Multi Agency Radiological Laboratory Analytical Protocols Manual (MARLAP) Analysis

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IMPLEMENTATION
PLANNING
ASSESSMENT
MARLAP
Multi-Agency Radiological
Laboratory Analytical Protocols Manual
Volume II: Chapters 10 – 17 and Appendix F
NUREG-1576
EPA 402-B-04-001B
NTIS PB2004-105421
July 2004
Disclaimer
References within this manual to any specific commercial product, process, or service by trade
name, trademark, manufacturer, or otherwise does not necessarily imply its endorsement or
recommendation by the United States Government. Neither the United States Government nor
any agency or branch thereof, nor any of their employees, makes any warranty, expressed or
implied, nor assumes any legal liability of responsibility for any third party’s use, or the results
of such use, of any information, apparatus, product, or process disclosed in this manual, nor
represents that its use by such third party would not infringe on privately owned rights.
NUREG-1576
EPA 402-B-04-001B
NTIS PB2004-105421
Multi-Agency Radiological
Laboratory Analytical Protocols Manual
(MARLAP)
Part II: Chapters 10 – 17
Appendix F
(Volume II)
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
III
JULY 2004 MARLAP
FOREWORD
MARLAP is organized into two parts. Part I, consisting of Chapters 1 through 9, is intended
primarily for project planners and managers. Part I introduces the directed planning process
central to MARLAP and provides guidance on project planning with emphasis on radioanalytical
planning issues and radioanalytical data requirements. Part II, 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.,
“B1”). Thus, “Section B.1.1” refers to section 1.1 of appendix B, while “Section B1.1” refers to
section 1 of attachment 1 to appendix B. Cross-references within the text are explicit in order to
avoid confusion.
Because of its length, the printed version of MARLAP is bound in three volumes. Volume I
(Chapters 1 through 9 and Appendices A through E) contains Part I. Because of its length, Part II
is split between Volumes II and III. Volume II (Chapters 10 through 17 and Appendix F) covers
most of the activities performed at radioanalytical laboratories, from field and sampling issues
that affect laboratory measurements through waste management. Volume III (Chapters 18
through 20 and Appendix G) covers laboratory quality control, measurement uncertainty and
detection and quantification capability. Each volume includes a table of contents, list of
acronyms and abbreviations, and a complete glossary of terms.
MARLAP and its periodic revisions are available online at www.epa.gov/radiation/marlap and
www.nrc.gov/reading-rm/doc-collections/nuregs/staff/sr1576/. The online version is updated
periodically and may differ from the last printed version. Although references to material found
on a web site bear the date the material was accessed, the material available on the date cited may
subsequently be removed from the site. Printed and CD-ROM versions of MARLAP are
available through the National Technical Information Service (NTIS). NTIS may be accessed
online at www.ntis.gov. The NTIS Sales Desk can be reached between 8:30 a.m. and 6:00 p.m.
Eastern Time, Monday through Friday at 1-800-553-6847; TDD (hearing impaired only) at 703-
487-4639 between 8:30 a.m. and 5:00 p.m Eastern Time, Monday through Friday; or fax at 703-
605-6900.
MARLAP is a living document, and future editions are already under consideration. Users are
urged to provide feedback on how MARLAP can be improved. While suggestions may not
always be acknowledged or adopted, commentors may be assured that they will be considered
carefully. Comments may be submitted electronically through a link on EPA’s MARLAP web
site (www.epa.gov/radiation/marlap).
V
JULY 2004 MARLAP
CONTENTS (VOLUME II)
Page
List of Figures .............................................................XVIII
List of Tables ............................................................... XX
Acronyms and Abbreviations..................................................XXIII
Unit Conversion Factors .....................................................XXXI
10 Field and Sampling Issues That Affect Laboratory Measurements ................. 10-1
Part A: Generic Issues .................................................... 10-1
10.1 Introduction ...................................................... 10-1
10.2 Field Sampling Plan: Non-Matrix-Specific Issues ......................... 10-3
10.2.1 Determination of Analytical Sample Size ............................ 10-3
10.2.2 Field Equipment and Supply Needs ................................. 10-3
10.2.3 Selection of Sample Containers .................................... 10-4
10.2.3.1 Container Material ........................................ 10-4
10.2.3.2 Container Opening and Closure .............................. 10-5
10.2.3.3 Sealing Containers ........................................ 10-5
10.2.3.4 Precleaned and Extra Containers ............................. 10-5
10.2.4 Container Label and Sample Identification Code ...................... 10-6
10.2.5 Field Data Documentation ........................................ 10-7
10.2.6 Field Tracking, Custody, and Shipment Forms ........................ 10-8
10.2.7 Chain of Custody ............................................... 10-9
10.2.8 Field Quality Control ........................................... 10-10
10.2.9 Decontamination of Field Equipment .............................. 10-10
10.2.10 Packing and Shipping ......................................... 10-11
10.2.11 Worker Health and Safety Plan .................................. 10-12
10.2.11.1 Physical Hazards ........................................ 10-13
10.2.11.2 Biohazards ............................................. 10-15
Part B: Matrix-Specific Issues That Impact Field Sample Collection, Processing, and
Preservation ........................................................ 10-16
10.3 Liquid Samples .................................................. 10-17
10.3.1 Liquid Sampling Methods ....................................... 10-18
10.3.2 Liquid Sample Preparation: Filtration .............................. 10-18
10.3.2.1 Example of Guidance for Ground-Water Sample Filtration ....... 10-19
10.3.2.2 Filters ................................................. 10-21
10.3.3 Field Preservation of Liquid Samples .............................. 10-22
10.3.3.1 Sample Acidification ..................................... 10-22
10.3.3.2 Non-Acid Preservation Techniques .......................... 10-23
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MARLAP JULY 2004
10.3.4 Liquid Samples: Special Cases ................................... 10-25
10.3.4.1 Radon-222 in Water ...................................... 10-25
10.3.4.1 Milk .................................................. 10-26
10.3.5 Nonaqueous Liquids and Mixtures ................................ 10-26
10.4 Solids ......................................................... 10-28
10.4.1 Soils ........................................................ 10-29
10.4.1.1 Soil Sample Preparation .................................. 10-29
10.4.1.2 Sample Ashing ......................................... 10-30
10.4.2 Sediments ................................................... 10-30
10.4.3 Other Solids ................................................. 10-31
10.4.3.1 Structural Materials ...................................... 10-31
10.4.3.2 Biota: Samples of Plant and Animal Products .................. 10-31
10.5 Air Sampling .................................................... 10-34
10.5.1 Sampler Components and Operation .............................. 10-34
10.5.2 Filter Selection Based on Destructive Versus Nondestructive Analysis .... 10-35
10.5.3 Sample Preservation and Storage ................................. 10-36
10.5.4 Special Cases: Collection of Gaseous and Volatile Air Contaminants ..... 10-36
10.5.4.1 Radioiodines ........................................... 10-36
10.5.4.2 Gases ................................................. 10-37
10.5.4.3 Tritium Air Sampling ..................................... 10-38
10.5.4.4 Radon Sampling in Air ................................... 10-39
10.6 Wipe Sampling for Assessing Surface Contamination .................... 10-41
10.6.1 Sample Collection Methods ..................................... 10-42
10.6.1.1 Dry Wipes ............................................. 10-42
10.6.1.2 Wet Wipes ............................................. 10-43
10.6.2 Sample Handling .............................................. 10-44
10.6.3 Analytical Considerations for Wipe Material Selection ................ 10-44
10.7 References ...................................................... 10-45
11 Sample Receipt, Inspection, and Tracking ..................................... 11-1
11.1 Introduction ...................................................... 11-1
11.2 General Considerations ............................................. 11-1
11.2.1 Communication Before Sample Receipt ............................. 11-1
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
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JULY 2004 MARLAP
11.4 Sample Inspection ................................................. 11-8
11.4.1 Physical Integrity of Package and Sample Containers ................... 11-8
11.4.2 Sample Identity Confirmation ..................................... 11-9
11.4.3 Confirmation of Field Preservation ................................. 11-9
11.4.4 Presence of Hazardous Materials ................................... 11-9
11.4.5 Corrective Action .............................................. 11-10
11.5 Laboratory Sample Tracking ........................................ 11-11
11.5.1 Sample Log-In ................................................ 11-11
11.5.2 Sample Tracking During Analyses ................................. 11-11
11.5.3 Storage of Samples ............................................. 11-12
11.6 References ...................................................... 11-13
12 Laboratory Sample Preparation ............................................. 12-1
12.1 Introduction ...................................................... 12-1
12.2 General Guidance for Sample Preparation ............................... 12-2
12.2.1 Potential Sample Losses During Preparation ......................... 12-2
12.2.1.1 Losses as Dust or Particulates ............................... 12-2
12.2.1.2 Losses Through Volatilization ............................... 12-3
12.2.1.3 Losses Due to Reactions Between Sample and Container .......... 12-5
12.2.2 Contamination from Sources in the Laboratory ........................ 12-6
12.2.2.1 Airborne Contamination ................................... 12-7
12.2.2.2 Contamination of Reagents ................................. 12-7
12.2.2.3 Contamination of Glassware and Equipment ................... 12-8
12.2.2.4 Contamination of Facilities ................................. 12-8
12.2.3 Cleaning of Labware, Glassware, and Equipment ...................... 12-8
12.2.3.1 Labware and Glassware .................................... 12-8
12.2.3.2 Equipment ............................................. 12-10
12.3 Solid Samples ................................................... 12-12
12.3.1 General Procedures ............................................ 12-12
12.3.1.1 Exclusion of Material ..................................... 12-14
12.3.1.2 Principles of Heating Techniques for Sample Pretreatment ....... 12-14
12.3.1.3 Obtaining a Constant Weight ............................... 12-23
12.3.1.4 Subsampling ............................................ 12-24
