NTIS PB2004-105421
         Multi-Agency Radiological
Laboratory Analytical Protocols Manual
                 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

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.

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
JULY 2004                                  III                                   MARLAP


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 and 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 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-

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 (

JULY 2004                                  V                                   MARLAP


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

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

EPA's Science Advisory Board (SAB) Radiation Advisory Committee's Review Subcommittee
that conducted an extensive peer review of the MARLAP includes:

   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



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

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
 Define the Action Level	2-12
 Identify Inputs to the Decision	2-13
 Define the Decision Boundaries  	2-13
 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
 Analytical Protocol Specifications	2-16
 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
 Data Verification  	2-21
 Data Validation 	2-22
 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

MARLAP                                    XII                                  JULY 2004



       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
 Develop MQOs for Select Method Performance Characteristics  	3-9
 The Role of MQOs in the Protocol Selection and Evaluation Process  . . . 3-14
 The Role of MQOs in the Project's Data Evaluation Process	3-14
       3.3.8  Determine Any Limitations on Analytical Options	3-15
 Gamma Spectrometry  	3-16
 Gross Alpha and Beta Analyses	3-16
 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
 Removal of Unwanted Materials	3-21
 Homogenization and Subsampling  	3-21
 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

JULY 2004                                 XIII                                  MARLAP

       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
 Data Verification 	4-15
 Data Validation  	4-15
 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

MARLAP                                  XIV                                 JULY 2004



       5.4.1 Sample Management	5-7
       5.4.2   Licenses, Permits and Environmental Regulations 	5-8
 Licenses	5-8
 Environmental and Transportation Regulations 	5-8
       5.4.3   Data Reporting and Communications  	5-9
 Data Deliverables	5-9
 Software Verification and Control	5-10
 Problem Notification and Communication  	5-10
 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
 Scoring and Evaluation Scheme  	5-12
 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
 Matrices	6-11
 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
 Method Uncertainty  	6-17
 Quantification Capability	6-18
 Detection Capability  	6-19
 Applicable Analyte Concentration Range	6-20
 Method Specificity	6-20

JULY 2004                                  XV                                    MARLAP

 Method Ruggedness  	6-21
 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
 Existing Methods Requiring No Additional Validation  	6-28
 Routine Methods Having No Project Method Validation	6-28
 Use of a Validated Method for Similar Matrices	6-28
 New Application of a Validated Method	6-29
 Newly Developed or Adapted Methods	6-30
       6.6.4   Testing for Bias 	6-31
 Absolute Bias	6-31
 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
 Method Validation  Documentation	7-3
 Internal Quality Control or External PE Program Reports 	7-4
 Method Experience, Previous Projects, and Clients  	7-5
 Internal and External Quality Assurance Assessments 	7-5
       7.2.2   Performance Requirements of the SOW—Analytical Protocol Specifications . 7-5
 Matrix and Analyte Identification 	7-6
 Radiological Holding and Turnaround Times	7-7
 Unique Processing  Specifications 	7-8
 Measurement Quality Objectives	7-8
 Bias Considerations	7-13

MARLAP                                  XVI                                 JULY 2004



   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
 Review of Internal QC Results  	7-18
 External PE Program Results	7-19
 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
 MQO Compliance 	7-22
 Other Parameters 	7-27
       7.4.2   Operational Aspects	7-28
 Desk Audits	7-28
 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
  Project Objectives	8-3
  Documenting Project Activities  	8-4
  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
 Sample Descriptors   	8-14
 Aliquant Size	8-15

