4.6.2.1 Data Verification 4-15
4.6.2.2 Data Validation 4-15
4.6.2.3 Data Quality Assessment 4-16
4.7 Summary of Recommendations 4-17
4.8 References 4-17
5 Obtaining Laboratory Services 5-1
5.1 Introduction 5-1
5.2 Importance of Writing a Technical and Contractual Specification Document 5-2
5.3 Statement of Work—Technical Requirements 5-2
5.3.1 Analytes 5-3
5.3.2 Matrix 5-3
5.3.3 Measurement Quality Objectives 5-3
5.3.4 Unique Analytical Process Requirements 5-4
5.3.5 Quality Control Samples and Participation in External Performance Evaluation
Programs 5-4
5.3.6 Laboratory Radiological Holding and Turnaround Times 5-5
5.3.7 Number of Samples and Schedule 5-5
5.3.8 Quality System 5-6
5.3.9 Laboratory's Proposed Methods 5-6
5.4 Request for Proposal—Generic Contractual Requirements 5-7
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5.4.1 Sample Management 5-7
5.4.2 Licenses, Permits and Environmental Regulations 5-8
5.4.2.1 Licenses 5-8
5.4.2.2 Environmental and Transportation Regulations 5-8
5.4.3 Data Reporting and Communications 5-9
5.4.3.1 Data Deliverables 5-9
5.4.3.2 Software Verification and Control 5-10
5.4.3.3 Problem Notification and Communication 5-10
5.4.3.4 Status Reports 5-11
5.4.4 Sample Re-Analysis Requirements 5-11
5.4.5 Subcontracted Analyses 5-11
5.5 Laboratory Selection and Qualification Criteria 5-11
5.5.1 Technical Proposal Evaluation 5-12
5.5.1.1 Scoring and Evaluation Scheme 5-12
5.5.1.2 Scoring Elements 5-13
5.5.2 Pre-Award Proficiency Evaluation 5-14
5.5.3 Pre-Award Assessments and Audits 5-15
5.6 Summary of Recommendations 5-15
5.7 References 5-16
5.7.1 Cited References 5-16
5.7.2 Other Sources 5-16
6 Selection and Application of an Analytical Method 6-1
6.1 Introduction 6-1
6.2 Method Definition 6-3
6.3 Life Cycle of Method Application 6-5
6.4 Generic Considerations for Method Development and Selection 6-9
6.5 Project-Specific Considerations for Method Selection 6-11
6.5.1 Matrix and Analyte Identification 6-11
6.5.1.1 Matrices 6-11
6.5.1.2. Analytes and Potential Interferences 6-14
6.5.2 Process Knowledge 6-14
6.5.3 Radiological Holding and Turnaround Times 6-15
6.5.4 Unique Process Specifications 6-16
6.5.5 Measurement Quality Objectives 6-17
6.5.5.1 Method Uncertainty 6-17
6.5.5.2 Quantification Capability 6-18
6.5.5.3 Detection Capability 6-19
6.5.5.4 Applicable Analyte Concentration Range 6-20
6.5.5.5 Method Specificity 6-20
JULY 2004 XV MARLAP
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6.5.5.6 Method Ruggedness 6-21
6.5.5.7 Bias Considerations 6-21
6.6 Method Validation 6-22
6.6.1 General Method Validation 6-24
6.6.2 Project Method Validation Protocol 6-25
6.6.3 Tiered Approach to Project Method Validation 6-26
6.6.3.1 Existing Methods Requiring No Additional Validation 6-28
6.6.3.2 Routine Methods Having No Project Method Validation 6-28
6.6.3.3 Use of a Validated Method for Similar Matrices 6-28
6.6.3.4 New Application of a Validated Method 6-29
6.6.3.5 Newly Developed or Adapted Methods 6-30
6.6.4 Testing for Bias 6-31
6.6.4.1 Absolute Bias 6-31
6.6.4.2 Relative Bias 6-32
6.6.5 Project Method Validation Documentation 6-32
6.7 Analyst Qualifications and Demonstrated Proficiency 6-32
6.8 Method Control 6-33
6.9 Continued Performance Assessment 6-34
6.10 Documentation To Be Sent to the Project Manager 6-35
6.11 Summary of Recommendations 6-36
6.12 References 6-36
Attachment 6A: Bias-Testing Procedure 6-39
6A.1 Introduction 6-39
6A.2 The Test 6-39
6A.3 Bias Tests at Multiple Concentrations 6-42
7 Evaluating Methods and Laboratories 7-1
7.1 Introduction 7-1
7.2 Evaluation of Proposed Analytical Methods 7-2
7.2.1 Documentation of Required Method Performance 7-2
7.2.1.1 Method Validation Documentation 7-3
7.2.1.2 Internal Quality Control or External PE Program Reports 7-4
7.2.1.3 Method Experience, Previous Projects, and Clients 7-5
7.2.1.4 Internal and External Quality Assurance Assessments 7-5
7.2.2 Performance Requirements of the SOW—Analytical Protocol Specifications . 7-5
7.2.2.1 Matrix and Analyte Identification 7-6
7.2.2.2 Radiological Holding and Turnaround Times 7-7
7.2.2.3 Unique Processing Specifications 7-8
7.2.2.4 Measurement Quality Objectives 7-8
7.2.2.5 Bias Considerations 7-13
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7.3 Initial Evaluation of a Laboratory 7-15
7.3.1 Review of Quality System Documents 7-15
7.3.2 Adequacy of Facilities, Instrumentation, and Staff Levels 7-17
7.3.3 Review of Applicable Prior Work 7-17
7.3.4 Review of General Laboratory Performance 7-18
7.3.4.1 Review of Internal QC Results 7-18
7.3.4.2 External PE Program Results 7-19
7.3.4.3 Internal and External Quality Assessment Reports 7-20
7.3.5 Initial Audit 7-20
7.4 Ongoing Evaluation of the Laboratory's Performance 7-20
7.4.1 Quantitative Measures of Quality 7-21
7.4.1.1 MQO Compliance 7-22
7.4.1.2 Other Parameters 7-27
7.4.2 Operational Aspects 7-28
7.4.2.1 Desk Audits 7-28
7.4.2.2 Onsite Audits 7-30
7.5 Summary of Recommendations 7-32
7.6 References 7-33
8 Radiochemical Data Verification and Validation 8-1
8.1 Introduction 8-1
8.2 Data Assessment Process 8-2
8.2.1 Planning Phase of the Data Life Cycle 8-2
8.2.2 Implementation Phase of the Data Life Cycle 8-3
8.2.2.1 Project Objectives 8-3
8.2.2.2 Documenting Project Activities 8-4
8.2.2.3 Quality Assurance/Quality Control 8-4
8.2.3 Assessment Phase of the Data Life Cycle 8-5
8.3 Validation Plan 8-7
8.3.1 Technical and Quality Objectives of the Project 8-8
8.3.2 Validation Tests 8-9
8.3.3 Data Qualifiers 8-9
8.3.4 Reporting and Documentation 8-10
8.4 Other Essential Elements for Data Validation 8-11
8.4.1 Statement of Work 8-11
8.4.2 Verified Data Deliverables 8-12
8.5 Data Verification and Validation Process 8-12
8.5.1 The Sample Handling and Analysis System 8-13
8.5.1.1 Sample Descriptors 8-14
8.5.1.2 Aliquant Size 8-15
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8.5.1.3 Dates of Sample Collection, Preparation, and Analysis 8-16
8.5.1.4 Preservation 8-16
8.5.1.5 Tracking 8-17
8.5.1.6 Traceability 8-17
8.5.1.7 QC Types and Linkages 8-18
8.5.1.8 Chemical Separation (Yield) 8-18
8.5.1.9 Self-Absorption 8-19
8.5.1.10 Efficiency, Calibration Curves, and Instrument Background 8-19
8.5.1.11 Spectrometry Resolution 8-20
8.5.1.12 Dilution and Correction Factors 8-20
8.5.1.13 Counts and Count Time (Duration) 8-21
8.5.1.14 Result of Measurement, Uncertainty, Minimum Detectable Concentration,
and Units 8-21
8.5.2 Quality Control Samples 8-22
8.5.2.1 Method Blank 8-23
8.5.2.2 Laboratory Control Samples 8-23
8.5.2.3 Laboratory Replicates 8-24
8.5.2.4 Matrix Spikes and Matrix Spike Duplicates 8-24
8.5.3 Tests of Detection and Unusual Uncertainty 8-25
8.5.3.1 Detection 8-25
8.5.3.2 Detection Capability 8-26
8.5.3.3 Large or Unusual Uncertainty 8-27
8.5.4 Final Qualification and Reporting 8-27
8.6 Validation Report 8-29
8.7 Summary of Recommendations 8-31
8.8 Bibliography 8-31
9 Data Quality Assessment 9-1
9.1 Introduction 9-1
9.2 Assessment Phase 9-2
9.3 Graded Approach to Assessment 9-3
9.4 The Data Quality Assessment Team 9-3
9.5 Data Quality Assessment Plan 9-4
9.6 Data Quality Assessment Process 9-5
9.6.1 Review of Project Documents 9-7
9.6.1.1 TheProjectDQOsandMQOs 9-7
9.6.1.2 The DQA Plan 9-8
9.6.1.3 Summary of the DQA Review 9-8
9.6.2 Sample Representativeness 9-9
9.6.2.1 Review of the Sampling Plan 9-9
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9.6.2.2 Sampling Plan Implementation 9-12
9.6.2.3 Data Considerations 9-13
9.6.3 Data Accuracy 9-14
9.6.3.1 Review of the Analytical Plan 9-18
9.6.3.2 Analytical Plan Implementation 9-19
9.6.4 Decisions and Tolerable Error Rates 9-21
9.6.4.1 Statistical Evaluation of Data 9-21
9.6.4.2 Evaluation of Decision Error Rates 9-24
9.7 Data Quality Assessment Report 9-25
9.8 Summary of Recommendations 9-26
9.9 References 9-27
9.9.1 Cited Sources 9-27
9.9.2 Other Sources 9-27
Volume II
10 Field and Sampling Issues That Affect Laboratory Measurements 10-1
Part A: Generic Issues 10-1
10.1 Introduction 10-1
10.2 Field Sampling Plan: Non-Matrix-Specific Issues 10-3
10.2.1 Determination of Analytical Sample Size 10-3
10.2.2 Field Equipment and Supply Needs 10-3
10.2.3 Selection of Sample Containers 10-4
10.2.3.1 Container Material 10-4