12.3.2 Soil/Sediment Samples ......................................... 12-27
12.3.2.1 Soils .................................................. 12-28
12.3.2.2 Sediments .............................................. 12-28
12.3.3 Biota Samples ................................................ 12-28
12.3.3.1 Food .................................................. 12-29
12.3.3.2 Vegetation ............................................. 12-29
12.3.3.3 Bone and Tissue ......................................... 12-30
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MARLAP JULY 2004
12.3.4 Other Samples ................................................ 12-30
12.4 Filters .......................................................... 12-30
12.5 Wipe Samples ................................................... 12-31
12.6 Liquid Samples .................................................. 12-32
12.6.1 Conductivity ................................................. 12-32
12.6.2 Turbidity ..................................................... 12-32
12.6.3 Filtration .................................................... 12-33
12.6.4 Aqueous Liquids .............................................. 12-33
12.6.5 Nonaqueous Liquids ........................................... 12-34
12.6.6 Mixtures ..................................................... 12-35
12.6.6.1 Liquid-Liquid Mixtures ................................... 12-35
12.6.6.2 Liquid-Solid Mixtures .................................... 12-35
12.7 Gases .......................................................... 12-36
12.8 Bioassay ........................................................ 12-36
12.9 References ...................................................... 12-37
12.9.1 Cited Sources ................................................. 12-37
12.9.2 Other Sources ................................................. 12-43
13 Sample Dissolution ...................................................... 13-1
13.1 Introduction ...................................................... 13-1
13.2 The Chemistry of Dissolution ........................................ 13-2
13.2.1 Solubility and the Solubility Product Constant, Ksp .................... 13-2
13.2.2 Chemical Exchange, Decomposition, and Simple Rearrangement Reactions . 13-3
13.2.3 Oxidation-Reduction Processes .................................... 13-4
13.2.4 Complexation .................................................. 13-5
13.2.5 Equilibrium: Carriers and Tracers .................................. 13-6
13.3 Fusion Techniques ................................................. 13-6
13.3.1 Alkali-Metal Hydroxide Fusions ................................... 13-9
13.3.2 Boron Fusions ................................................ 13-11
13.3.3 Fluoride Fusions ............................................... 13-12
13.3.4 Sodium Hydroxide Fusion ....................................... 13-12
13.4 Wet Ashing and Acid Dissolution Techniques .......................... 13-12
13.4.1 Acids and Oxidants ............................................ 13-13
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
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JULY 2004 MARLAP
13.7.1 Liquid Samples ............................................... 13-23
13.7.2 Solid Samples ................................................ 13-24
13.7.3 Filters ....................................................... 13-24
13.7.4 Wipe Samples ................................................ 13-24
13.8 Comparison of Total Dissolution and Acid Leaching ..................... 13-25
13.9 References ...................................................... 13-27
13.9.1 Cited References .............................................. 13-27
13.9.2 Other Sources ................................................. 13-29
14 Separation Techniques .................................................... 14-1
14.1 Introduction ...................................................... 14-1
14.2 Oxidation-Reduction Processes ....................................... 14-2
14.2.1 Introduction ................................................... 14-2
14.2.2 Oxidation-Reduction Reactions .................................... 14-3
14.2.3 Common Oxidation States ........................................ 14-6
14.2.4 Oxidation State in Solution ...................................... 14-10
14.2.5 Common Oxidizing and Reducing Agents .......................... 14-11
14.2.6 Oxidation State and Radiochemical Analysis ........................ 14-13
14.3 Complexation .................................................... 14-18
14.3.1 Introduction .................................................. 14-18
14.3.2 Chelates ..................................................... 14-20
14.3.3 The Formation (Stability) Constant ................................ 14-22
14.3.4 Complexation and Radiochemical Analysis ......................... 14-23
14.3.4.1 Extraction of Laboratory Samples and Ores .................... 14-23
14.3.4.2 Separation by Solvent Extraction and Ion-Exchange Chromatography 14-23
14.3.4.3 Formation and Dissolution of Precipitates ..................... 14-24
14.3.4.4 Stabilization of Ions in Solution ............................. 14-24
14.3.4.5 Detection and Determination ................................ 14-25
14.4 Solvent Extraction ................................................ 14-25
14.4.1 Extraction Principles ........................................... 14-25
14.4.2 Distribution Coefficient ......................................... 14-26
14.4.3 Extraction Technique ........................................... 14-27
14.4.4 Solvent Extraction and Radiochemical Analysis ...................... 14-30
14.4.5 Solid-Phase Extraction .......................................... 14-32
14.4.5.1 Extraction Chromatography Columns ........................ 14-33
14.4.5.2 Extraction Membranes .................................... 14-34
14.4.6 Advantages and Disadvantages of Solvent Extraction ................. 14-35
14.4.6.1 Advantages of Liquid-Liquid Solvent Extraction ............... 14-35
14.4.6.2 Disadvantages of Liquid-Liquid Solvent Extraction ............. 14-35
14.4.6.3 Advantages of Solid-Phase Extraction Media .................. 14-35
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MARLAP JULY 2004
14.4.6.4 Disadvantages of Solid-Phase Extraction Media ................ 14-36
14.5 Volatilization and Distillation ....................................... 14-36
14.5.1 Introduction .................................................. 14-36
14.5.2 Volatilization Principles ........................................ 14-36
14.5.3 Distillation Principles .......................................... 14-38
14.5.4 Separations in Radiochemical Analysis ............................. 14-39
14.5.5 Advantages and Disadvantages of Volatilization ..................... 14-40
14.5.5.1 Advantages ............................................. 14-40
14.5.5.2 Disadvantages .......................................... 14-40
14.6 Electrodeposition ................................................. 14-41
14.6.1 Electrodeposition Principles ..................................... 14-41
14.6.2 Separation of Radionuclides ..................................... 14-42
14.6.3 Preparation of Counting Sources .................................. 14-43
14.6.4 Advantages and Disadvantages of Electrodeposition .................. 14-43
14.6.4.1 Advantages ............................................. 14-43
14.6.4.2 Disadvantages ............................................ 14-43
14.7 Chromatography .................................................. 14-44
14.7.1 Chromatographic Principles ...................................... 14-44
14.7.2 Gas-Liquid and Liquid-Liquid Phase Chromatography ................. 14-45
14.7.3 Adsorption Chromatography ..................................... 14-45
14.7.4 Ion-Exchange Chromatography ................................... 14-46
14.7.4.1 Principles of Ion Exchange ................................ 14-46
14.7.4.2 Resins ................................................. 14-48
14.7.5 Affinity Chromatography ........................................ 14-54
14.7.6 Gel-Filtration Chromatography ................................... 14-54
14.7.7 Chromatographic Laboratory Methods ............................. 14-55
14.7.8 Advantages and Disadvantages of Chromatographic Systems ........... 14-56
14.7.8.1 Advantages ............................................. 14-56
14.7.8.2 Disadvantages .......................................... 14-56
14.8 Precipitation and Coprecipitation .................................... 14-56
14.8.1 Introduction .................................................. 14-56
14.8.2 Solutions .................................................... 14-57
14.8.3 Precipitation .................................................. 14-59
14.8.3.1 Solubility and the Solubility Product Constant, Ksp .............. 14-59
14.8.3.2 Factors Affecting Precipitation ............................. 14-64
14.8.3.3 Optimum Precipitation Conditions .......................... 14-69
14.8.4 Coprecipitation ................................................ 14-69
14.8.4.1 Coprecipitation Processes ................................. 14-70
14.8.4.2 Water as an Impurity ..................................... 14-74
14.8.4.3 Postprecipitation ........................................ 14-74
Contents
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JULY 2004 MARLAP
14.8.4.4 Coprecipitation Methods .................................. 14-75
14.8.5 Colloidal Precipitates ........................................... 14-78
14.8.6 Separation of Precipitates ....................................... 14-81
14.8.7 Advantages and Disadvantages of Precipitation and Coprecipitation ...... 14-82
14.8.7.1 Advantages ............................................. 14-82
14.8.7.2 Disadvantages .......................................... 14-82
14.9 Carriers and Tracers ............................................... 14-82
14.9.1 Introduction .................................................. 14-82
14.9.2 Carriers ...................................................... 14-83
14.9.2.1 Isotopic Carriers ......................................... 14-83
14.9.2.2 Nonisotopic Carriers ..................................... 14-84
14.9.2.3 Common Carriers ........................................ 14-85
14.9.2.4 Holdback Carriers ....................................... 14-89
14.9.2.5 Yield of Isotopic Carriers .................................. 14-89
14.9.3 Tracers ...................................................... 14-90
14.9.3.1 Characteristics of Tracers .................................. 14-92
14.9.3.2 Coprecipitation .......................................... 14-93
14.9.3.3 Deposition on Nonmetallic Solids ........................... 14-93
14.9.3.4 Radiocolloid Formation .................................. 14-94
14.9.3.5 Distribution (Partition) Behavior ............................ 14-95
14.9.3.6 Vaporization ............................................ 14-95
14.9.3.7 Oxidation and Reduction .................................. 14-96
14.10 Analysis of Specific Radionuclides ................................... 14-97
14.10.1 Basic Principles of Chemical Equilibrium ........................ 14-97
14.10.2 Oxidation State ............................................ 14-100
14.10.3 Hydrolysis ................................................ 14-100
14.10.4 Polymerization ............................................. 14-102
14.10.5 Complexation ............................................. 14-103
14.10.6 Radiocolloid Interference .................................... 14-103