JULY 2004                                 XVII                                  MARLAP

 Dates of Sample Collection, Preparation, and Analysis  	8-16
 Preservation	8-16
 Tracking	8-17
 Traceability  	8-17
 QC Types and Linkages	8-18
 Chemical Separation (Yield)	8-18
 Self-Absorption 	8-19
 Efficiency, Calibration Curves, and Instrument Background  	8-19
 Spectrometry Resolution  	8-20
 Dilution and Correction Factors	8-20
 Counts and Count Time (Duration)	8-21
 Result of Measurement, Uncertainty, Minimum Detectable Concentration,
              and Units  	8-21
       8.5.2   Quality Control Samples 	8-22
 Method Blank	8-23
 Laboratory Control Samples  	8-23
 Laboratory Replicates   	8-24
 Matrix Spikes and Matrix Spike Duplicates  	8-24
       8.5.3   Tests of Detection and Unusual Uncertainty	8-25
 Detection   	8-25
 Detection Capability 	8-26
 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
 TheProjectDQOsandMQOs	9-7
 The DQA Plan	9-8
 Summary of the DQA Review	9-8
       9.6.2   Sample Representativeness  	9-9
 Review of the Sampling Plan	9-9

MARLAP                                  XVIII                                 JULY 2004



 Sampling Plan Implementation 	9-12
 Data Considerations	9-13
       9.6.3  Data Accuracy 	9-14
 Review of the Analytical Plan	9-18
  Analytical Plan Implementation	9-19
       9.6.4  Decisions and Tolerable Error Rates	9-21
 Statistical Evaluation of Data  	9-21
  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
   Container Material	10-4
  Container Opening and Closure	10-5
   Sealing Containers	10-5
  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
  Physical Hazards 	10-13
  Biohazards	10-15
   Part B: Matrix-Specific Issues That Impact Field Sample Collection, Processing, and
       Preservation	10-16
   10.3   Liquid Samples  	10-17

JULY 2004                                 XIX                                   MARLAP

       10.3.1 Liquid Sampling Methods	10-18
       10.3.2 Liquid Sample Preparation: Filtration	10-18
   Example of Guidance for Ground-Water Sample Filtration  	10-19
   Filters	10-21
       10.3.3 Field Preservation of Liquid Samples 	10-22
   Sample Acidification	10-22
   Non-Acid Preservation Techniques	10-23
       10.3.4 Liquid Samples: Special Cases  	10-25
   Radon-222 in Water	10-25
   Milk	10-26
       10.3.5 Nonaqueous Liquids and Mixtures  	10-26
    10.4   Solids  	10-28
       10.4.1 Soils	10-29
   Soil Sample Preparation  	10-29
   Sample Ashing  	10-30
       10.4.2 Sediments  	10-30
       10.4.3 Other Solids  	10-31
   Structural  Materials	10-31
   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
   Radioiodines  	10-36
   Gases  	10-37
   Tritium Air Sampling	10-38
   Radon Sampling in Air  	10-39
    10.6   Wipe Sampling for Assessing Surface Contamination 	10-41
       10.6.1 Sample Collection Methods 	10-42
   Dry Wipes  	10-42
   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

MARLAP                                   XX                                 JULY 2004



       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
   Losses as Dust or Particulates 	12-2
   Losses Through Volatilization	12-3
   Losses Due to Reactions Between Sample and Container	12-5
       12.2.2  Contamination from  Sources in the Laboratory	12-6
   Airborne Contamination  	12-7
   Contamination of Reagents 	12-7
   Contamination of Glassware and Equipment  	12-8
   Contamination of Facilities 	12-8
       12.2.3  Cleaning of Labware, Glassware, and Equipment	12-8
   Labware and  Glassware	12-8
   Equipment 	12-10
    12.3   Solid Samples  	12-12
       12.3.1  General Procedures  	12-12
   Exclusion of Material	12-14
   Principles of Heating Techniques for Sample Pretreatment  	12-14
   Obtaining a Constant Weight	12-23
   Subsampling	12-24

JULY 2004                                 XXI                                  MARLAP

       12.3.2  Soil/Sediment Samples  	12-27
   Soils	12-28
   Sediments	12-28
       12.3.3  Biota Samples  	12-28
   Food	12-29
   Vegetation  	12-29
   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
   Liquid-Liquid Mixtures	12-35
   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