10.2.3.2 Container Opening and Closure 10-5
10.2.3.3 Sealing Containers 10-5
10.2.3.4 Precleaned and Extra Containers 10-5
10.2.4 Container Label and Sample Identification Code 10-6
10.2.5 Field Data Documentation 10-7
10.2.6 Field Tracking, Custody, and Shipment Forms 10-8
10.2.7 Chain of Custody 10-9
10.2.8 Field Quality Control 10-10
10.2.9 Decontamination of Field Equipment 10-10
10.2.10 Packing and Shipping 10-11
10.2.11 Worker Health and Safety Plan 10-12
10.2.11.1 Physical Hazards 10-13
10.2.11.2 Biohazards 10-15
Part B: Matrix-Specific Issues That Impact Field Sample Collection, Processing, and
Preservation 10-16
10.3 Liquid Samples 10-17
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10.3.1 Liquid Sampling Methods 10-18
10.3.2 Liquid Sample Preparation: Filtration 10-18
10.3.2.1 Example of Guidance for Ground-Water Sample Filtration 10-19
10.3.2.2 Filters 10-21
10.3.3 Field Preservation of Liquid Samples 10-22
10.3.3.1 Sample Acidification 10-22
10.3.3.2 Non-Acid Preservation Techniques 10-23
10.3.4 Liquid Samples: Special Cases 10-25
10.3.4.1 Radon-222 in Water 10-25
10.3.4.1 Milk 10-26
10.3.5 Nonaqueous Liquids and Mixtures 10-26
10.4 Solids 10-28
10.4.1 Soils 10-29
10.4.1.1 Soil Sample Preparation 10-29
10.4.1.2 Sample Ashing 10-30
10.4.2 Sediments 10-30
10.4.3 Other Solids 10-31
10.4.3.1 Structural Materials 10-31
10.4.3.2 Biota: Samples of Plant and Animal Products 10-31
10.5 Air Sampling 10-34
10.5.1 Sampler Components and Operation 10-34
10.5.2 Filter Selection Based on Destructive Versus Nondestructive Analysis .... 10-35
10.5.3 Sample Preservation and Storage 10-36
10.5.4 Special Cases: Collection of Gaseous and Volatile Air Contaminants 10-36
10.5.4.1 Radioiodines 10-36
10.5.4.2 Gases 10-37
10.5.4.3 Tritium Air Sampling 10-38
10.5.4.4 Radon Sampling in Air 10-39
10.6 Wipe Sampling for Assessing Surface Contamination 10-41
10.6.1 Sample Collection Methods 10-42
10.6.1.1 Dry Wipes 10-42
10.6.1.2 Wet Wipes 10-43
10.6.2 Sample Handling 10-44
10.6.3 Analytical Considerations for Wipe Material Selection 10-44
10.7 References 10-45
11 Sample Receipt, Inspection, and Tracking 11-1
11.1 Introduction 11-1
11.2 General Considerations 11-1
11.2.1 Communication Before Sample Receipt 11-1
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11.2.2 Standard Operating Procedures 11-3
11.2.3 Laboratory License 11-4
11.2.4 Sample Chain-of-Custody 11-4
11.3 Sample Receipt 11-5
11.3.1 Package Receipt 11-5
11.3.2 Radiological Surveying 11-6
11.3.3 Corrective Action 11-8
11.4 Sample Inspection 11-8
11.4.1 Physical Integrity of Package and Sample Containers 11-8
11.4.2 Sample Identity Confirmation 11-9
11.4.3 Confirmation of Field Preservation 11-9
11.4.4 Presence of Hazardous Materials 11-9
11.4.5 Corrective Action 11-10
11.5 Laboratory Sample Tracking 11-11
11.5.1 Sample Log-In 11-11
11.5.2 Sample Tracking During Analyses 11-11
11.5.3 Storage of Samples 11-12
11.6 References 11-13
12 Laboratory Sample Preparation 12-1
12.1 Introduction 12-1
12.2 General Guidance for Sample Preparation 12-2
12.2.1 Potential Sample Losses During Preparation 12-2
12.2.1.1 Losses as Dust or Particulates 12-2
12.2.1.2 Losses Through Volatilization 12-3
12.2.1.3 Losses Due to Reactions Between Sample and Container 12-5
12.2.2 Contamination from Sources in the Laboratory 12-6
12.2.2.1 Airborne Contamination 12-7
12.2.2.2 Contamination of Reagents 12-7
12.2.2.3 Contamination of Glassware and Equipment 12-8
12.2.2.4 Contamination of Facilities 12-8
12.2.3 Cleaning of Labware, Glassware, and Equipment 12-8
12.2.3.1 Labware and Glassware 12-8
12.2.3.2 Equipment 12-10
12.3 Solid Samples 12-12
12.3.1 General Procedures 12-12
12.3.1.1 Exclusion of Material 12-14
12.3.1.2 Principles of Heating Techniques for Sample Pretreatment 12-14
12.3.1.3 Obtaining a Constant Weight 12-23
12.3.1.4 Subsampling 12-24
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12.3.2 Soil/Sediment Samples 12-27
12.3.2.1 Soils 12-28
12.3.2.2 Sediments 12-28
12.3.3 Biota Samples 12-28
12.3.3.1 Food 12-29
12.3.3.2 Vegetation 12-29
12.3.3.3 Bone and Tissue 12-30
12.3.4 Other Samples 12-30
12.4 Filters 12-30
12.5 Wipe Samples 12-31
12.6 Liquid Samples 12-32
12.6.1 Conductivity 12-32
12.6.2 Turbidity 12-32
12.6.3 Filtration 12-33
12.6.4 Aqueous Liquids 12-33
12.6.5 Nonaqueous Liquids 12-34
12.6.6 Mixtures 12-35
12.6.6.1 Liquid-Liquid Mixtures 12-35
12.6.6.2 Liquid-Solid Mixtures 12-35
12.7 Gases 12-36
12.8 Bioassay 12-36
12.9 References 12-37
12.9.1 Cited Sources 12-37
12.9.2 Other Sources 12-43
13 Sample Dissolution 13-1
13.1 Introduction 13-1
13.2 The Chemistry of Dissolution 13-2
13.2.1 Solubility and the Solubility Product Constant, Ksp 13-2
13.2.2 Chemical Exchange, Decomposition, and Simple Rearrangement Reactions . 13-3
13.2.3 Oxidation-Reduction Processes 13-4
13.2.4 Complexation 13-5
13.2.5 Equilibrium: Carriers and Tracers 13-6
13.3 Fusion Techniques 13-6
13.3.1 Alkali-Metal Hydroxide Fusions 13-9
13.3.2 Boron Fusions 13-11
13.3.3 Fluoride Fusions 13-12
13.3.4 Sodium Hydroxide Fusion 13-12
13.4 Wet Ashing and Acid Dissolution Techniques 13-12
13.4.1 Acids and Oxidants 13-13
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13.4.2 Acid Digestion Bombs 13-20
13.5 Microwave Digestion 13-21
13.5.1 Focused Open-Vessel Systems 13-21
13.5.2 Low-Pressure, Closed-Vessel Systems 13-22
13.5.3 High-Pressure, Closed-Vessel Systems 13-22
13.6 Verification of Total Dissolution 13-23
13.7 Special Matrix Considerations 13-23
13.7.1 Liquid Samples 13-23
13.7.2 Solid Samples 13-24
13.7.3 Filters 13-24
13.7.4 Wipe Samples 13-24
13.8 Comparison of Total Dissolution and Acid Leaching 13-25
13.9 References 13-27
13.9.1 Cited References 13-27
13.9.2 Other Sources 13-29
14 Separation Techniques 14-1
14.1 Introduction 14-1
14.2 Oxidation-Reduction Processes 14-2
14.2.1 Introduction 14-2
14.2.2 Oxidation-Reduction Reactions 14-3
14.2.3 Common Oxidation States 14-6
14.2.4 Oxidation State in Solution 14-10
14.2.5 Common Oxidizing and Reducing Agents 14-11
14.2.6 Oxidation State and Radiochemical Analysis 14-13
14.3 Complexation 14-18
14.3.1 Introduction 14-18
14.3.2 Chelates 14-20
14.3.3 The Formation (Stability) Constant 14-22
14.3.4 Complexation and Radiochemical Analysis 14-23
14.3.4.1 Extraction of Laboratory Samples and Ores 14-23
14.3.4.2 Separation by Solvent Extraction and Ion-Exchange Chromatography 14-23
14.3.4.3 Formation and Dissolution of Precipitates 14-24
14.3.4.4 Stabilization of Ions in Solution 14-24
14.3.4.5 Detection and Determination 14-25
14.4 Solvent Extraction 14-25
14.4.1 Extraction Principles 14-25
14.4.2 Distribution Coefficient 14-26
14.4.3 Extraction Technique 14-27
14.4.4 Solvent Extraction and Radiochemical Analysis 14-30
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14.4.5 Solid-Phase Extraction 14-32
14.4.5.1 Extraction Chromatography Columns 14-33
14.4.5.2 Extraction Membranes 14-34
14.4.6 Advantages and Disadvantages of Solvent Extraction 14-35
14.4.6.1 Advantages of Liquid-Liquid Solvent Extraction 14-35
14.4.6.2 Disadvantages of Liquid-Liquid Solvent Extraction 14-35
14.4.6.3 Advantages of Solid-Phase Extraction Media 14-35
14.4.6.4 Disadvantages of Solid-Phase Extraction Media 14-36
14.5 Volatilization and Distillation 14-36
14.5.1 Introduction 14-36
14.5.2 Volatilization Principles 14-36
14.5.3 Distillation Principles 14-38
14.5.4 Separations in Radiochemical Analysis 14-39
14.5.5 Advantages and Disadvantages of Volatilization 14-40
14.5.5.1 Advantages 14-40
14.5.5.2 Disadvantages 14-40
14.6 Electrodeposition 14-41
14.6.1 Electrodeposition Principles 14-41
14.6.2 Separation of Radionuclides 14-42
14.6.3 Preparation of Counting Sources 14-43
14.6.4 Advantages and Disadvantages of Electrodeposition 14-43
14.6.4.1 Advantages 14-43
14.6.4.2 Disadvantages 14-43
14.7 Chromatography 14-44
14.7.1 Chromatographic Principles 14-44
14.7.2 Gas-Liquid and Liquid-Liquid Phase Chromatography 14-45
14.7.3 Adsorption Chromatography 14-45
14.7.4 Ion-Exchange Chromatography 14-46
14.7.4.1 Principles of Ion Exchange 14-46
14.7.4.2 Resins 14-48
14.7.5 Affinity Chromatography 14-54
14.7.6 Gel-Filtration Chromatography 14-54
14.7.7 Chromatographic Laboratory Methods 14-55
14.7.8 Advantages and Disadvantages of Chromatographic Systems 14-56