14.10.7 Isotope Dilution Analysis .................................... 14-104
14.10.8 Masking and Demasking ..................................... 14-105
14.10.9 Review of Specific Radionuclides .............................. 14-109
14.10.9.1 Americium ............................................ 14-109
14.10.9.2 Carbon ............................................... 14-114
14.10.9.3 Cesium ............................................... 14-116
14.10.9.4 Cobalt ................................................ 14-119
14.10.9.5 Iodine ................................................ 14-125
14.10.9.6 Neptunium ............................................ 14-132
14.10.9.7 Nickel ................................................ 14-136
14.10.9.8 Plutonium ............................................. 14-139
Contents
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MARLAP JULY 2004
14.10.9.9 Radium ............................................... 14-148
14.10.9.10 Strontium ............................................. 14-155
14.10.9.11 Sulfur and Phosphorus ................................... 14-160
14.10.9.12 Technetium ........................................... 14-163
14.10.9.13 Thorium .............................................. 14-169
14.10.9.14 Tritium ............................................... 14-175
14.10.9.15 Uranium .............................................. 14-180
14.10.9.16 Zirconium ............................................. 14-191
14.10.9.17 Progeny of Uranium and Thorium .......................... 14-198
14.11 References ..................................................... 14-201
14.12 Selected Bibliography ............................................ 14-218
14.12.1 Inorganic and Analytical Chemistry ............................ 14-218
14.12.2 General Radiochemistry ..................................... 14-219
14.12.3 Radiochemical Methods of Separation .......................... 14-219
14.12.4 Radionuclides ............................................. 14-220
14.12.5 Separation Methods ......................................... 14-222
Attachment 14A Radioactive Decay and Equilibrium .......................... 14-223
14A.1 Radioactive Equilibrium ....................................... 14-223
14A.1.1 Secular Equilibrium ..................................... 14-223
14A.1.2 Transient Equilibrium ................................... 14-225
14A.1.3 No Equilibrium ........................................ 14-226
14A.1.4 Summary of Radioactive Equilibria ......................... 14-227
14A.1.5 Supported and Unsupported Radioactive Equilibria ................ 14-228
14A.2 Effects of Radioactive Equilibria on Measurement Uncertainty ......... 14-229
14A.2.1 Issue ................................................. 14-229
14A.2.2 Discussion ............................................ 14-229
14A.2.3 Examples of Isotopic Distribution: Natural, Enriched, and Depleted
Uranium .............................................. 14-231
14A.3 References .................................................. 14-232
15 Quantification of Radionuclides ............................................ 15-1
15.1 Introduction ...................................................... 15-1
15.2 Instrument Calibrations ............................................. 15-2
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
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15.3.1 Electrodeposition ............................................... 15-8
15.3.2 Precipitation/Coprecipitation ..................................... 15-11
15.3.3 Evaporation .................................................. 15-12
15.3.4 Thermal Volatilization/Sublimation ................................ 15-15
15.3.5 Special Source Matrices ......................................... 15-16
15.3.5.1 Radioactive Gases ....................................... 15-16
15.3.5.2 Air Filters .............................................. 15-17
15.3.5.3 Swipes ................................................ 15-18
15.4 Alpha Detection Methods .......................................... 15-18
15.4.1 Introduction .................................................. 15-18
15.4.2 Gas Proportional Counting ...................................... 15-20
15.4.2.1 Detector Requirements and Characteristics ..................... 15-20
15.4.2.2 Calibration and Test Source Preparation ...................... 15-25
15.4.2.3 Detector Calibration ..................................... 15-25
15.4.2.4 Troubleshooting ......................................... 15-27
15.4.3 Solid-State Detectors ........................................... 15-29
15.4.3.1 Detector Requirements and Characteristics .................... 15-30
15.4.3.2 Calibration- and Test-Source Preparation ..................... 15-33
15.4.3.3 Detector Calibration ...................................... 15-33
15.4.3.4 Troubleshooting ......................................... 15-34
15.4.3.5 Detector or Detector Chamber Contamination ................. 15-35
15.4.3.6 Degraded Spectrum ...................................... 15-37
15.4.4 Fluorescent Detectors ........................................... 15-38
15.4.4.1 Zinc Sulfide ............................................ 15-38
15.4.4.2 Calibration- and Test-Source Preparation ..................... 15-40
15.4.4.3 Detector Calibration ...................................... 15-41
15.4.4.4 Troubleshooting ......................................... 15-41
15.4.5 Photon Electron Rejecting Alpha Liquid Scintillation (PERALS®) ....... 15-42
15.4.5.1 Detector Requirements and Characteristics .................... 15-42
15.4.5.2 Calibration- and Test-Source Preparation ..................... 15-44
15.4.5.3 Detector Calibration ...................................... 15-45
15.4.5.4 Quench ................................................ 15-45
15.4.5.5 Available Cocktails ...................................... 15-46
15.4.5.6 Troubleshooting ......................................... 15-46
15.5 Beta Detection Methods ............................................ 15-46
15.5.1 Introduction ................................................... 15-46
15.5.2 Gas Proportional Counting/Geiger-Mueller Tube Counting ............. 15-49
15.5.2.1 Detector Requirements and Characteristics .................... 15-49
15.5.2.2 Calibration- and Test-Source Preparation ..................... 15-53
15.5.2.3 Detector Calibration ...................................... 15-54
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15.5.2.4. Troubleshooting ......................................... 15-57
15.5.3 Liquid Scintillation ............................................ 15-57
15.5.3.1 Detector Requirements and Characteristics .................... 15-58
15.5.3.2 Calibration- and Test-Source Preparation ..................... 15-61
15.5.3.3 Detector Calibration ...................................... 15-62
15.5.3.4 Troubleshooting ......................................... 15-68
15.6 Gamma Detection Methods ......................................... 15-68
15.6.1 Sample Preparation Techniques ................................... 15-70
15.6.1.1 Containers ............................................. 15-71
15.6.1.2 Gases ................................................. 15-71
15.6.1.3 Liquids ................................................ 15-72
15.6.1.4 Solids ................................................. 15-72
15.6.2 Sodium Iodide Detector ......................................... 15-73
15.6.2.1 Detector Requirements and Characteristics .................... 15-73
15.6.2.2 Operating Voltage ....................................... 15-76
15.6.2.3 Shielding .............................................. 15-76
15.6.2.4 Background ............................................ 15-76
15.6.2.5 Detector Calibration ...................................... 15-77
15.6.2.6 Troubleshooting ......................................... 15-77
15.6.3 High Purity Germanium ......................................... 15-78
15.6.3.1 Detector Requirements and Characteristics .................... 15-78
15.6.3.2 Gamma Spectrometer Calibration ........................... 15-82
15.6.3.3 Troubleshooting ......................................... 15-84
15.6.4 Extended Range Germanium Detectors ............................ 15-88
15.6.4.1 Detector Requirements and Characteristics .................... 15-89
15.6.4.2 Detector Calibration ...................................... 15-89
15.6.4.3 Troubleshooting ......................................... 15-90
15.6.5 Special Techniques for Radiation Detection ......................... 15-90
15.6.5.1 Other Gamma Detection Systems ........................... 15-90
15.6.5.2 Coincidence Counting .................................... 15-91
15.6.5.3 Anti-Coincidence Counting ................................ 15-93
15.7 Specialized Analytical Techniques ................................... 15-94
15.7.1 Kinetic Phosphorescence Analysis by Laser (KPA) ................... 15-94
15.7.2 Mass Spectrometry ............................................. 15-95
15.7.2.1 Inductively Coupled Plasma-Mass Spectrometry ............... 15-96
15.7.2.2 Thermal Ionization Mass Spectrometry ....................... 15-99
15.7.2.3 Accelerator Mass Spectrometry ............................ 15-100
15.8 References ..................................................... 15-101
15.8.1 Cited References ............................................. 15-101
15.8.2 Other Sources ................................................ 15-115
Contents
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JULY 2004 MARLAP
16 Data Acquisition, Reduction, and Reporting for Nuclear Counting Instrumentation .... 16-1
16.1 Introduction ...................................................... 16-1
16.2 Data Acquisition .................................................. 16-2
16.2.1 Generic Counting Parameter Selection .............................. 16-3
16.2.1.1 Counting Duration ........................................ 16-4
16.2.1.2 Counting Geometry ....................................... 16-5
16.2.1.3 Software .................................................. 16-5
16.2.2 Basic Data Reduction Calculations ................................. 16-6
16.3 Data Reduction on Spectrometry Systems .............................. 16-8
16.3.1 Gamma-Ray Spectrometry ........................................ 16-9
16.3.1.1 Peak Search or Identification ................................. 16-10
16.3.1.2 Singlet/Multiplet Peaks ................................... 16-13
16.3.1.3 Definition of Peak Centroid and Energy ........................ 16-14
16.3.1.4 Peak Width Determination ................................... 16-15
16.3.1.5 Peak Area Determination .................................. 16-17
16.3.1.6 Calibration Reference File ................................. 16-19
16.3.1.7 Activity and Concentration ................................ 16-20
16.3.1.8 Summing Considerations .................................. 16-21
16.3.1.9 Uncertainty Calculation ..................................... 16-22
16.3.2 Alpha Spectrometry ............................................ 16-23
16.3.2.1 Radiochemical Yield ..................................... 16-27
16.3.2.2 Uncertainty Calculation ................................... 16-28
16.3.3 Liquid Scintillation Spectrometry ................................. 16-29
16.3.3.1 Overview of Liquid Scintillation Counting ...................... 16-29
16.3.3.2 Liquid Scintillation Spectra ................................ 16-29
16.3.3.3 Pulse Characteristics ..................................... 16-29
16.3.3.4 Coincidence Circuitry .................................... 16-30
16.3.3.5 Quenching ............................................. 16-30