MARLAP                                 XXII                                 JULY 2004



       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
  Extraction of Laboratory Samples and Ores	14-23
  Separation by Solvent Extraction and Ion-Exchange Chromatography  14-23
  Formation and Dissolution of Precipitates  	14-24
  Stabilization of Ions in Solution  	14-24
  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

JULY 2004                                 XXIII                                  MARLAP

       14.4.5  Solid-Phase Extraction	14-32
   Extraction Chromatography Columns	14-33
   Extraction Membranes	14-34
       14.4.6  Advantages and Disadvantages of Solvent Extraction 	14-35
   Advantages of Liquid-Liquid Solvent Extraction  	14-35
   Disadvantages of Liquid-Liquid Solvent Extraction	14-35
   Advantages of Solid-Phase Extraction Media	14-35
   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
   Advantages	14-40
   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
   Advantages	14-43
 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
   Principles of Ion Exchange  	14-46
   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
   Advantages	14-56
   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

MARLAP                                  XXIV                                 JULY 2004



    Solubility and the Solubility Product Constant, Ksp	14-59
    Factors Affecting Precipitation  	14-64
    Optimum Precipitation Conditions 	14-69
       14.8.4 Coprecipitation	14-69
    Coprecipitation Processes  	14-70
    Water as an Impurity  	14-74
    Postprecipitation  	14-74
    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
    Advantages	14-82
    Disadvantages  	14-82
    14.9    Carriers and Tracers	14-82
       14.9.1 Introduction 	14-82
       14.9.2 Carriers	14-83
    Isotopic Carriers	14-83
    Nonisotopic Carriers  	14-84
    Common Carriers	14-85
    Holdback Carriers  	14-89
    Yield of Isotopic Carriers	14-89
       14.9.3 Tracers	14-90
    Characteristics of Tracers	14-92
    Coprecipitation	14-93
    Deposition on Nonmetallic Solids	14-93
    Radiocolloid Formation  	14-94
    Distribution (Partition) Behavior	14-95
    Vaporization	14-95
    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
   Americium	14-109

JULY 2004                                  XXV                                   MARLAP

  Carbon  	14-114
  Cesium	14-116
  Cobalt	14-119
  Iodine	14-125
  Neptunium	14-132
  Nickel	14-136
  Plutonium	14-139
  Radium	14-148
 Strontium	14-155
 Sulfur and Phosphorus	14-160
 Technetium  	14-163
 Thorium	14-169
 Tritium	14-175
 Uranium	14-180
 Zirconium	14-191
 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

MARLAP                                  XXVI                                 JULY 2004



       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
    Radioactive Gases 	15-16
    Air Filters	15-17
    Swipes  	15-18
    15.4   Alpha Detection Methods  	15-18
       15.4.1  Introduction  	15-18
       15.4.2  Gas Proportional Counting  	15-20
 Detector Requirements and Characteristics  	15-20
    Calibration and Test Source Preparation	15-25
    Detector Calibration  	15-25
    Troubleshooting	15-27
       15.4.3  Solid-State Detectors	15-29
    Detector Requirements and Characteristics	15-30
    Calibration- and Test-Source Preparation  	15-33
    Detector Calibration	15-33
    Troubleshooting	15-34
    Detector or Detector Chamber Contamination 	15-35
    Degraded Spectrum 	15-37
       15.4.4  Fluorescent Detectors	15-38
    Zinc Sulfide	15-38
    Calibration- and Test-Source Preparation  	15-40
    Detector Calibration	15-41
    Troubleshooting	15-41
       15.4.5  Photon Electron Rejecting Alpha Li quid Scintillation (PERALS®)  	15-42
    Detector Requirements and Characteristics	15-42
    Calibration- and Test-Source Preparation  	15-44
    Detector Calibration	15-45
    Quench	15-45
    Available Cocktails 	15-46