14.7.8.1 Advantages 14-56
14.7.8.2 Disadvantages 14-56
14.8 Precipitation and Coprecipitation 14-56
14.8.1 Introduction 14-56
14.8.2 Solutions 14-57
14.8.3 Precipitation 14-59
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14.8.3.1 Solubility and the Solubility Product Constant, Ksp 14-59
14.8.3.2 Factors Affecting Precipitation 14-64
14.8.3.3 Optimum Precipitation Conditions 14-69
14.8.4 Coprecipitation 14-69
14.8.4.1 Coprecipitation Processes 14-70
14.8.4.2 Water as an Impurity 14-74
14.8.4.3 Postprecipitation 14-74
14.8.4.4 Coprecipitation Methods 14-75
14.8.5 Colloidal Precipitates 14-78
14.8.6 Separation of Precipitates 14-81
14.8.7 Advantages and Disadvantages of Precipitation and Coprecipitation 14-82
14.8.7.1 Advantages 14-82
14.8.7.2 Disadvantages 14-82
14.9 Carriers and Tracers 14-82
14.9.1 Introduction 14-82
14.9.2 Carriers 14-83
14.9.2.1 Isotopic Carriers 14-83
14.9.2.2 Nonisotopic Carriers 14-84
14.9.2.3 Common Carriers 14-85
14.9.2.4 Holdback Carriers 14-89
14.9.2.5 Yield of Isotopic Carriers 14-89
14.9.3 Tracers 14-90
14.9.3.1 Characteristics of Tracers 14-92
14.9.3.2 Coprecipitation 14-93
14.9.3.3 Deposition on Nonmetallic Solids 14-93
14.9.3.4 Radiocolloid Formation 14-94
14.9.3.5 Distribution (Partition) Behavior 14-95
14.9.3.6 Vaporization 14-95
14.9.3.7 Oxidation and Reduction 14-96
14.10 Analysis of Specific Radionuclides 14-97
14.10.1 Basic Principles of Chemical Equilibrium 14-97
14.10.2 Oxidation State 14-100
14.10.3 Hydrolysis 14-100
14.10.4 Polymerization 14-102
14.10.5 Complexation 14-103
14.10.6 Radiocolloid Interference 14-103
14.10.7 Isotope Dilution Analysis 14-104
14.10.8 Masking and Demasking 14-105
14.10.9 Review of Specific Radionuclides 14-109
14.10.9.1 Americium 14-109
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14.10.9.2 Carbon 14-114
14.10.9.3 Cesium 14-116
14.10.9.4 Cobalt 14-119
14.10.9.5 Iodine 14-125
14.10.9.6 Neptunium 14-132
14.10.9.7 Nickel 14-136
14.10.9.8 Plutonium 14-139
14.10.9.9 Radium 14-148
14.10.9.10 Strontium 14-155
14.10.9.11 Sulfur and Phosphorus 14-160
14.10.9.12 Technetium 14-163
14.10.9.13 Thorium 14-169
14.10.9.14 Tritium 14-175
14.10.9.15 Uranium 14-180
14.10.9.16 Zirconium 14-191
14.10.9.17 Progeny of Uranium and Thorium 14-198
14.11 References 14-201
14.12 Selected Bibliography 14-218
14.12.1 Inorganic and Analytical Chemistry 14-218
14.12.2 General Radiochemistry 14-219
14.12.3 Radiochemical Methods of Separation 14-219
14.12.4 Radionuclides 14-220
14.12.5 Separation Methods 14-222
Attachment 14A Radioactive Decay and Equilibrium 14-223
14A.1 Radioactive Equilibrium 14-223
14A.1.1 Secular Equilibrium 14-223
14A.1.2 Transient Equilibrium 14-225
14A.1.3 No Equilibrium 14-226
14A.1.4 Summary of Radioactive Equilibria 14-227
14A.1.5 Supported and Unsupported Radioactive Equilibria 14-228
14A.2 Effects of Radioactive Equilibria on Measurement Uncertainty 14-229
14A.2.1 Issue 14-229
14A.2.2 Discussion 14-229
14A.2.3 Examples of Isotopic Distribution: Natural, Enriched, and Depleted
Uranium 14-231
14A.3 References 14-232
15 Quantification of Radionuclides 15-1
15.1 Introduction 15-1
15.2 Instrument Calibrations 15-2
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15.2.1 Calibration Standards 15-3
15.2.2 Congruence of Calibration and Test-Source Geometry 15-3
15.2.3 Calibration and Test-Source Homogeneity 15-5
15.2.4 Self-Absorption, Attenuation, and Scattering Considerations for Source
Preparations 15-5
15.2.5 Calibration Uncertainty 15-7
15.3 Methods of Source Preparation 15-8
15.3.1 Electrodeposition 15-8
15.3.2 Precipitation/Coprecipitation 15-11
15.3.3 Evaporation 15-12
15.3.4 Thermal Volatilization/Sublimation 15-15
15.3.5 Special Source Matrices 15-16
15.3.5.1 Radioactive Gases 15-16
15.3.5.2 Air Filters 15-17
15.3.5.3 Swipes 15-18
15.4 Alpha Detection Methods 15-18
15.4.1 Introduction 15-18
15.4.2 Gas Proportional Counting 15-20
15.4.2.1 Detector Requirements and Characteristics 15-20
15.4.2.2 Calibration and Test Source Preparation 15-25
15.4.2.3 Detector Calibration 15-25
15.4.2.4 Troubleshooting 15-27
15.4.3 Solid-State Detectors 15-29
15.4.3.1 Detector Requirements and Characteristics 15-30
15.4.3.2 Calibration- and Test-Source Preparation 15-33
15.4.3.3 Detector Calibration 15-33
15.4.3.4 Troubleshooting 15-34
15.4.3.5 Detector or Detector Chamber Contamination 15-35
15.4.3.6 Degraded Spectrum 15-37
15.4.4 Fluorescent Detectors 15-38
15.4.4.1 Zinc Sulfide 15-38
15.4.4.2 Calibration- and Test-Source Preparation 15-40
15.4.4.3 Detector Calibration 15-41
15.4.4.4 Troubleshooting 15-41
15.4.5 Photon Electron Rejecting Alpha Li quid Scintillation (PERALS®) 15-42
15.4.5.1 Detector Requirements and Characteristics 15-42
15.4.5.2 Calibration- and Test-Source Preparation 15-44
15.4.5.3 Detector Calibration 15-45
15.4.5.4 Quench 15-45
15.4.5.5 Available Cocktails 15-46
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15.4.5.6 Troubleshooting 15-46
15.5 Beta Detection Methods 15-46
15.5.1 Introduction 15-46
15.5.2 Gas Proportional Counting/Geiger-Mueller Tube Counting 15-49
15.5.2.1 Detector Requirements and Characteristics 15-49
15.5.2.2 Calibration- and Test-Source Preparation 15-53
15.5.2.3 Detector Calibration 15-54
15.5.2.4. Troubleshooting 15-57
15.5.3 Liquid Scintillation 15-57
15.5.3.1 Detector Requirements and Characteristics 15-58
15.5.3.2 Calibration- and Test-Source Preparation 15-61
15.5.3.3 Detector Calibration 15-62
15.5.3.4 Troubleshooting 15-68
15.6 Gamma Detection Methods 15-68
15.6.1 Sample Preparation Techniques 15-70
15.6.1.1 Containers 15-71
15.6.1.2 Gases 15-71
15.6.1.3 Liquids 15-72
15.6.1.4 Solids 15-72
15.6.2 Sodium Iodide Detector 15-73
15.6.2.1 Detector Requirements and Characteristics 15-73
15.6.2.2 Operating Voltage 15-76
15.6.2.3 Shielding 15-76
15.6.2.4 Background 15-76
15.6.2.5 Detector Calibration 15-77
15.6.2.6 Troubleshooting 15-77
15.6.3 High Purity Germanium 15-78
15.6.3.1 Detector Requirements and Characteristics 15-78
15.6.3.2 Gamma Spectrometer Calibration 15-82
15.6.3.3 Troubleshooting 15-84
15.6.4 Extended Range Germanium Detectors 15-88
15.6.4.1 Detector Requirements and Characteristics 15-89
15.6.4.2 Detector Calibration 15-89
15.6.4.3 Troubleshooting 15-90
15.6.5 Special Techniques for Radiation Detection 15-90
15.6.5.1 Other Gamma Detection Systems 15-90
15.6.5.2 Coincidence Counting 15-91
15.6.5.3 Anti-Coincidence Counting 15-93
15.7 Specialized Analytical Techniques 15-94
15.7.1 Kinetic Phosphorescence Analysis by Laser (KPA) 15-94
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15.7.2 Mass Spectrometry 15-95
15.7.2.1 Inductively Coupled Plasma-Mass Spectrometry 15-96
15.7.2.2 Thermal lonization Mass Spectrometry 15-99
15.7.2.3 Accelerator Mass Spectrometry 15-100
15.8 References 15-101
15.8.1 Cited References 15-101
15.8.2 Other Sources 15-115
16 Data Acquisition, Reduction, and Reporting for Nuclear Counting Instrumentation .... 16-1
16.1 Introduction 16-1
16.2 Data Acquisition 16-2
16.2.1 Generic Counting Parameter Selection 16-3
16.2.1.1 Counting Duration 16-4
16.2.1.2 Counting Geometry 16-5
16.2.1.3 Software 16-5
16.2.2 Basic Data Reduction Calculations 16-6
16.3 Data Reduction on Spectrometry Systems 16-8
16.3.1 Gamma-Ray Spectrometry 16-9
16.3.1.1 Peak Search or Identification 16-10
16.3.1.2 Singlet/MultipletPeaks 16-13
16.3.1.3 Definition of Peak Centroid and Energy 16-14
16.3.1.4 Peak Width Determination 16-15
16.3.1.5 Peak Area Determination 16-17
16.3.1.6 Calibration Reference File 16-19
16.3.1.7 Activity and Concentration 16-20
16.3.1.8 Summing Considerations 16-21
16.3.1.9 Uncertainty Calculation 16-22
16.3.2 Alpha Spectrometry 16-23
16.3.2.1 Radiochemical Yield 16-27
16.3.2.2 Uncertainty Calculation 16-28
16.3.3 Liquid Scintillation Spectrometry 16-29
16.3.3.1 Overview of Liquid Scintillation Counting 16-29
16.3.3.2 Liquid Scintillation Spectra 16-29
16.3.3.3 Pulse Characteristics 16-29
16.3.3.4 Coincidence Circuitry 16-30
16.3.3.5 Quenching 16-30
16.3.3.6 Luminescence 16-31
16.3.3.7 Test-Source Vials 16-31
16.3.3.8 Data Reduction for Liquid Scintillation Counting 16-31
16.4 Data Reduction on Non-Spectrometry Systems 16-32
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16.5 Internal Review of Data by Laboratory Personnel 16-36