16.3.3.6 Luminescence ........................................... 16-31
16.3.3.7 Test-Source Vials ........................................ 16-31
16.3.3.8 Data Reduction for Liquid Scintillation Counting ............... 16-31
16.4 Data Reduction on Non-Spectrometry Systems .......................... 16-32
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
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MARLAP JULY 2004
16.7 Data Reporting Packages ........................................... 16-39
16.8 Electronic Data Deliverables ........................................ 16-41
16.9 References ...................................................... 16-41
16.9.1 Cited References .............................................. 16-41
16.9.2 Other Sources ................................................. 16-44
17 Waste Management in a Radioanalytical Laboratory ............................ 17-1
17.1 Introduction ...................................................... 17-1
17.2 Types of Laboratory Wastes ......................................... 17-1
17.3 Waste Management Program ......................................... 17-2
17.3.1 Program Integration ............................................. 17-3
17.3.2 Staff Involvement ............................................... 17-3
17.4 Waste Minimization ................................................ 17-3
17.5 Waste Characterization ............................................. 17-6
17.6 Specific Waste Management Requirements ............................. 17-6
17.6.1 Sample/Waste Exemptions ....................................... 17-9
17.6.2 Storage ....................................................... 17-9
17.6.2.1 Container Requirements ..................................... 17-10
17.6.2.2 Labeling Requirements ..................................... 17-10
17.6.2.3 Time Constraints .......................................... 17-11
17.6.2.4 Monitoring Requirements ................................... 17-11
17.6.3 Treatment .................................................... 17-12
17.6.4 Disposal ..................................................... 17-12
17.7 Contents of a Laboratory Waste Management Plan/Certification Plan ........ 17-13
17.7.1 Laboratory Waste Management Plan ............................... 17-13
17.7.2 Waste Certification Plan/Program ................................. 17-14
17.8 Useful Web Sites ................................................. 17-15
17.9 References ...................................................... 17-17
17.9.1 Cited References .............................................. 17-17
17.9.2 Other Sources ................................................. 17-17
Contents
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JULY 2004 MARLAP
Appendix (Volume II)
Appendix F Laboratory Subsampling ............................................ F-1
F.1 Introduction .......................................................... F-1
F.2Basic Concepts........................................................ F-2
F.3Sources 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.4Implementation 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-11
F.4.4 Scenario 3 – Particle Surface Contamination ......................... F-13
F.5Summary ........................................................... F-15
F.6References .......................................................... F-16
Glossary .......................................................... End of volume
Contents
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MARLAP JULY 2004
List of Figures (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
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 NaI(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
Contents
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JULY 2004 MARLAP
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
Contents
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MARLAP JULY 2004
List of Tables (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 EC ........... 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
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
Contents
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JULY 2004 MARLAP
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
XXIII
JULY 2004 MARLAP
ACRONYMS AND ABBREVIATIONS
AC ......... alternating current
ADC ........ analog to digital convertor
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
ATD ........ 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 officers 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
Acronyms and Abbreviations
XXIV
MARLAP JULY 2004
d ........... day[s]
D........... homogeneous distribution coefficient
DAAP ....... diamylamylphosphonate
DC ......... direct current
DCGL....... derived concentration guideline level
DHS ........ U.S. Department of Homeland Security
DIN......... di-isopropylnaphthalene
DL ......... discrimination limit
DoD ........ U.S. Department of Defense
DOE ........ U.S. Department of Energy
DOELAP .... DOE Laboratory Accreditation Program
DOT ........ U.S. Department of Transportation
DOP ........ dispersed oil particulate
dpm ........ disintegrations per minute
DPPP ....... dipentylpentylphosphonate
DQA........ data quality assessment
DQI......... data quality indicator
DQO........ data quality objective
DTPA ....... diethylene triamine pentaacetic acid
DVB ........ divinylbenzene
Ee.......... emission probability per decay event
Eβmax ........ maximum beta-particle energy
EDD ........ electronic data deliverable
EDTA....... ethylene diamine tetraacetic acid
EGTA....... ethyleneglycol bis(2-aminoethylether)-tetraacetate
EMEDD ..... environmental management electronic data deliverable (DOE)
EPA ........ U.S. Environmental Protection Agency
ERPRIMS . . . Environmental Resources Program Management System (U.S. Air Force)
ESC ........ expedited site characterization; expedited site conversion
eV.......... electron volts
FAR ........ Federal Acquisition Regulations, CFR Title 48
FBO ........ Federal Business Opportunities [formerly Commerce Business Daily]
FDA ........ U.S. Food and Drug Administration
FEP......... full energy peak
fg .......... femtogram
FOM........ figure of merit
FWHM ...... full width of a peak at half maximum
FWTM ...... full width of a peak at tenth maximum
Acronyms and Abbreviations
XXV
JULY 2004 MARLAP
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, H1....... 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
LIMS ....... 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
Acronyms and Abbreviations
XXVI
MARLAP JULY 2004
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)
MARSSIM . . . Multi-Agency Radiation Survey and Site Investigation Manual
MCA ....... multichannel analyzer
MCL........ maximum contaminant limit
MDA ....... minimum detectable amount; minimum detectable activity
MDC ....... minimum detectable concentration
MDL........ method detection limit
MeV ........ mega electron volts
MIBK ....... methyl isobutyl ketone
min ......... minute[s]
MPa ........ megapascals
MQC ....... minimum quantifiable concentration
MQO ....... measurement quality objective
MS ......... matrix spike; mass spectrometer
MSD........ matrix spike duplicate
MVRM...... method validation reference material
NAA........ neutron activation analysis
NaI(Tl) ...... thallium-activated sodium iodide [detector]
NCP ........ National Oil and Hazardous Substances Pollution Contingency Plan
NCRP ....... National Council on Radiation Protection and Measurement
NELAC ..... National Environmental Laboratory Accreditation Conference
NESHAP .... National Emission Standards for Hazardous Air Pollutants (EPA)
NIM ........ nuclear instrumentation module
NIST........ National Institute of Standards and Technology
NPL ........ National Physics Laboratory (United Kingdom); National Priorities List (United
States)
NRC ........ U.S. Nuclear Regulatory Commission
NRIP ....... NIST Radiochemistry Intercomparison Program
NTA (NTTA) . nitrilotriacetate
NTU ........ nephelometric turbidity units
NVLAP ..... National Voluntary Laboratory Accreditation Program (NIST)
OA ......... observational approach
OFHC....... oxygen-free high-conductivity
Acronyms and Abbreviations
XXVII
JULY 2004 MARLAP
OFPP ....... Office of Federal Procurement Policy
φMR ......... required relative method uncertainty
Pa .......... pascals
PARCC ..... precision, accuracy, representativeness, completeness, and comparability
PBBO ....... 2-(4'-biphenylyl) 6-phenylbenzoxazole
PCB ........ polychlorinated biphenyl
pCi ......... picocurie
pdf ......... probability density function
PE.......... performance evaluation
PERALS..... Photon Electron Rejecting Alpha Liquid Scintillation®
PFA ........ perfluoroalcoholoxil
PIC ......... pressurized ionization chamber
PIPS ........ planar implanted passivated silicon [detector]
PM ......... project manager
PMT ........ photomultiplier tube
PT.......... performance testing
PTB ........ Physikalisch-Technische bundesanstalt (Germany)
PTFE ....... polytetrafluoroethylene
PUREX ..... plutonium uranium reduction extraction
PVC ........ polyvinyl chloride
QA ......... quality assurance
QAP ........ Quality Assessment Program (DOE)
QAPP ....... quality assurance project plan
QC ......... quality control
rad ......... radiation absorbed dose
RCRA ....... Resource Conservation and Recovery Act
REE ........ rare earth elements
REGe ....... reverse-electrode germanium
rem ......... roentgen equivalent: man
RFP ........ request for proposals
RFQ ........ request for quotations
RI/FS ....... remedial investigation/feasibility study
RMDC ...... required minimum detectable concentration
ROI......... region of interest
RPD ........ relative percent difference
RPM ........ remedial project manager
RSD ........ relative standard deviation
RSO ........ radiation safety officer
Acronyms and Abbreviations
XXVIII
MARLAP JULY 2004
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]
t½ .......... 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
Acronyms and Abbreviations
XXIX
JULY 2004 MARLAP
TSDF ....... treatment, storage, or disposal facility
tSIE ........ transfomed spectral index of the external standard
TTA ........ thenoyltrifluoroacetone
U........... expanded uncertainty
uMR ......... required absolute method uncertainty
uc(y) ........ combined standard uncertainty
UBGR ...... upper bound of the gray region
UCL ........ upper control limit
USACE ..... 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]
XXXI
JULY 2004 MARLAP
UNIT CONVERSION FACTORS
To Convert To Multiply by To Convert To Multiply by
Years (y) Seconds (s)
Minutes (min)
Hours (h)
3.16 × 107
5.26 × 105
8.77 × 103
s
min
h
y 3.17 × 10!8
1.90 × 10!6
1.14 × 10!4
Disintegrations
per second (dps)
Becquerels (Bq) 1.0 Bq dps 1.0
Bq
Bq/kg
Bq/m3
Bq/m3
Picocuries (pCi)
pCi/g
pCi/L
Bq/L
27.03
2.7 × 10!2
2.7 × 10!2
103
pCi
pCi/g
pCi/L
Bq/L
Bq
Bq/kg
Bq/m3
Bq/m3
3.7 × 10!2
37
37
10!3
Microcuries per
milliliter
(µCi/mL)
pCi/L 109pCi/L µCi/mL 10!9
Disintegrations
per minute (dpm)
µCi
pCi
4.5 × 10!7
4.5 × 10!1
pCi dpm 2.22
Gallons (gal) Liters (L) 3.78 Liters Gallons 0.265
Gray (Gy) rad 100 rad Gy 10!2
Roentgen
Equivalent Man
(rem)
Sievert (Sv) 10!2Sv rem 102
10-1
JULY 2004 MARLAP
10 FIELD AND SAMPLING ISSUES THAT AFFECT
LABORATORY MEASUREMENTS
Part A: Generic Issues
10.1 Introduction
This chapter provides guidance to project managers, planners, laboratory personnel, and the
radioanalytical specialists tasked with developing a field sampling plan. It emphasizes those
activities conducted at the time of sample collection and other activities conducted after sample
collection that could affect subsequent laboratory analyses.