JULY 2004                                 XXVII                                  MARLAP

   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
    Detector Requirements and Characteristics	15-49
   Calibration- and Test-Source Preparation 	15-53
    Detector Calibration	15-54
   Troubleshooting	15-57
       15.5.3  Liquid Scintillation  	15-57
    Detector Requirements and Characteristics	15-58
   Calibration- and Test-Source Preparation 	15-61
    Detector Calibration	15-62
   Troubleshooting	15-68
    15.6   Gamma Detection Methods	15-68
       15.6.1  Sample Preparation Techniques	15-70
    Containers  	15-71
   Gases 	15-71
    Liquids	15-72
   Solids	15-72
       15.6.2  Sodium Iodide Detector	15-73
    Detector Requirements and Characteristics	15-73
   Operating Voltage  	15-76
    Shielding  	15-76
   Background  	15-76
    Detector Calibration	15-77
   Troubleshooting	15-77
       15.6.3  High Purity Germanium	15-78
    Detector Requirements and Characteristics	15-78
   Gamma Spectrometer Calibration	15-82
    Troubleshooting	15-84
       15.6.4  Extended Range Germanium Detectors  	15-88
    Detector Requirements and Characteristics	15-89
   Detector Calibration	15-89
    Troubleshooting	15-90
       15.6.5  Special Techniques for Radiation Detection	15-90
    Other Gamma Detection Systems 	15-90
   Coincidence Counting	15-91
    Anti-Coincidence Counting	15-93
    15.7   Specialized Analytical Techniques  	15-94
       15.7.1  Kinetic Phosphorescence Analysis by Laser (KPA) 	15-94

MARLAP                                 XXVIII                                 JULY 2004



       15.7.2  Mass Spectrometry	15-95
   Inductively Coupled Plasma-Mass Spectrometry  	15-96
   Thermal lonization Mass Spectrometry	15-99
   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
   Counting Duration	16-4
   Counting Geometry  	16-5
 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
 Peak Search or Identification	16-10
   Singlet/MultipletPeaks 	16-13
 Definition of Peak Centroid and Energy  	16-14
 Peak Width Determination	16-15
   Peak Area Determination	16-17
   Calibration Reference File	16-19
   Activity and Concentration 	16-20
   Summing Considerations	16-21
 Uncertainty Calculation	16-22
       16.3.2  Alpha Spectrometry	16-23
   Radiochemical Yield	16-27
   Uncertainty Calculation	16-28
       16.3.3  Liquid Scintillation Spectrometry 	16-29
 Overview of Liquid Scintillation Counting	16-29
   Liquid Scintillation Spectra	16-29
   Pulse Characteristics  	16-29
   Coincidence Circuitry  	16-30
   Quenching 	16-30
   Luminescence	16-31
   Test-Source Vials	16-31
   Data Reduction for Liquid Scintillation Counting	16-31
    16.4   Data Reduction on Non-Spectrometry Systems	16-32

JULY 2004                                 XXIX                                  MARLAP

    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
 Container Requirements	17-10
 Labeling Requirements  	17-10
 Time Constraints 	17-11
 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
MARLAP                                  XXX                                 JULY 2004

                                       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
   Energy Calibrations	18-29
   Peak Resolution and Tailing 	18-32
       18.5.4  Gas Proportional Systems  	18-36
   Voltage Plateaus	18-36
   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
   Gas Proportional Counting Systems  	18-42
   Gamma-Ray Detectors and Spectrometry Systems	18-45
   Alpha Detector and Spectrometry Systems	18-49
   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

JULY 2004                                 XXXI                                  MARLAP

       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
MARLAP                                 XXXII                                JULY 2004



 Type A Evaluations	19-13
 Type B Evaluations	19-16
       19.4.3 Combined Standard Uncertainty 	19-20
 Uncertainty Propagation Formula	19-20
 Components of Uncertainty  	19-24
 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
 Uncertainty Propagation for Nonlinear Models  	19-29
 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
 Binomial Model 	19-35
 Poisson Approximation	19-36
       19.5.3 Count Time and Count Rate  	19-38
 Dead Time	19-39
 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