16.5.1 Primary Review 16-37
16.5.2 Secondary Review 16-37
16.6 Reporting Results 16-38
16.6.1 Sample and Analysis Method Identification 16-38
16.6.2 Units and Radionuclide Identification 16-38
16.6.3 Values, Uncertainty, and Significant Figures 16-39
16.7 Data Reporting Packages 16-39
16.8 Electronic Data Deliverables 16-41
16.9 References 16-41
16.9.1 Cited References 16-41
16.9.2 Other Sources 16-44
17 Waste Management in a Radioanalytical Laboratory 17-1
17.1 Introduction 17-1
17.2 Types of Laboratory Wastes 17-1
17.3 Waste Management Program 17-2
17.3.1 Program Integration 17-3
17.3.2 Staff Involvement 17-3
17.4 Waste Minimization 17-3
17.5 Waste Characterization 17-6
17.6 Specific Waste Management Requirements 17-6
17.6.1 Sample/Waste Exemptions 17-9
17.6.2 Storage 17-9
17.6.2.1 Container Requirements 17-10
17.6.2.2 Labeling Requirements 17-10
17.6.2.3 Time Constraints 17-11
17.6.2.4 Monitoring Requirements 17-11
17.6.3 Treatment 17-12
17.6.4 Disposal 17-12
17.7 Contents of a Laboratory Waste Management Plan/Certification Plan 17-13
17.7.1 Laboratory Waste Management Plan 17-13
17.7.2 Waste Certification Plan/Program 17-14
17.8 Useful Web Sites 17-15
17.9 References 17-17
17.9.1 Cited References 17-17
17.9.2 Other Sources 17-17
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Contents
Volume III
18 Laboratory Quality Control 18-1
18.1 Introduction 18-1
18.1.1 Organization of Chapter 18-2
18.1.2 Format 18-2
18.2 Quality Control 18-3
18.3 Evaluation of Performance Indicators 18-3
18.3.1 Importance of Evaluating Performance Indicators 18-3
18.3.2 Statistical Means of Evaluating Performance Indicators — Control Charts .. 18-5
18.3.3 Tolerance Limits 18-7
18.3.4 Measurement Uncertainty 18-8
18.4 Radiochemistry Performance Indicators 18-9
18.4.1 Method and Reagent Blank 18-9
18.4.2 Laboratory Replicates 18-13
18.4.3 Laboratory Control Samples, Matrix Spikes, and Matrix Spike Duplicates . 18-16
18.4.4 Certified Reference Materials 18-18
18.4.5 Chemical/Tracer Yield 18-21
18.5 Instrumentation Performance Indicators 18-24
18.5.1 Instrument Background Measurements 18-24
18.5.2 Efficiency Calibrations 18-26
18.5.3 Spectrometry Systems 18-29
18.5.3.1 Energy Calibrations 18-29
18.5.3.2 Peak Resolution and Tailing 18-32
18.5.4 Gas Proportional Systems 18-36
18.5.4.1 Voltage Plateaus 18-36
18.5.4.2 Self-Absorption, Backscatter, and Crosstalk 18-37
18.5.5 Liquid Scintillation 18-38
18.5.6 Summary Guidance on Instrument Calibration, Background,
and Quality Control 18-40
18.5.6.1 Gas Proportional Counting Systems 18-42
18.5.6.2 Gamma-Ray Detectors and Spectrometry Systems 18-45
18.5.6.3 Alpha Detector and Spectrometry Systems 18-49
18.5.6.4 Liquid Scintillation Systems 18-51
18.5.7 Non-Nuclear Instrumentation 18-53
18.6 Related Concerns 18-54
18.6.1 Detection Capability 18-54
18.6.2 Radioactive Equilibrium 18-54
18.6.3 Half-Life 18-57
18.6.4 Interferences 18-58
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18.6.5 Negative Results 18-60
18.6.6 Blind Samples 18-61
18.6.7 Calibration of Apparatus Used for Mass and Volume Measurements 18-63
18.7 References 18-65
18.7.1 Cited Sources 18-65
18.7.2 Other Sources 18-67
Attachment ISA: Control Charts 18-69
18A.1 Introduction 18-69
18A.2 JTCharts 18-69
18A.3 X Charts 18-72
18A.4 R Charts 18-74
18A.5 Control Charts for Instrument Response 18-75
18A.6 References 18-79
Attachment 18B: Statistical Tests for QC Results 18-81
18B.1 Introduction 18-81
18B.2 Tests for Excess Variance in the Instrument Response 18-81
18B.3 Instrument Background Measurements 18-88
18B.3.1 Detection of Background Variability 18-88
18B.3.2 Comparing a Single Observation to Preset Limits 18-90
18B.3.3 Comparing the Results of Consecutive Measurements 18-93
18B.4 Negative Activities 18-96
18B.5 References 18-96
19 Measurement Uncertainty 19-1
19.1 Overview 19-1
19.2 The Need for Uncertainty Evaluation 19-1
19.3 Evaluating and Expressing Measurement Uncertainty 19-3
19.3.1 Measurement, Error, and Uncertainty 19-3
19.3.2 The Measurement Process 19-4
19.3.3 Analysis of Measurement Uncertainty 19-6
19.3.4 Corrections for Systematic Effects 19-7
19.3.5 Counting Uncertainty 19-7
19.3.6 Expanded Uncertainly 19-7
19.3.7 Significant Figures 19-8
19.3.8 Reporting the Measurement Uncertainty 19-9
19.3.9 Recommendations 19-10
19.4 Procedures for Evaluating Uncertainty 19-11
19.4.1 Identifying Sources of Uncertainty 19-12
19.4.2 Evaluation of Standard Uncertainties 19-13
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19.4.2.1 Type A Evaluations 19-13
19.4.2.2 Type B Evaluations 19-16
19.4.3 Combined Standard Uncertainty 19-20
19.4.3.1 Uncertainty Propagation Formula 19-20
19.4.3.2 Components of Uncertainty 19-24
19.4.3.3 Special Forms of the Uncertainty Propagation Formula 19-25
19 A A The Estimated Covariance of Two Output Estimates 19-26
19.4.5 Special Considerations for Nonlinear Models 19-29
19.4.5.1 Uncertainty Propagation for Nonlinear Models 19-29
19.4.5.2 Bias due to Nonlinearity 19-31
19.4.6 Monte Carlo Methods 19-34
19.5 Radiation Measurement Uncertainty 19-34
19.5.1 Radioactive Decay 19-34
19.5.2 Radiation Counting 19-35
19.5.2.1 Binomial Model 19-35
19.5.2.2 Poisson Approximation 19-36
19.5.3 Count Time and Count Rate 19-38
19.5.3.1 Dead Time 19-39
19.5.3.2 A Confidence Interval for the Count Rate 19-40
19.5.4 Instrument Background 19-41
19.5.5 Radiochemical Blanks 19-42
19.5.6 Counting Efficiency 19-43
19.5.7 Radionuclide Half-Life 19-47
19.5.8 Gamma-Ray Spectrometry 19-48
19.5.9 Balances 19-48
19.5.10 Pipets and Other Volumetric Apparatus 19-52
19.5.11 Digital Displays and Rounding 19-54
19.5.12 Subsampling 19-55
19.5.13 The Standard Uncertainty for a Hypothetical Measurement 19-56
19.6 References 19-58
19.6.1 Cited Sources 19-58
19.6.2 Other Sources 19-61
Attachment 19A: Statistical Concepts and Terms 19-63
19A. 1 Basic Concepts 19-63
19A.2 Probability Distributions 19-66
19A.2.1 Normal Distributions 19-67
19A.2.2 Log-normal Distributions 19-68
19A.2.3 Chi-squared Distributions 19-69
19A.2.4 T-Distributions 19-70
19A.2.5 Rectangular Distributions 19-71
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19A.2.6 Trapezoidal and Triangular Distributions 19-72
19A.2.7 Exponential Distributions 19-73
19A.2.8 Binomial Distributions 19-73
19A.2.9 Poisson Distributions 19-74
19A.3 References 19-76
Attachment 19B: Example Calculations 19-77
19B.1 Overview 19-77
19B.2 Sample Collection and Analysis 19-77
19B.3 The Measurement Model 19-78
19B.4 The Combined Standard Uncertainty 19-80
Attachment 19C: Multicomponent Measurement Models 19-83
19C.1 Introduction 19-83
19C.2 The Covariance Matrix 19-83
19C.3 Least-Squares Regression 19-83
19C.4 References 19-84
Attachment 19D: Estimation of Coverage Factors 19-85
19D. 1 Introduction 19-85
19D.2 Procedure 19-85
19D.2.1 Basis of Procedure 19-85
19D.2.2 Assumptions 19-85
19D.2.3 Effective Degrees of Freedom 19-86
19D.2.4 Coverage Factor 19-87
19D.3 Poisson Counting Uncertainty 19-88
19D.4 References 19-91
Attachment 19E: Uncertainties of Mass and Volume Measurements 19-93
19E.1 Purpose 19-93
19E.2 Mass Measurements 19-93
19E.2.1 Considerations 19-93
19E.2.2 Repeatability 19-94
19E.2.3 Environmental Factors 19-95
19E.2.4 Calibration 19-97
19E.2.5 Linearity 19-98
19E.2.6 Gain or Loss of Mass 19-98
19E.2.7 Air-Buoyancy Corrections 19-99
19E.2.8 Combining the Components 19-103
19E.3 Volume Measurements 19-105
19E.3.1 First Approach 19-105
19E.3.2 Second Approach 19-108
19E.3.3 Third Approach 19-111
19E.4 References 19-111
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20 Detection and Quantification Capabilities 20-1
20.1 Overview 20-1
20.2 Concepts and Definitions 20-1
20.2.1 Analyte Detection Decisions 20-1
20.2.2 The Critical Value 20-3
20.2.3 The Blank 20-5
20.2.4 The Minimum Detectable Concentration 20-5
20.2.6 Other Detection Terminologies 20-9
20.2.7 The Minimum Quantifiable Concentration 20-10
20.3 Recommendations 20-11
20.4 Calculation of Detection and Quantification Limits 20-12
20.4.1 Calculation of the Critical Value 20-12
20.4.1.1 Normally Distributed Signals 20-13
20.4.1.2 Poisson Counting 20-13
20.4.1.3 Batch Blanks 20-17
20.4.2 Calculation of the Minimum Detectable Concentration 20-18