A field sampling plan should provide comprehensive guidance for collecting, preparing,
preserving, shipping, and tracking field samples and recording field data. The principal objective
of a well-designed sampling plan is to provide representative samples of the proper size for
analysis. Critical to the sampling plan are outputs of the systematic planning process, which
commonly define the Analytical Protocol Specifications (APSs) and the measurement quality
objectives (MQOs) that must be met. While comprehensive discussions on actual field sample
collection and sampling strategies are beyond the scope of MARLAP, specific aspects of sample
collection methods and the physical preparation and preservation of samples warrant further
discussion because they impact the analytical process and the data quality.
This chapter has two main parts. Part A identifies general elements of a field sampling plan and
provides project planners with general guidance. Part B provides detailed, matrix-specific
guidance and technical data for liquid, solid, airborne, and surface contaminants requiring field
sampling. This information will assist project planners further in the development of standard
operating procedures (SOPs) and training for field personnel engaged in preparation and
preservation of field samples.
The need to specify sample collection methods,
and to prepare and preserve field samples, is
commonly dictated by one or more of the
following:
The systematic planning process that
identifies the type, quality, and quantity of
data needed to satisfy a decision process;
The potential alteration of field samples by
physical, chemical, and biological processes
during the time between collection and
Contents
Part A: Generic Issues ...................... 10-1
10.1 Introduction .......................... 10-1
10.2 Field Sampling Plan: Non-Matrix-Specific
Issues............................... 10-3
Part B: Matrix-Specific Issues That Impact Field
Sample Collection, Processing, and
Preservation......................... 10-16
10.3 Liquid Samples ...................... 10-17
10.4 Solids ............................. 10-28
10.5 Air Sampling ....................... 10-34
10.6 Wipe Sampling for Assessing Surface
Contamination ...................... 10-41
10.7 References ......................... 10-45
Field and Sampling Issues That Affect Laboratory Measurements
10-2
MARLAP JULY 2004
analysis;
Requirements specified by the analytical laboratory pertaining to sample analysis;
Requirements of analytical methods; and
Requirements of regulators (e.g., Department of Transportation).
10.1.1 The Need for Establishing Channels of Communication
To design an effective sampling plan, it is critical to obtain the input and recommendations of
representatives of (1) the field sampling team, (2) the health physics professional staff, (3) the
analytical laboratory, (4) statistical and data analysts, (5) quality assurance personnel, and (6)
end-users of data.
Beyond the initial input that assist the project planners in the design of the sampling plan, it is
equally important to maintain open channels of communication among key members of the
project team throughout the process. For example, the analytical laboratory should be provided
with contacts within the field sampling team to ensure that modifications, discrepancies, and
changes are addressed and potential problems may be resolved in a timely manner.
Communication among project staff, field personnel, and the laboratory offer a means to
coordinate activities, schedules, and sample receipt. Project planning documents generated from
the systematic planning process, such as APSs and statements of work (SOWs), should be
consulted, but they cannot address all details. Additional communication will be necessary to
convey information about the number and type of samples the laboratory can expect at a certain
time. Documentation with special instructions regarding the samples should be received before
the samples arrive. This information notifies the laboratory of any health and safety concerns so
that laboratory personnel can implement proper contamination management practices. Health and
safety concerns may affect analytical procedures, sample disposition, etc. The analytical
laboratory should have an initial understanding about the relative number of samples that will be
received and the types of analyses that are expected for specific samples. Furthermore, advance
communications allow laboratory staff to adjust to modifications, discrepancies, and changes.
10.1.2 Developing Field Documentation
The field organization must conduct its operations in such a manner as to provide reliable
information that meets the data quality objectives (DQOs). To achieve this goal, all relevant
procedures pertaining to sample collection and processing should be based on documented
standard operating procedures that may include, but are not limited to, the following activities:
Developing a technical basis for defining the size of individual samples;
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Selecting field equipment and instrumentation;
Using proper sample containers and preservatives;
Using consistent container labels and sample identification codes;
Documenting field sample conditions and exceptions;
Documenting sample location;
Tracking, accountability, custody, and shipment forms;
Legal accountability, such as chain-of-custody record, when required;
Selecting samples for field quality control (QC) program;
Decontaminating equipment and avoiding sample cross-contamination;
Specifying sample packaging, radiological surveys of samples, shipping, and tracking; and
Documenting the health and safety plan.
10.2 Field Sampling Plan: Non-Matrix-Specific Issues
10.2.1 Determination of Analytical Sample Size
When collecting environmental samples for radiochemical analysis, an important parameter for
field personnel is the mass or volume of an individual sample that must be collected. The
required minimum sample size is best determined through the collective input of project
planners, field technicians, and laboratory personnel who must consider the likely range of the
contaminant concentrations, the type of radiation emitted by constituents or analytes (alpha, beta,
and gamma emitters), field logistics, and the radioanalytical methods that are to be employed. It
is important to have a quantitative understanding of the relationship between sample size and
project specific requirements in order for samples to yield useful data.
10.2.2 Field Equipment and Supply Needs
Before starting field sampling activities, all necessary equipment and supplies should be
identified, checked for proper operation and availability, and—when appropriate—pre-
assembled. Instrumentation and equipment needs will depend not only on the matrix to be
sampled, but also on the accessibility of the matrix and the physical and chemical properties of
radionuclide contaminants under investigation.
In addition to specialized field equipment and instrumentation, field sampling supplies
commonly include, but are not limited to, the following:
Sampling devices (e.g., trowel, hand auger, soil core sampler, submersible water pump, high
volume air filter, etc.);
Sampling preparation equipment (e.g., weighing scales, volume measuring devices, soil
screening sieves, water filtering equipment, etc.);
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Sample preservation equipment and agents (e.g., refrigeration, ice, formaldehyde or acid
additives);
Personnel protective gear (e.g., respiratory protective devices, protective clothing such as
gloves and booties, life-preservers, etc.);
Proper writing utensils (e.g., permanent pens and markers);
Field logbooks and field tracking forms;
Maps, distance measuring equipment, global positioning systems, or other location-
determining equipment;
Field sampling flags or paint;
Chain-of-custody (COC) forms;
Sample tags, labels, and documents;
Appropriately labeled sample containers;
Shipment containers and packing materials that meet national and international shipping
regulations (see Section 10.2.10);
Shipment forms;
Analysis request forms identifying the type of radioanalysis to be performed; and
Items required by the health and safety plan (medical kit, etc.).
10.2.3 Selection of Sample Containers
There are several physical and chemical characteristics to consider when selecting a suitable
container for shipping and storing samples. These include the container material and its size,
configuration, and method for ensuring a proper seal.
10.2.3.1 Container Material
Sample containers must provide reasonable assurance of maintaining physical integrity (i.e.,
against breakage, rupture, or leakage) during handling, transport, and potentially long periods of
storage. The most important factor to consider in container selection is the chemical
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compatibility between container material and sample. Containers may be made from ordinary
bottle glass, borosilicate glass (such as Pyrex® or Corex®), plastics (e.g., high-density
polyethylene, HDPE), low-density polyethylene, polycarbonate, polyvinyl chloride (PVC),
fluorinated ethylene or propylene (Teflon), or polymethylpentene. For certain samples, the
choice of containers may require metal construction or be limited to paper envelopes.
10.2.3.2 Container Opening and Closure
A suitable container also should be shaped appropriately for the purpose. For example, a wide-
mouthed container will provide easier access for the introduction and withdrawal of sample
material and eliminate spills or the need for additional tools or equipment (e.g., funnel) that may
become a source of cross contamination among samples.
Equally important is the container’s closure. As a rule, snap-on caps should not be considered for
liquid samples because they do not ensure a proper seal. Even when screw caps are used, it is
frequently prudent to protect against vibration by securing the cap with electrical or duct tape. A
proper seal is important for air samples, such as radon samples. The container cap material, if
different from the container material, must be equally inert with regard to sample constituents.
10.2.3.3 Sealing Containers
Tamper-proof seals offer an additional measure to ensure sample integrity. A simple example
includes placing a narrow strip of paper over a bottle cover and then affixing this to the container
with a wide strip of clear tape (EPA, 1987, Exhibit 5-6 provides examples of custody seals). The
paper strip can be initialed and dated in the field to indicate the staff member who sealed the
sample and the date of the seal. Individually sealing each sample with a custody seal with the
collector’s initials and the date the sample was sealed may be required by the project. The seal
ensures legal defensibility and integrity of the sample at collection. Tamper-proof seals should
only be applied once field processing and preservation steps are completed. Reopening this type
of sealed container in the field might warrant using a new container or collecting another sample.
10.2.3.4 Precleaned and Extra Containers
The reuse of sample containers is discouraged because traces of radionuclides might persist from
initial container use to subsequent use. The use of new containers for each collection removes
doubts concerning radionuclides from previous sampling. New containers might also require
cleaning (ASTM D5245) to remove any plasticizer used in production or to pretreat glass
surfaces. Retaining extra empty containers from a new lot or a special batch of precleaned and
treated containers can provide the laboratory container blanks for use as part of quality control.