JULY 2004                                XXXIII                                 MARLAP

          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

MARLAP                               XXXIV                               JULY 2004

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
 Normally Distributed Signals	20-13
 Poisson Counting 	20-13
 Batch Blanks	20-17
       20.4.2 Calculation of the Minimum Detectable Concentration  	20-18
 The Minimum Detectable Net Instrument Signal	20-19
 Normally Distributed Signals	20-20
 Poisson Counting 	20-24
 More Conservative Approaches  	20-28
 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
JULY 2004                               XXXV                                MARLAP



                                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

MARLAP                                XXXVI                                JULY 2004



       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

JULY 2004                               XXXVII                                 MARLAP

   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

MARLAP                               XXXVIII                               JULY 2004



       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
JULY 2004                               XXXIX                                 MARLAP



                               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
MARLAP                                  XL                                 JULY 2004



                                  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

JULY 2004                                  XLI                                   MARLAP

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

MARLAP                                  XLII                                 JULY 2004



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

JULY 2004                                 XLIII                                  MARLAP

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
MARLAP                                   XLIV                                  JULY 2004



                                  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

JULY 2004                                 XLV                                  MARLAP

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

MARLAP                                  XLVI                                 JULY 2004



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

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

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

Acronyms and Abbreviations
DAAP . . .
DCGL. . .
DHS ....
DoD ....
DOE ....
DOT ....
OOP ....
dpm  ....
DPPP  . . .
DQA ....
DQO ....
DTPA . . .
DVB ....
EDO ....
EDTA . . .
EGTA . . .
EPA  ....
ESC  ....

FAR  ....
FBO  ....
FDA ....
FOM ....
FWHM . .
FWTM . .
homogeneous distribution coefficient
direct current
derived concentration guideline level
U.S. Department of Homeland Security
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
data quality assessment
data quality indicator
data quality objective
diethylene triamine pentaacetic acid

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
figure of merit
full width  of a peak at half maximum
full width  of a peak at tenth maximum
                                                              JULY 2004

                                                           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

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
NELAC  ....
NESHAP . . .

NVLAP  ....

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
U.S. Nuclear Regulatory Commission
NIST Radiochemistry Intercomparison Program
nephelometric turbidity units
National Voluntary Laboratory Accreditation Program (NIST)

observational approach
oxygen-free high-conductivity
JULY 2004

                                                             Acronyms and Abbreviations


               Office of Federal Procurement Policy

               required relative method uncertainty
               precision, accuracy, representativeness, completeness, and comparability
               2-(4'-biphenylyl) 6-phenylbenzoxazole
               polychlorinated biphenyl
               probability density function
               performance evaluation
               Photon Electron Rejecting Alpha Li quid Scintillation®
               pressurized ionization chamber
               planar implanted passivated silicon [detector]
               project manager
               photomultiplier tube
               performance testing
               Physikalisch-Technische bundesanstalt (Germany)
               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

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
JULY 2004

                                                             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


To Convert
Years (y)
per second (dps)
Microcuries per
per minute (dpm)
Gallons (gal)
Gray (Gy)
Equivalent Man
Seconds (s)
Minutes (min)
Hours (h)
Becquerels (Bq)
Picocuries (pCi)
Liters (L)
Sievert (Sv)
Multiply by
3.16x 107
5.26 x 105
8.77 x 103
2.7 x io-2
2.7 x io-2
4.5 x io-7
4.5 x KT1
To Convert
Sv ' '
Gy ' ' •;_
Multiply by
1,90 x lQ-« .
1.14 x 1Q~4
3.7. xlQ-2 •
37 '
37 . ' •
io~3 - .
2:22 :.".
IO2 ,
JULY 2004