20.4.2.1 The Minimum Detectable Net Instrument Signal 20-19
20.4.2.2 Normally Distributed Signals 20-20
20.4.2.3 Poisson Counting 20-24
20.4.2.4 More Conservative Approaches 20-28
20.4.2.5 Experimental Verification of the MDC 20-28
20.4.3 Calculation of the Minimum Quantifiable Concentration 20-29
20.5 References 20-33
20.5.1 Cited Sources 20-33
20.5.2 Other Sources 20-35
Attachment 20A: Low-Background Detection Issues 20-37
20A.1 Overview 20-37
20A.2 Calculation of the Critical Value 20-37
20A.2.1 Normally Distributed Signals 20-37
20A.2.2 Poisson Counting 20-39
20A.3 Calculation of the Minimum Detectable Concentration 20-53
20A.3.1 Normally Distributed Signals 20-54
20A.3.2 Poisson Counting 20-58
20A.4 References 20-62
Glossary End of each volume
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Appendices - Volume I
A Directed Planning Approaches A-l
A.I Introduction A-l
A.2 Elements Common to Directed Planning Approaches A-2
A.3 Data Quality Objectives Process A-2
A.4 Observational Approach A-3
A. 5 Streamlined Approach for Environmental Restoration A-4
A.6 Technical Project Planning A-4
A.7 Expedited Site Characterization A-4
A.8 Value Engineering A-5
A.9 Systems Engineering A-6
A. 10 Total Quality Management A-6
A. 11 Partnering A-7
A. 12 References A-7
A.12.1 Data Quality Objectives A-7
A. 12.2 Observational Approach A-9
A. 12.3 Streamlined Approach for Environmental Restoration (Safer) A-10
A. 12.4 Technical Project Planning A-l 1
A. 12.5 Expedited Site Characterization A-l 1
A. 12.6 Value Engineering A-12
A. 12.7 Systems Engineering A-13
A. 12.8 Total Quality Management A-15
A. 12.9 Partnering A-16
Appendix B The Data Quality Objectives Process B-l
B. 1 Introduction B-l
B.2Overview of the DQO Process B-2
B.3 The Seven Steps of the DQO Process B-3
B.3.1 DQO Process Step 1: State the Problem B-3
B.3.2 DQO Process Step 2: Identify the Decision B-4
B.3.3 DQO Process Step 3: Identify Inputs to the Decision B-5
B.3.4 DQO Process Step 4: Define the Study Boundaries B-6
B.3.5 Outputs of DQO Process Steps 1 through 4 Lead Into Steps 5 through 7 B-7
B.3.6 DQO Process Step 5: Develop a Decision Rule B-7
B.3.7 DQO Process Step 6: Specify the Limits on Decision Errors B-9
B.3.8 DQO Process Step 7: Optimize the Design for Obtaining Data B-22
B.4References B-24
Attachment B1: Decision Error Rates and the Gray Region for Decisions About
Mean Concentrations B-26
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Bl.l Introduction B-26
B1.2 The Region of Interest B-26
B1.3 Measurement Uncertainty at the Action Level B-26
B1.4 The Null Hypothesis B-29
Case 1: Assume the True Concentration is Over 1.0 B-30
Case 2: Assume the True Concentration is 0.9 B-32
B1.5 The Gray Region B-32
B1.6 Summary B-34
Attachment B2: Decision Error Rates and the Gray Region for Detection Decisions .... B-36
B2.1 Introduction B-36
B2.2 The DQO Process Applied to the Detection Limit Problem B-36
B2.3 Establish the Concentration Range of Interest B-37
B2.4 Estimate the Measurement Variability when Measuring a Blank B-41
Appendix C Measurement Quality Objectives for Method Uncertainty and Detection and
Quantification Capability C-l
C.I Introduction C-l
C.2Hypothesis Testing C-l
C.3Development of MQOs for Analytical Protocol Selection C-3
C.4The Role of the MQO for Method Uncertainty in Data Evaluation C-9
C.4.1 Uncertainty Requirements at Various Concentrations C-9
C.4.2 Acceptance Criteria for Quality Control Samples C-ll
C.SReferences C-17
Appendix D Content of Project Plan Documents D-l
D.I Introduction D-l
D.2Group A: Project Management D-5
D.2.1 Project Management (Al): Title and Approval Sheet D-5
D.2.2 Project Management (A2): Table of Contents D-7
D.2.3 Project Management (A3): Distribution List D-7
D.2.4 Project Management (A4): Project/Task Organization D-7
D.2.5 Project Management (A5): Problem Definition/Background D-8
D.2.6 Project Management (A6): Project/Task Description D-9
D.2.7 Project Management (A7): Quality Objectives and Criteria for Measurement
Data D-ll
D.2.7.1 Project's Quality Objectives D-ll
D.2.7.2 Specifying Measurement Quality Objectives D-12
D.2.7.3 Relation between the Project DQOs, MQOs, and QC Requirements D-13
D.2.8 Proj ect Management (A8): Special Training Requirements/Certification . . . D-13
D.2.9 Proj ect Management (A9): Documentation and Record D-13
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D.SGroup B: Measurement/Data Acquisition D-14
D.3.1 Measurement/Data Acquisition (Bl): Sampling Process Design D-15
D.3.2 Measurement/Data Acquisition (B2): Sampling Methods Requirements ... D-16
D.3.3 Measurement/Data Acquisition (B3): Sample Handling and Custody
Requirements D-18
D.3.4 Measurement/Data Acquisition (B4): Analytical Methods Requirements .. D-19
D.3.5 Measurement/Data Acquisition (B5): Quality Control Requirements D-21
D.3.6 Measurement/Data Acquisition (B6): Instrument/Equipment Testing, Inspection,
and Maintenance Requirements D-22
D.3.7 Measurement/Data Acquisition (B7): Instrument Calibration and Frequency D-23
D.3.8 Measurement/Data Acquisition (B8): Inspection/Acceptance Requirements for
Supplies and Consumables D-23
D.3.9 Measurement/Data Acquisition (B9): Data Acquisition Requirements for Non-
Direct Measurement Data D-24
D.3.10 Measurement/Data Acquisition (BIO): Data Management D-25
D.4Group C: Assessment/Oversight D-26
D.4.1 Assessment/Oversight (Cl): Assessment and Response Actions D-26
D.4.2 Assessment/Oversight (C2): Reports to Management D-27
D.SGroup D: Data Validation and Usability D-28
D.5.1 Data Validation and Usability (Dl): Verification and Validation
Requirements D-28
D.5.2 Data Validation and Usability (D2): Verification and Validation Methods . D-29
D.5.2.1 Data Verification D-29
D.5.2.2 Data Validation D-30
D.5.3 Data Validation and Usability (D3): Reconciliation with Data Quality
Objectives D-30
D.6References D-31
Appendix E Contracting Laboratory Services E-l
E. 1 Introduction E-l
E.2 Procurement of Services E-4
E.2.1 Request for Approval of Proposed Procurement Action E-5
E.2.2 Types of Procurement Mechanisms E-6
E.3 Request for Proposals—The Solicitation E-7
E.3.1 Market Research E-8
E.3.2 Period of Contract E-9
E.3.3 Subcontracts E-9
E.4Proposal Requirements E-10
E.4.1 RFP and Contract Information E-l 1
E.4.2 Personnel E-13
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E.4.3 Instrumentation E-15
E.4.3.1 Type, Number, and Age of Laboratory Instruments E-16
E.4.3.2 Service Contract E-16
E.4.4 Narrative to Approach E-16
E.4.4.1 Analytical Methods or Protocols E-16
E.4.4.2 Meeting Contract Measurement Quality Objectives E-17
E.4.4.3 Data Package E-17
E.4.4.4 Schedule E-17
E.4.4.5 Sample Storage and Disposal E-18
E.4.5 Quality Manual E-18
E.4.6 Licenses and Accreditations E-19
E.4.7 Experience E-20
E.4.7.1 Previous or Current Contracts E-20
E.4.7.2 Quality of Performance E-20
E.5 Proposal Evaluation and Scoring Procedures E-21
E.5.1 Evaluation Committee E-21
E.5.2 Ground Rules — Questions E-22
E.5.3 Scoring/Evaluating Scheme E-22
E.5.3.1 Review of Technical Proposal and Quality Manual E-23
E.5.3.2 Review of Laboratory Accreditation E-25
E.5.3.3 Review of Experience E-25
E.5.4 Pre-Award Proficiency Samples E-25
E.5.5 Pre-Award Audit E-26
E.5.6 Comparison of Prices E-30
E.5.7 Debriefing of Unsuccessful Vendors E-30
E.6The Award E-31
E.7For the Duration of the Contract E-31
E.7.1 Managing a Contract E-32
E.7.2 Responsibility of the Contractor E-32
E.7.3 Responsibility of the Agency E-32
E.7.4 Anomalies and Nonconformance E-33
E.7.5 Laboratory Assessment E-33
E.7.5.1 Performance Testing and Quality Control Samples E-33
E.7.5.2 Laboratory Performance Evaluation Programs E-34
E.7.5.3 Laboratory Evaluations Performed During the Contract Period E-35
E.8 Contract Completion E-36
E.9References E-36
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Appendices - Volume II
Appendix F Laboratory Subsampling F-l
F.I Introduction F-l
F.2 Basic Concepts F-2
F.3 Sources of Measurement Error F-3
F.3.1 Sampling Bias F-4
F.3.2 Fundamental Error F-5
F.3.3 Grouping and Segregation Error F-6
F.4 Implementation of the Particulate Sampling Theory F-9
F.4.1 The Fundamental Variance F-10
F.4.2 Scenario 1 -Natural Radioactive Minerals F-10