Extra containers are also useful for taking additional samples as needed during field collection
and to replace broken or leaking containers.
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10.2.4 Container Label and Sample Identification Code
Each sample can only be identified over the life of a study if a form of permanent identification is
provided with or affixed to the container or available in sample log. The most useful form of
identification utilizes a unique identifier for each sample. Such unique identification codes
ensure the project’s ability to track individual samples. The standard operating procedure (SOP)
that addresses sample identification should describe the method to be used to assure that samples
are properly identified and controlled in a consistent manner. Containers sometimes may be pre-
labeled with identification numbers already in place.
Any identification recorded on a container or a label affixed to the container should remain with
the container throughout sample processing and storage. The identification information should be
written with a permanent marker—especially if the labels are exposed to liquids. Information can
be recorded directly on the container or on plastic or paper tags securely fixed to the container.
However, tags are more likely to become separated from containers than are properly secured
labels.
Labels, tags, and bar codes should be durable enough so no information is lost or compromised
during field work, sample transport, or laboratory processing. Transparent tape can be used to
cover the label once it is completed. The tape protects the label, adds moisture resistance,
prevents tampering with the sample information, and helps secure the label to the container.
The project manager needs to determine if a field-sample identification (ID) scheme may
introduce bias into the analysis process, such as allowing the laboratory to become aware of
trends or locations from the sample identification. This could influence their judgment about the
anticipated result and thereby introduce actions on the part of laboratory personnel that they
would not otherwise take (such as reanalyzing the sample). The project manager needs to
determine the applicability of electronic field data recorders and the issue of electronic signatures
for the project.
A unique identifier can include a code for a site, the sample location at the site, or a series of
digits identifying the year and day of year (e.g., “1997-127” uses the Julian date, and “062296”
describes a month, day, and year). Alternatively, a series of digits can be assigned sequentially by
site, date, and laboratory destination. The use of compass headings and grid locations also
provides additional unique information (e.g., “NW fence, sampled at grid points: A1 through
C25, 072196, soil”). With this approach, samples arriving at a laboratory are then unique in two
ways. First, each sample can be discriminated from materials collected at other sites. Second, if
repeat samples are made at a single site, then subsequent samples from the same location are
unique only by date. Labeling samples sequentially might not be appropriate for all studies. Bar
coding may reduce transcription errors and should be evaluated for a specific project.
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10.2.5 Field Data Documentation
All information pertinent to field sampling is documented in a log book or on a data form. The
log book should be bound and the pages numbered consecutively, and forms should be page-
numbered and dated. Where the same information is requested routinely, preprinted log books or
data sheets will minimize the effort and will standardize the presentation of data. Even when
standardized preprinted forms are used, all information recorded should be in indelible ink, with
all entry errors crossed out with a single line and initialed. The color of ink used should be
compatible with the need to copy that information. All entries should be dated and signed on the
date of entry. Initials should be legible and traceable, so that it is clear who made the entry.
Whenever appropriate, log or data form entries should contain—but are not limited to—the
following:
Identification of Project Plan or Sampling Plan;
Location of sampling (e.g., reference to grid location, maps, photographs, location in a
room);
Date and time of sample collection;
Sample matrix (e.g., surface water, soil, sediment, sludge, etc.);
Suspected radionuclide constituents;
Sample-specific ID;
Sample volume, weight, depth;
Sample type (e.g., grab, composite);
Sample preparation used (e.g., removal of extraneous matter);
Sample preservation used;
Requested analyses to be performed (e.g., gross beta/gamma, gamma spectroscopy for a
specific radionuclide, radiochemical analysis);
Sample destination, including name and address of analytical laboratory;
Names of field people responsible for collecting sample;
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Physical and meteorological conditions at time of sample collection;
Special handling or safety precautions;
Results of field radiation measurements, including surveys of sample containers; and
Signatures or initials of appropriate field personnel. When using initials, ensure that they can
be uniquely identified with an individual.
Labels affixed to individual sample containers should contain key information that forms an
abstract of log book data sheets. When this is not practical, a copy of individual sample data
sheets may be included along with the appropriately ID-labeled sample.
10.2.6 Field Tracking, Custody, and Shipment Forms
A sample tracking procedure must be in place for all projects in order that the proper location and
identification of samples is maintained throughout the process from collection through handling,
preservation, storage, transfer to laboratory, and disposal. The term “tracking” means an
accountability process that meets generally acceptable laboratory practices as described by
accrediting bodies, but is less stringent than a formal chain-of-custody process. Tracking also
develops a record of all individuals responsible for the custody and transfer of the samples.
Chapter 4 (Project Plan Documents) discusses the process of tracking and accountability. Also,
Chapter 11 (Sample Receipt, Inspection, and Tracking) discusses the laboratory process of
tracking.
When transferring the possession of samples, the individuals relinquishing and the individuals
receiving the samples should sign, date, and note the time on the form. A standardized form
should be designed for recording tracking or formal chain-of-custody information related to
tracking sample possession. An example of a COC form is shown in Figure 10.1. Additional
information and examples of custody forms are illustrated by EPA (1987 and 1994). If samples
are to be split and distributed to more than one analytical laboratory, multiple forms will be
needed to accompany sample sets. The sample collector is responsible for initiating the sample
tracking record. The following information is considered minimal for sample tracking:
Name of project;
Sampler’s signature;
Sample ID;
Sample location
Date and time sampled;
Sample type;
Preservatives;
Number of containers;
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Analysis required;
Signatures of persons relinquishing, receiving, and transporting the samples;
Signature for laboratory receipt;
Method of shipment or carrier and air bill when shipped or shipping manifest identification
upon receipt; and
Comments regarding the integrity of shipping container and individual samples.
10.2.7 Chain of Custody
The legal portion of the tracking and handling process that ensures legal defensibility from
sample collection to data reporting has become relatively standardized and is referred to as the
CHAIN-OF-CUSTODY RECORD
FIELD
IDENTIFI-
CATION
NUMBER
FIELD
LOCATION DATE TIME
SAMPLED BY:
SAMPLE MATRIX SEQ.
No.
No. of
Containers
Analysis
Required
Water Soil Other
Relinquished by: Date/Time
/
Received by: Date/Time
/
Relinquished by: Date/Time
/
Received by: Date/Time
/
Relinquished by: Date/Time
/
Received by: Date/Time
/
Relinquished by: Date/Time
/
Received by: Date/Time
/
Relinquished by: Date/Time
/
Received by laboratory for field analysis: Date/Time
/
Method of Shipment:
Distribution: Orig. - Accompany Shipment
1 Copy – Survey Coordinator Field Files
FIGURE 10.1—Example of chain-of-custody record
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COC process (APHA, 1998). Guidance is provided in ASTM D4840 and NIOSH (1983). The
level of security required to maintain an adequate chain of custody is that necessary to establish a
“reasonable probability” that the sample has not been tampered with. For court proceedings, the
requirements are established in law. COC procedures are important in demonstrating sample
control when litigation is involved. In many cases, federal, state or local agencies may require
that COC be maintained for specific projects. COC is usually not required for samples that are
generated and immediately tested within a facility or continuous (rather than discrete or integra-
ted) samples that are subject to real- or near-real-time analysis (e.g., continuous screening).
When COC is required, the custody information is recorded on a COC form. Chain-of-custody
documents vary by organization and by project. Communication between field and laboratory
personnel is critical to the successful use of COC. Any error made on a custody form is crossed
out with a single line and dated and initialed. Use of correction ink or obliteration of data is not
acceptable. Inform the laboratory when COC is required before the samples are received (see
Section 11.2.4, “Sample Chain-of-Custody,” for further information). The COC documents are
signed by personnel who collect the samples. A COC record accompanies the shipment and one
or more copies are distributed to the project coordinator or other office(s) where field and
laboratory records are maintained.
10.2.8 Field Quality Control
A project plan should have been developed to ensure that all data are accurate and that decisions
based on these data are technically sound and defensible. The implementation of a project plan
requires QC procedures. QC procedures, therefore, represent specific tools for measuring the
degree to which quality assurance objectives are met. Field QC measures are discussed
comprehensively in ASTM D5283.
While some types of QC samples are used to assess analytical process, field QC samples are used
to assess the actual sampling process. The type and frequency of these field QC samples must be
specified by the project planning process along with being included in the project planning
documents and identified in the sampling plan. Definitions for certain types of field QC samples
can be found in ASTM D5283 and MARSSIM (2000).
10.2.9 Decontamination of Field Equipment
Sampling SOPs must describe the recommended procedure for cleaning field equipment before
and during the sample collection process, as well as any pretreatment of sample containers. The
SOPs should include the cleaning materials and solvents used, the purity of rinsing solution or
water, the order of washing and rinsing, associated personnel safety precautions, and the disposal
of cleaning agents.
Detailed procedures for the decontamination of field equipment used in the sampling of low-
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activity soils, soil gas, sludges, surface water, and ground water are given in ASTM D5608.
10.2.10 Packing and Shipping
The final responsibility of field sampling personnel is to prepare and package samples properly
for transport or shipment by a commercial carrier. All applicable state and federal shipping
requirements, discussed later in this section, must be followed. When samples must be shipped
by commercial carrier or the U.S. Postal Service, containers must be designed to protect samples
against crushing forces, impacts, and severe temperature fluctuations. Within each shipping
container, the cushioning material (sawdust, rubber, polystyrene, urethane foam, or material with
similar resiliency) should encase each sample completely. The cushioning between the samples
and walls of the shipping containers should have a minimum thickness of 2.5 cm. A minimum
thickness of five centimeters should be provided on the container floor.
Samples should also be protected from the potentially adverse impacts of temperature fluctua-
tions. When appropriate, protection from freezing, thawing, sublimation, evaporation, or extreme
temperature variation may require that the entire interior surface of the shipping container be
lined with an adequate layer of insulation. In many instances, the insulating material also may
serve as the cushioning material.
The requirements for container security, cushioning, and insulation apply regardless of container
material. For smaller volume and low-weight samples, properly lined containers constructed
from laminated fiberboard, plastic, or reinforced cardboard outer walls also may be used.
When samples are shipped as liquids in glass or other breakable sample containers, additional
packaging precautions may have to be taken. Additional protection is obtained when sample
containers are shipped in nested containers, in which several smaller containers (i.e., inner
containers) are packed inside a second larger container (i.e., the outer pack or overpack). To
contain any spills of sample material within the shipping container, it is advisable either to wrap
individual samples or to line the shipping container with absorbent material, such as asbestos-
free vermiculite or pearlite.
For proper packaging of liquid samples, additional guidance has been given by EPA (1987) and
includes the following:
All sample bottles are taped closed;
Each sample bottle is placed in a plastic bag and the bag is sealed;
Each sample bottle may be placed in a separate metal can filled with vermiculite or other
packing material, and the lid taped to the can;
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The cans are placed upright in a cooler that has its drain plug taped closed, inside and out,
and lined with a plastic bag; and
The cooler is filled with packing material—“bubble wrap” or cardboard separators may be
used—and closed with sealing tape.
Field screening measurements are made for compliance with U.S. Department of Transportation
regulations, 49 CFR Parts 170 through 189, as well as compliance with the laboratory’s license
from the U.S. Nuclear Regulatory Commission (NRC; 10 CFR Part 71) and Agreement State (if
applicable). International requirements may also apply. See the International Air Transport
Association’s Dangerous Goods Regulations for additional guidance. These regulations not only
set contamination and radiation levels for shipping containers, but also describe the types of
containers and associated materials that are to be used based on the total activity and quantity of
materials shipped. When the samples are screened in the field with survey instrumentation, the
results should be provided to the laboratory. This information should also state the distance used
from the probe to the packing container wall. Measurements normally are made in contact or at
one meter. The readings in contact are most appropriate for laboratory use. The screening
measurements in the field are mainly for compliance with transportation requirements and are
usually in units of exposure. Laboratory license requirements are usually by isotope and activity.
Project planning and communication are essential to ensure that a specific set of samples can be
transported, received, and analyzed safely while complying with applicable rules and regulations.
The external surface of each shipping container must be labeled clearly, contain information
regarding the sender and receiver, and should include the respective name and telephone number
of a contact. When required, proper handling instructions and precautions should be clearly
marked on shipping containers. Copies of instructions, shipping manifest or container inventory,
chain of custody, and any other paperwork that are enclosed within a shipping container should
be safeguarded by placing documents within a sealed protected envelope.
10.2.11 Worker Health and Safety Plan
In some cases, field samples will be collected where hazardous agents or site conditions might
pose health and safety considerations for field personnel. These can include chemical, biological,
and radiological agents, as well as common industrial hazards associated with machinery, noise
levels, and heat stress. The health and safety plan established in the planning process should be
followed. For the U.S. Department of Defense, these plans may include imminent threats to life,
such as unexploded ordnance, land mines, hostile forces, chemical agents, etc. A few of the
hazards particular to field sampling are discussed in the following sections, but these should not
be construed as a comprehensive occupational health and safety program. The Occupational
Safety and Health Administration’s (OSHA) regulations governing laboratory chemical hygiene
plans are located at 29 CFR 1910.1450. These requirements should apply as well to field
sampling.
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10.2.11.1 Physical Hazards
MECHANICAL EQUIPMENT
Personnel working with hand-held tools (e.g., sledge hammers used for near-surface coring) or
power tools and equipment are subject to a variety of hazards. For example, personnel drilling
monitoring wells are exposed to a variety of potential mechanical hazards, including moving
machinery, high-pressure lines (e.g., hydraulic lines), falling objects, drilling through under-
ground utilities, flying machinery parts, and unsafe walking and working surfaces. The
consequences of accidents involving these physical hazards can range from minor to fatal injury.
At a minimum, workers should be required to wear protective clothing, which includes hard hats,
gloves, safety glasses, coveralls (as an option) and steel-toed safety shoes. Workers required to
climb (e.g., ladders, drilling masts) must be trained according to OSHA standards in the proper
use of devices to prevent falls.
For sampling operations that require drilling, open boreholes and wells must be covered or
secured when unattended, including during crew breaks.
ELECTRICAL HAZARDS
Electric power often is supplied by gasoline or diesel engine generators. Working conditions may
be wet, and electrical shock with possibly fatal consequences may occur. In addition, drilling
operations may encounter overhead or buried electrical utilities, potentially resulting in exposure
to very high voltages, which could be fatal or initiate fires.
All electrical systems used during field operations should be checked for proper grounding
during the initial installation. Temporary electrical power provided to the drill site shall be
protected by ground-fault circuit interrupters.
NOISE HAZARDS
Power equipment is capable of producing sound levels in excess of 85 dB(A), the eight-hour
threshold limit value recommended by the American Conference of Governmental Industrial
Hygienists. Exposure to noise levels in excess of 85 dB(A) for long periods of time can cause
irreversible hearing loss. If noise levels exceed
85dB(A), a controlled area must be maintained
at this distance with a posting at each entrance
to the controlled area to read:
CAUTION
NOISE HAZARD
Hearing Protection Required Beyond This Point
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HEAT STRESS
The use of protective clothing during summer months significantly increases the potential for
personnel to experience heat stress. Adverse effects from heat stress include heat cramps,
dehydration, skin rash, heat edema, heat exhaustion, heat stroke, or death. When heat stress
conditions exist, the following ought to be available:
A cool and shaded rest area;
Regular rest breaks;
An adequate supply of drinking water; and
Cotton coveralls rather than impermeable Tyvek® coveralls.
CHEMICAL AND RADIOLOGICAL HAZARDS
The health and safety plan should contain information about a site’s potential radionuclides and
hazards that might be encountered during implementation of field sampling and survey
procedures. All field personnel should read the health and safety plan and acknowledge an
understanding of the radiological hazards associated with a site. Site specific training must be
provided that addresses the chemical and radiological hazards likely to be associated with a site.
Field procedures should include either information relating to these hazards or should reference
appropriate sections of the health and safety plan. References related to the use of protective
clothing are given in EPA (1987), DOE (1987, Appendix J), and in 29 CFR 1910, Subpart I.
When procuring environmental solid and liquid samples, unusual characteristics such as color,
suspended material, or number of phases and unusual odors should be noted and a description
should be provided to the on-site safety officer as well as the analytical laboratory. Additional
information concerning field methods for rapid screening of hazardous materials is presented in
EPA (1987). This source primarily addresses the appearance and presence of organic compounds
that might be present on occasions when one is collecting materials to detect radioactivity.
Checking samples for chemical or radiological hazards can be as simple as visual inspection or
using a hand-held radiation meter to detect radiation levels. Adjustments to laboratory proce-
dures, particularly those involving sample handling and preparation, can only be made when
pertinent field information is recorded and relayed to the project planner and to the laboratory. In
some cases, a laboratory might not have clearance to receive certain types of samples (such as
explosives or chemical agents) because of their content, and it will be necessary to divert these
samples to an alternate laboratory. It might be necessary to reduce the volume sampled in order
to meet shipping regulations if high concentrations of radioactivity are present in the samples. In
some cases, the activity of one radionuclide might be much higher than others in the same
sample. Adjustments made on the basis of the radionuclide of higher activity might result in
collection of too little of another radionuclide to provide adequate detection and thus prevent
identification of these radionuclides because of their relatively low minimum detectable
concentrations. These situations should be considered during planning and documented in the
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appropriate sampling plan document.
10.2.11.2 Biohazards
Precautions should be taken when handling unknown samples in the field. Some examples are
wearing gloves, coveralls or disposable garments, plastic booties, dust masks or other respiratory
protection. Some biohazards may be snakes, ticks, spiders, and rodents (Hanta virus). Prevention
of potential exposure is the goal of a safety program. The type of protective equipment in the
field should be discussed in the planning process and specified in the appropriate plan document.
Since there are many specifics that are site dependent, it is difficult to create a comprehensive
list. But the information is discussed to provide an awareness and starting point for additional
discussion.
PERSONNEL TRAINING AND QUALIFICATION
All field operations that could lead to injury for sample collectors should be performed by
personnel trained to documented procedures. When sampling is conducted in radiologically
controlled areas (RCAs) as defined in regulatory standards (i.e., 10 CFR 20, 10 CFR 835).
Formal training and qualification of field personnel may be required.
Training may require both classroom and practical applications in order to familiarize personnel
with the basic theory of radiation and radioactivity and the basic rules for minimizing external
exposures through time, distance, shielding, and avoidance of internal exposure (by complying
with rules regarding smoking, drinking, eating, and washing of hands). Other topics to cover
include common routes of exposure (e.g., inhalation, ingestion, skin contact); proper use of
equipment and the safe handling of samples; proper use of safety equipment such as protective
clothing, respirators, portable shielding, etc.
Guidance for the training and qualification of workers handling radioactive material has been
issued by the Nuclear Regulatory Commission (see appropriate NRC NUREGs and Regulatory
Guides on training of radiation workers), Department of Energy (1994a–d), and the Institute of
Nuclear Power Operations (INPO 88-010). These and other documents should be consulted for
the purpose of training and qualifying field personnel.
PERSONNEL MONITORING AND BIOASSAY SAMPLING
When conditions dictate the need for personnel monitoring, various methods are commonly
employed to assess external and internal exposure that might have resulted from the inhalation or
ingestion of a radionuclide.