F.4.3 Scenario 2 - Hot Particles F-l 1
F.4.4 Scenario 3 - Particle Surface Contamination F-13
F.5 Summary F-l5
F.6 References F-16
Appendices - Volume III
G Statistical Tables G-l
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List of Figures
Figure 1.1 The data life cycle 1-4
Figure 1.2 Typical components of an analytical process 1-6
Figure 1.3 The MARLAP process 1-14
Figure 1.4 Key MARLAP terms and processes 1-15
Figure 3.1 Typical components of an analytical process 3-2
Figure 3.2 Analytical protocol specifications 3-25
Figure 3.3 Example analytical protocol specifications 3-26
Figure 3B.1 The critical value of the net signal 3-35
Figure 6.1 Analytical process 6-2
Figure 6.2 Method application life cycle 6-6
Figure 6.3 Expanded Figure 6.2 addressing the laboratory's method evaluation process .... 6-7
Figure 6.4 Relationship between level of laboratory effort, method validation level, and degree
of assurance of method performance under the tiered approach to method validation . . . 6-27
Figure 7.1 Considerations for the initial evaluation of a laboratory 7-16
Figure 8.1 The assessment process 8-5
Figure 9.1 Using physical samples to measure a characteristic of the population
representatively 9-10
Figure 9.2 Types of sampling and analytical errors 9-17
Volume II
Figure 10.1 Example of chain-of-custody record 10-9
Figure 11.1 Overview of sample receipt, inspection, and tracking 11-2
Figure 12.1 Degree of error in laboratory sample preparation relative to other activities . . . 12-1
Figure 12.2 Laboratory sample preparation flowchart (for solid samples) 12-13
Figure 14.1 Ethylene diamine tetraacetic acid (EDTA) 14-20
Figure 14.2 Crown ethers 14-21
Figure 14.3 The behavior of elements in concentrated hydrochloric acid on cation-exchange
resins 14-52
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Figure 14.4 The behavior of elements in concentrated hydrochloric acid on anion-exchange
resins 14-53
Figure 14.5 The electrical double layer 14-79
Figure 14A. 1 Decay chain for 238U 14-224
Figure 14A.2 Secular equilibrium of 210Pb/210Bi 14-225
Figure 14A.3 Transient equilibrium of 95Zr/95Nb 14-226
Figure 14A.4 No equilibrium of 239U/239Np 14-227
Figure 15.1 Alpha plateau generated by a 210Po source on a GP counter using P-10 gas . . . 15-23
Figure 15.2 Gas proportional counter self-absorption curve for 230Th 15-28
Figure 15.3 Beta plateau generated by a 90Sr/Y source on a GP counter using P-10 gas . . . 15-52
Figure 15.4 Gas proportional counter self-absorption curve for 90Sr/Y 15-56
Figure 15.5 Representation of a beta emitter energy spectrum 15-65
Figure 15.6 Gamma-ray interactions with high-purity germanium 15-70
Figure 15.7 Nal(Tl) spectrum of 137Cs 15-75
Figure 15.8 Energy spectrum of 22Na 15-80
Figure 15.9 Different geometries for the same germanium detector and the same sample in
different shapes or position 15-83
Figure 15.10 Extended range coaxial germanium detector 15-88
Figure 15.11 Typical detection efficiencies comparing extended range with a normal coaxial
germanium detector 15-90
Figure 15.12 Beta-gamma coincidence efficiency curve for 131I 15-93
Figure 16.1 Gamma-ray spectrum 16-9
Figure 16.2 Gamma-ray analysis flow chart and input parameters 16-11
Figure 16.3 Low-energy tailing 16-16
Figure 16.4 Photopeak baseline continuum 16-17
Figure 16.5 Photopeak baseline continuum-step function 16-18
Figure 16.6 Alpha spectrum (238U, 235U, 234U, 239/240pu, 241Am) 16-23
Volume III
Figure 18.1 Problems leading to loss of analytical control 18-4
Figure 18.2 Control chart for daily counting of a standard reference source, with limits corrected
for decay 18-7
Figure 18.3 Three general categories of blank changes 18-12
Figure 18.4 Failed performance indicator: replicates 18-15
Figure 18.5 Failed performance indicator: chemical yield 18-23
Figure 19.1 Addition of uncertainty components 19-25
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Figure 19.2 Expected fraction of atoms remaining at time t 19-35
Figure 19.3 A symmetric distribution 19-64
Figure 19.4 An asymmetric distribution 19-65
Figure 19.5 A normal distribution 19-67
Figure 19.6 A log-normal distribution 19-68
Figure 19.7 Chi-squared distributions 19-69
Figure 19.8 The ^-distribution with 3 degrees of freedom 19-70
Figure 19.9 A rectangular distribution 19-72
Figure 19.10 A trapezoidal distribution 19-72
Figure 19.11 An exponential distribution 19-73
Figure 19.12a Poisson distribution vs. normal distribution, ft = 3 19-75
Figure 19.12b Poisson distribution vs. normal distribution, // = 100 19-76
Figure 19.13 Nonlinear balance response curve 19-98
Figure 20.1 The critical net signal, Sc, and minimum detectable net signal, SD 20-6
Figure 20.2 Type I error rates for Table 20.1 20-41
Figure 20.3 Type I error rate for the Poisson-normal approximation (tB = ^s) 20-42
Figure 20.4 Type I error rates for Formula A 20-44
Figure 20.5 Type I error rates for Formula B 20-45
Figure 20.6 Type I error rates for Formula C 20-46
Figure 20.7 Type I error rates for the Stapleton approximation 20-48
Figure 20.8 Type I error rates for the nonrandomized exact test 20-49
Figure B.I Seven steps of the DQO process B-2
Figure B.2(a) Decision performance goal diagram null hypothesis: the parameter exceeds the
action level B-l 1
Figure B.2(b) Decision performance goal diagram null hypothesis: the parameter is less than the
action level B-l 1
Figure B.3 Plot is made showing the range of the parameter of interest on the x-axis B-15
Figure B.4 A line showing the action level, the type of decision error possible at a given value of
the true concentration, and ay-axis showing the acceptable limits on making a decision error
have been added to Figure B.3 B-16
Figure B.5 The gray region is a specified range of values of the true concentration where the
consequences of a decision error are considered to be relatively minor B-17
Figure B.6 Three possible ways of setting the gray region B-17
Figure B.7 Example decision performance goal diagram B-19
Figure B.8 A power curve constructed from the decision performance goal diagram in Figure
B.7 B-20
Figure B.9 Example power curve showing the key parameters used to determine the appropriate
number of samples to take in the survey unit B-21
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Figure B. 10 How proximity to the action level determines what is an acceptable level of
uncertainty B-24
Figure B 1.1 The action level is 1.0 B-26
Figure B 1.2 The true mean concentration is 1.0 B-27
Figure B 1.3 The true mean concentration is 0.9 B-28
Figure B 1.4 If 0.95 is measured, is the true mean concentration 1.0 (right) or 0.9 (left)? . . . B-28
Figure B 1.5 When the true mean concentration is 1.0, and the standard uncertainty of the
distribution of measured concentrations is 0.1, a measured concentration of 0.84 or less will
be observed only about 5 percent of the time B-30
Figure Bl.6 When the true mean concentration is 0.84, and the standard uncertainty of the
distribution of measured concentrations is 0.1, a measured concentration of 0.84 or less will
be observed only about half the time B-31
Figure Bl.7 When the true mean concentration is 0.68 and the standard uncertainty of the
distribution of measured concentrations is 0.1, a measured concentration over 0.84 will be
observed only about 5 percent of the time B-31
Figure Bl.8 The true mean concentration is 0.9 (left) and 1.22 (right) B-32
Figure Bl.9 The true mean concentration is 0.84 (left) and 1.0 (right) B-34
Figure B2.1 Region of interest for the concentration around the action level of 1.0 B-38
Figure B2.2 (a) The distribution of blank (background) readings, (b) The true concentration is
0.0. The standard deviation of the distribution of measured concentrations is 0.2 B-38
Figure B2.3 The true concentration is 0.0, and the standard deviation of the distribution of
measured concentrations is 0.2 B-39
Figure B2.4 The true concentration is 0.2 and the standard deviation of the distribution of
measured concentrations is 0.2 B-39
Figure B2.5 The true value of the concentration is 0.66 and the standard deviation of the
distribution of measured concentrations is 0.2 B-41
Figure B2.6 The true value of the measured concentration is 0.0 and the standard deviation of
the measured concentrations is 0.2 B-41
Figure B2.7 The standard deviation of the normally distributed measured concentrations
is 0.2 B-42
Figure C.I Required analytical standard deviation (%eq) C-10
Figure E. 1 General sequence initiating and later conducting work with a contract laboratory E-4
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List of Tables
Table 2.1 — Summary of the directed planning process and radioanalytical specialists
participation 2-9
Table 3.1 Common matrix-specific analytical planning issues 3-20
Table 4.1 Elements of project plan documents 4-7
Table 4.2 Crosswalk between project plan document elements and directed planning
process 4-10
Table 6.1 Tiered project method validation approach 6-26
Table 7.1 Cross reference of information available for method evaluation 7-3
Table 9.1 Summary of the DQA process 9-6
Volume II
Table 10.1 Summary of sample preservation techniques 10-25
Table 11.1 Typical topics addressed in standard operating procedures related to sample receipt,
inspection, and tracking 11-3
Table 12.1 Examples of volatile radionuclides 12-4
Table 12.2 Properties of sample container materials 12-5
Table 12.3 Examples of dry-ashing temperatures (platinum container) 12-23
Table 12.4 Preliminary ashing temperature for food samples 12-29
Table 13.1 Common fusion fluxes 13-7
Table 13.2 Examples of acids used for wet ashing 13-13
Table 13.3 Standard reduction potentials of selected half-reactions at 25 °C 13-14
Table 14.1 Oxidation states of elements 14-8
Table 14.2 Oxidation states of selected elements 14-10
Table 14.3 Redox reagents for radionuclides 14-13
Table 14.4 Common ligands 14-19
Table 14.5 Radioanalytical methods employing solvent extraction 14-32
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Table 14.6 Radioanalytical methods employing extraction chromatography 14-33
Table 14.7 Elements separable by volatilization as certain species 14-37
Table 14.8 Typical functional groups of ion-exchange resins 14-49
Table 14.9 Common ion-exchange resins 14-50
Table 14.10 General solubility behavior of some cations of interest 14-58
Table 14.11 Summary of methods for utilizing precipitation from homogeneous solution . 14-68
Table 14.12 Influence of precipitation conditions on the purity of precipitates 14-69
Table 14.13 Common coprecipitating agents for radionuclides 14-76
Table 14.14 Coprecipitation behavior of plutonium and neptunium 14-78
Table 14.15 Atoms and mass of select radionuclides equivalent to 500 dpm 14-83
Table 14.16 Masking agents for ions of various metals 14-106
Table 14.17 Masking agents for anions and neutral molecules 14-108
Table 14.18 Common radiochemical oxidizing and reducing agents for iodine 14-129
Table 14.19 Redox agents in plutonium chemistry 14-142
Table 14A. 1 Relationships of radioactive equilibria 14-228
Table 15.1 Radionuclides prepared by coprecipitation or precipitation 15-12
Table 15.2 Nuclides for alpha calibration 15-20
Table 15.3 Typical gas operational parameters for gas proportional alpha counting 15-22
Table 15.4 Nuclides for beta calibration 15-48
Table 15.5 Typical operational parameters for gas proportional beta counting 15-50
Table 15.6 Typical FWHM values as a function of energy 15-79
Table 15.7 Typical percent gamma-ray efficiencies for a 55 percent HPGe detector with various
counting geometries 15-83
Table 15.8 AMS detection limits for selected radionuclides 15-100
Table 16.1 Units for data reporting 16-39
Table 16.2 Example elements of a radiochemistry data package 16-40
Table 17.1 Examples of laboratory-generated wastes 17-2
Volume III
Table 18. la Certified Massic activities for natural radionuclides with a normal distribution of
measurement results 18-20
Table 18. Ib Certified Massic activities for anthropogenic radionuclides with a Weibull
distribution of measurement results 18-20
Table 18. Ic Uncertified Massic activities 18-20
Table 18.2 Instrument background evaluation 18-26
Table 18.3 Root-cause analysis of performance check results for spectrometry systems . . . 18-35
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Table 18.4 Some causes of excursions in liquid scintillation analysis 18-40
Table 18.5 Example gas proportional instrument calibration, background frequency, and
performance criteria 18-44
Table 18.6 Example gamma spectrometry instrument calibration, background frequency, and
performance criteria 18-48
Table 18.7 Example alpha spectrometry instrument calibration, background frequency, and
performance criteria 18-50
Table 18.8 Example liquid scintillation counting systems calibration, background frequency, and
performance criteria 18-53
Table 18A.I Bias-correction factor for the experimental standard deviation 18-70
Table 19.1 Differentiation rules 19-21
Table 19.2 Applications of the first-order uncertainty propagation formula 19-21
Table 19.3 95 % confidence interval for a Poisson mean 19-75
Table 19.4 Input estimates and standard uncertainties 19-81
Table 19.5 Coefficients of cubical expansion 19-107
Table 19.6 Density of air-free water 19-109
Table 20.1 Critical gross count (well-known blank) 20-40
Table 20.2 Bias factor for the experimental standard deviation 20-55
Table 20.3 Estimated and true values of SD (tB = ^s) 20-62
Table B.I Possible decision errors B-12
Table B.2 Example of possible decision errors with null hypothesis that the average
concentration in a survey unit is above the action level B-15
Table B.3 Example decision error limits table B-19
Table D.I QAPP groups and elements D-2
Table D.2 Comparison of project plan contents D-3
Table D.3 Content of the three elements that constitute the project description D-8
Table E.I Examples of procurement options to obtain materials or services E-6
Table E.2 SOW checklists for the agency and proposer E-12
Table E.3 Laboratory technical supervisory personnel listed by position title and examples for
suggested minimum qualifications E-14
Table E.4 Laboratory technical personnel listed by position title and examples for suggested
minimum qualifications and examples of optional staff members E-14
Table E.5 Laboratory technical personnel listed by position title and examples for suggested
minimum qualifications E-15
Table E.6 Example of a proposal evaluation plan E-23
JULY 2004 XLVII MARLAP
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Contents
age
Table G.I Quantiles of the standard normal distribution G-l
Table G.2 Quantiles of Student's t distribution G-3
Table G.3 Quantiles of chi-square G-5
Table G.4 Critical values for the nonrandomized exact test G-7
Table G.5 Summary of probability distributions G-l 1
MARLAP XLVIII JULY 2004
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ACRONYMS AND ABBREVIATIONS
AC alternating current
ADC analog to digital convenor
AEA Atomic Energy Act
AL action level
AMS accelerator mass spectrometry
ANSI American National Standards Institute
AOAC Association of Official Analytical Chemists
APHA American Public Health Association
APS analytical protocol specification
ARAR applicable or relevant and appropriate requirement (CERCLA/Superfund)
ASL analytical support laboratory
ASQC American Society for Quality Control
ASTM American Society for Testing and Materials
AID alpha track detector
BGO bismuth germanate [detector]
BNL Brookhaven National Laboratory (DOE)
BOA basic ordering agreement
CAA Clean Air Act
CC charcoal canisters
CEDE committed effective dose equivalent
CERCLA .... Comprehensive Environmental Response, Compensation, and Liability Act of
1980 ("Superfund")
c.f carrier free [tracer]
cfm cubic feet per minute
CFR Code of Federal Regulations
CL central line (of a control chart)
CMPO [octyl(phenyl)]-N,N-diisobutylcarbonylmethylphosphine oxide
CMST Characterization, Monitoring, and Sensor Technology Program (DOE)
CO contracting officer
COC chain of custody
COR contracting officer's representative
cpm counts per minute
cps counts per second
CRM (1) continuous radon monitor; (2) certified reference material
CSU combined standard uncertainty
CV coefficient of variation
CWA Clean Water Act
CWLM continuous working level monitor
JULY 2004
XLIX
MARLAP
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Acronyms and Abbreviations
D
DAAP . . .
DC
DCGL. . .
DHS ....
DIN
DL
DoD ....
DOE ....
DOELAP
DOT ....
OOP ....
dpm ....
DPPP . . .
DQA ....
DQI
DQO ....
DTPA . . .
DVB ....
EDO ....
EDTA . . .
EGTA . . .
EMEDD .
EPA ....
ERPRIMS
ESC ....
eV
FAR ....
FBO ....
FDA ....
FEP
fg
FOM ....
FWHM . .
FWTM . .
day[s]
homogeneous distribution coefficient
diamylamylphosphonate
direct current
derived concentration guideline level
U.S. Department of Homeland Security
di-isopropylnaphthalene
discrimination limit
U.S. Department of Defense
U.S. Department of Energy
DOE Laboratory Accreditation Program
U.S. Department of Transportation
dispersed oil particulate
disintegrations per minute
dipentylpentylphosphonate
data quality assessment
data quality indicator
data quality objective
diethylene triamine pentaacetic acid
divinylbenzene
emission probability per decay event
maximum beta-particle energy
electronic data deliverable
ethylene diamine tetraacetic acid
ethyleneglycol bis(2-aminoethylether)-tetraacetate
environmental management electronic data deliverable (DOE)
U.S. Environmental Protection Agency
Environmental Resources Program Management System (U.S. Air Force)
expedited site characterization; expedited site conversion
electron volts
Federal Acquisition Regulations, CFR Title 48
Federal Business Opportunities [formerly Commerce Business Daily]
U.S. Food and Drug Administration
full energy peak
femtogram
figure of merit
full width of a peak at half maximum
full width of a peak at tenth maximum
MARLAP
JULY 2004
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Acronyms and Abbreviations
GC gas chromatography
GLPC gas-liquid phase chromatography
GM Geiger-Mueller [detector]
GP gas proportional [counter]
GUM Guide to the Expression of Uncertainty in Measurement (ISO)
Gy gray[s]
h hour[s]
H0 null hypothesis
HA, Hj alternative hypothesis
HDBP dibutylphosphoric acid
HDEHP bis(2-ethylhexyl) phosphoric acid
HDPE high-density polyethylene
HLW high-level [radioactive] waste
HPGe high-purity germanium
HPLC high-pressure liquid chromatography; high-performance liquid chromatography
HTRW hazardous, toxic, and radioactive waste
IAEA International Atomic Energy Agency
ICRU International Commission on Radiation Units and Measurements
ICP-MS inductively coupled plasma-mass spectroscopy
IPPD integrated product and process development
ISO International Organization for Standardization
IUPAC International Union of Pure and Applied Chemistry
k coverage factor
keV kilo electron volts
KPA kinetic phosphorimeter analysis
LAN local area network
LANL Los Alamos National Laboratory (DOE)
LBGR lower bound of the gray region
LCL lower control limit
LCS laboratory control samples
LDPE low-density polyethylene
LEGe low-energy germanium
LEVIS laboratory information management system
LLD lower limit of detection
LLNL Lawrence Livermore National Laboratory (DOE)
LLRW low-level radioactive waste
LLRWPA .... Low Level Radioactive Waste Policy Act
JULY 2004
LI
MARLAP
-------
Acronyms and Abbreviations
LOMI low oxidation-state transition-metal ion
LPC liquid-partition chromatography; liquid-phase chromatography
LS liquid scintillation
LSC liquid scintillation counter
LWL lower warning limit
MAPEP Mixed Analyte Performance Evaluation Program (DOE)
MARS SIM . . . Multi-Agency Radiation Survey and Site Investigation Manual
MCA multichannel analyzer
MCL maximum contaminant limit
MDA minimum detectable amount; minimum detectable activity
MDC minimum detectable concentration
MDL method detection limit
MeV mega electron volts
MIBK methyl isobutyl ketone
min minute[s]
MPa megapascals
MQC minimum quantifiable concentration
MQO measurement quality objective
MS matrix spike; mass spectrometer
MSD matrix spike duplicate
MVRM method validation reference material
NAA
Nal(Tl)
NCP
NCRP
NELAC ....
NESHAP . . .
MM
MST
NPL
NRC
NRIP
NTA (NTTA)
NTU
NVLAP ....
OA
OFHC
neutron activation analysis
thallium-activated sodium iodide [detector]
National Oil and Hazardous Substances Pollution Contingency Plan
National Council on Radiation Protection and Measurement
National Environmental Laboratory Accreditation Conference
National Emission Standards for Hazardous Air Pollutants (EPA)
nuclear instrumentation module
National Institute of Standards and Technology
National Physics Laboratory (United Kingdom); National Priorities List (United
States)
U.S. Nuclear Regulatory Commission
NIST Radiochemistry Intercomparison Program
nitrilotriacetate
nephelometric turbidity units
National Voluntary Laboratory Accreditation Program (NIST)
observational approach
oxygen-free high-conductivity
MARLAP
LII
JULY 2004
-------
Acronyms and Abbreviations
OFPP
Pa
PARCC
PBBO
PCB
pCi
pdf
PE
PERALS
PFA
PIC
PIPS
PM
PMT
PT
PTB
PTFE
PUREX
PVC
QA
QAP
QAPP
QC
rad
RCRA
REE
REGe
rem
RFP
RFQ
RI/FS
RMDC
ROI
RPD
RPM
RSD
RSO
Office of Federal Procurement Policy
required relative method uncertainty
pascals
precision, accuracy, representativeness, completeness, and comparability
2-(4'-biphenylyl) 6-phenylbenzoxazole
polychlorinated biphenyl
picocurie
probability density function
performance evaluation
Photon Electron Rejecting Alpha Li quid Scintillation®
perfluoroalcoholoxil™
pressurized ionization chamber
planar implanted passivated silicon [detector]
project manager
photomultiplier tube
performance testing
Physikalisch-Technische bundesanstalt (Germany)
polytetrafluoroethylene
plutonium uranium reduction extraction
polyvinyl chloride
quality assurance
Quality Assessment Program (DOE)
quality assurance project plan
quality control
radiation absorbed dose
Resource Conservation and Recovery Act
rare earth elements
reverse-electrode germanium
roentgen equivalent: man
request for proposals
request for quotations
remedial investigation/feasibility study
required minimum detectable concentration
region of interest
relative percent difference
remedial project manager
relative standard deviation
radiation safety officer
JULY 2004
LIII
MARLAP
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Acronyms and Abbreviations
s second[s]
SA spike activity
Sc critical value
SAFER Streamlined Approach for Environmental Restoration Program (DOE)
SAM site assessment manager
SAP sampling and analysis plan
SEDD staged electronic data deliverable
SI international system of units
SMO sample management office[r]
SOP standard operating procedure
SOW statement of work
SQC statistical quality control
SPE solid-phase extraction
SR unspiked sample result
SRM standard reference material
SSB silicon surface barrier [alpha detector]
SSR spiked sample result
Sv sievert[s]
t,/2 half-life
TAT turnaround time
TBP tributylphosphate
TC to contain
TCLP toxicity characteristic leaching procedure
TD to deliver
TEC technical evaluation committee
TEDE total effective dose equivalent
TEC technical evaluation committee (USGS)
TES technical evaluation sheet (USGS)
TFM tetrafluorometoxil™
TIMS thermal ionization mass spectrometry
TIOA triisooctylamine
TLD thermoluminescent dosimeter
TnOA tri-n-octylamine
TOPO trioctylphosphinic oxide
TPO technical project officer
TPP technical project planning
TPU total propagated uncertainty
TQM Total Quality Management
TRUEX trans-uranium extraction
TSCA Toxic Substances Control Act
MARLAP
LIV
JULY 2004
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Acronyms and Abbreviations
TSDF treatment, storage, or disposal facility
tSIE transfomed spectral index of the external standard
TTA thenoyltrifluoroacetone
U expanded uncertainty
WMK required absolute method uncertainty
uc(y) combined standard uncertainty
UBGR upper bound of the gray region
UCL upper control limit
USAGE United States Army Corps of Engineers
USGS United States Geological Survey
UV ultraviolet
UWL upper warning limit
V volt[s]
WCP waste certification plan
XML extensible mark-up language
XtGe® extended-range germanium
y year[s]
Y response variable
ZnS(Ag) silver-activated zinc sulfide [detector]
JULY 2004 LV MARLAP
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UNIT CONVERSION FACTORS
To Convert
Years (y)
Disintegrations
per second (dps)
Bq
Bq/kg
Bq/m3
Bq/m3
Microcuries per
milliliter
(|iCi/mL)
Disintegrations
per minute (dpm)
Gallons (gal)
Gray (Gy)
Roentgen
Equivalent Man
(rem)
To
Seconds (s)
Minutes (min)
Hours (h)
Becquerels (Bq)
Picocuries (pCi)
pCi/g
pCi/L
Bq/L
pCi/L
|iCi
pCi
Liters (L)
rad
Sievert (Sv)
Multiply by
3.16x 107
5.26 x 105
8.77 x 103
1.0
27.03
2.7 x io-2
2.7 x io-2
103
109
4.5 x io-7
4.5 x KT1
3.78
100
io-2
To Convert
s
min
h
Bq
pCi
pCi/g
pCi/L
Bq/L
pCi/L
pCi
Liters
rad
Sv ' '
To
y
dps
Bq
Bq/kg
Bq/m3
Bq/m3
jiCi/mL
dpm
Gallons
Gy ' ' •;_
rem
Multiply by
3,17x:iO~8
1,90 x lQ-« .
1.14 x 1Q~4
1.0,
3.7. xlQ-2 •
37 '
37 . ' •
io~3 - .
iQ-9
2:22 :.".
0.265
io-2
IO2 ,
JULY 2004
LVII
MARLAP
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