Thermoluminescent dosimeters, film badges, or other personnel dosimeters may be used to
monitor and document a worker’s external exposures to the whole body or extremities. For
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internal exposures, assessment of dose may be based on: (1) air monitoring of the work area or
the worker’s breathing zone; (2) in vivo bioassay (whole-body counting); or (3) in vitro bioassays
that normally involve urinalysis but also may include fecal analysis and nasal smears. For in vitro
bioassays (i.e., urine or fecal), the standard method involves a 24-hour sample collection in a
sealable container. Samples may be kept under refrigeration until laboratory analysis can be
performed to retard bacterial action. (Bioassay sample collection is normally not performed in the
“field.”)
The following guidance documents may be used for personnel monitoring and the collection and
preservation of bioassay samples:
ANSI/ANS HPS N13.30 (1996), Performance Criteria for Radiobioassay;
ANSI/ANS HPS N13.14 (1994), Internal Dosimetry Programs for Tritium Exposure—
Minimum Requirements;
ANSI/ANS HPS 13.22 (1995), Bioassay Programs for Uranium;
ANSI/ANS HPS 13.42 (1997), Internal Dosimetry for Mixed Fission Activation Products;
DOE Implementation Guide, Internal Dosimetry Program, G-10 CFR 835/C1—Rev. 1 Dec.
1994a;
DOE Implementation Guide, External Dosimetry Program, G-10 CFR 835/C2—Rev. 1 Dec.
1994b;
DOE Implementation Guide, Workplace Air Monitoring, G-10 CFR 835/E2-Rev. 1 Dec.
1994c;
DOE Radiological Control Manual, DOE/EH-0256T, Rev. 1, 1994d;
NRC Regulatory Guide 8.9, Acceptable Concepts, Models, Equations, and Assumptions for a
Bioassay Program (September 1993);
NRC Regulatory Guide 8.11, Applications of Bioassay for Uranium (Revision 1, July 1993);
NRC Regulatory Guide 8.20, Applications of Bioassay for 125I and 131I (June 1974);
NRC Regulatory Guide 8.22, Bioassays at Uranium Mills (Revision 1, August 1988);
NRC Regulatory Guide 8.26, Applications of Bioassay for Fission and Activation Products
(September 1980);
NRC Regulatory Guide 8.32, Criteria for Establishing a Tritium Bioassay Program (July
1988);
NCRP (1987), Use of Bioassay Procedures for Assessment of Internal Radionuclides
Deposition; and
INPO (1988), Guidelines for Radiological Protection at Nuclear Power Stations.
Part B: Matrix-Specific Issues That Impact Field Sample Collection,
Processing, and Preservation
Field processing should be planned in advance so that all necessary materials are available during
field work. Preparing checklists of processing equipment, instruments, and expendable
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materials—exemplified in part by lists accompanying sampling procedures described by EPA
(1994)—helps this planning effort and serves to organize field methods. Field personnel who
communicate problems should prevent loss of time, effort, and improper sample collection, as
well as documents exactly what equipment, instruments, etc. were used.
The initial steps taken in the field frequently are critical to laboratory analysis performed hours,
days, or even weeks after a sample is obtained. Various sample preparation steps may be required
before samples are packaged and shipped for laboratory analysis. The need for sample processing
and preservation is commonly determined by the sample matrix, the DQOs of the analysis, the
nature of the radionuclide, and the analytical method.
The goal of sample preservation is to maintain the integrity of the sample between the time the
sample is collected and the time it is analyzed, thus assuring that the analysis is performed on a
sample representative of the matrix collected. Sample preservation should limit biological and
chemical actions that might alter the concentration or physical state of the radionuclide
constituents or analytes. For example, cations at very low concentrations can be lost from
solution (e.g., cesium can exchange with potassium in the glass container, and radionuclides can
be absorbed by algae or slime growths in samples or containers that remain in the field for
extended periods). Requirements for sample preservation should be determined during project
planning when analytical protocols are selected. Sample preservation in the field typically
follows or accompanies processing activities. Sample preservatives may be added to sample
collection containers before they are sent to the field.
This section provides matrix-specific guidance that focuses on the preparation and processing of
field samples. In order to assist project planners in developing a sampling plan, a limited
discussion is also provided that describes matrix-specific methods commonly employed for the
collection of field samples. Guidance is presented for only the most common materials or
environmental media, which are generically classified as liquids, solids, and air. In some
instances, a solid material to be analyzed involves particulate matter filtered from a liquid or air
suspension. Because filter media can affect analytical protocols, a separate discussion is provided
that addresses sample materials contained on filter materials, including surface contamination
associated with wipe samples.
10.3 Liquid Samples
Liquid samples typically are classified as aqueous, nonaqueous, or mixtures. Aqueous samples
requiring analysis are likely to represent surface water, ground water, drinking water,
precipitation, tanks and lagoons, and runoff. Nonaqueous liquids may include a variety of
solvents, oils and other organic liquids. Mixtures of liquids represent a combination of aqueous
and nonaqueous liquids or a solid suspended in either aqueous and nonaqueous liquids.
Standardized water sampling procedures are described in numerous documents (APHA, 1998;
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EPA, 1985; EPA, 1987; DOE, 1997; ASTM D3370). Important decisions include the choice of
instrument or tool used to obtain the sample, the sample container material, the need for sample
filtration, and the use of sample preservatives.
10.3.1 Liquid Sampling Methods
The effect of the sample collection process on the sample integrity needs to be understood and
managed. Two examples are dissolved gases and cross-contamination. It may be necessary to
minimize dissolved oxygen and carbon dioxide, which can cause some dissolved metals to
undergo reaction or precipitation.
Sampling is discussed in NAVSEA (1997) and USACE (1995). The latter reference has been
superseded, but the revision does not include sampling. The sampling references listed in
USACE (1995) are:
U.S. Environmental Protection Agency (EPA). 1984. Characterization of Hazardous Waste
Sites—A Method Manual, Vol. II, Available Sampling Methods, Second Edition, EPA 600-4-
84-076.
U.S. Environmental Protection Agency (EPA). 1982. Handbook for Sampling and Sample
Preservation of Water and Wastewater, EPA 600-4-82-029.
U.S. Environmental Protection Agency (EPA). 1986. Compendium of Methods for
Determination of Superfund Field Operation Methods, EPA 600-4-87/006.
U.S. Environmental Protection Agency (EPA). 1987. A Compendium of Methods for
Determination of Superfund Field Operation Methods, EPA 540-P-87-001a, OSWER
Directive 9355.0-14.
U.S. Department of the Interior (DOI). 1980. National Handbook of Recommended Methods
for Water for Water-Data Acquisition, Volume I and II.
10.3.2 Liquid Sample Preparation: Filtration
Filtration of a water sample may be a key analytical planning issue and is discussed in Section
3.4.3, “Filters and Wipes.” A decision needs to be made during project planning whether or not
to filter the sample in the field. Filtration of water or other liquids may be required to determine
contaminant concentrations in solubilized form, suspended particulates, or sediment. The method
of filtration will depend on the required sample volume, the amount and size of suspended
particulates, and the availability of portable equipment and resources (e.g., electricity).
The potential need to filter a water sample principally depends on the source of water and the
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objectives of the project investigation. If, for example, the intent is to assess human exposure
from ingestion of drinking water “at-the-spigot,” unfiltered tap water samples are likely to be
required. Conversely, filtration may be required for water taken from an unlined field monitor
well that is likely to contain significant amounts of particulate matter. These solids are of little
relevance but may interfere with radioanalytical protocols (e.g., sample absorption may occur
during gross alpha or beta counting where the analytical procedure involves the simple
evaporation of a water aliquant on a planchet).
For remote sampling sites, sample processing may be restricted to gravity filtration that requires a
minimum of equipment and resources. Drawing samples through filters by pressure or suction
that is created by syringe, vacuum pump, or aspiration are alternative options. If filter papers or
membranes capture materials that will be retained for analysis, they should be handled with clean
rubber or plastic gloves, forceps, or other instruments to prevent sample contamination.
Each federal agency may have unique guidance to determine the need and process for filtering
samples. One performance-based example is that of EPA, discussed in the next section. This
guidance applies to either the field or laboratory filtration.
10.3.2.1 Example of Guidance for Ground-Water Sample Filtration
After considering whether or not to filter ground-water samples when analyzing for metals, the
Environmental Engineering Committee of EPA’s Science Advisory Board (EPA, 1997)
recommended:
Several factors could introduce errors in the sampling and analysis of ground water for metals
or metallic radionuclides. Well construction, development, sampling, and field filtering are
among the steps that could influence the metals measured in the ground-water samples. Field
filtering is often a smaller source of variability and bias compared to these other factors.
Therefore, the Agency should emphasize in its guidance the importance of proper well
construction, development, purging, and water pumping rates so that the field filtering
decisions can also be made accurately.
Under ideal conditions, field-filtered ground-water samples should yield identical metals
concentrations when compared to unfiltered samples. However, under non-ideal conditions,
the sampling process may introduce geological materials into the sample and would require
field filtration. Under such conditions, filtering to remove the geological artifacts has the
potential of removing colloids (small particles that may have migrated as suspended materials
that are mobile in the aquifer). Available scientific evidence indicates that when wells have
been properly constructed, developed, and purged, and when the sample has been collected
without stirring or agitating the aquifer materials (turbidity less than 5 nephelometric
turbidity units, NTU), then field filtering should not be necessary. For Superfund site
assessments, the low-flow sampling technique without filtration is the preferred sampling
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approach for subsequent metal analysis when well construction, well maintenance, and
hydrogeological conditions such as flow rate allow. Under such conditions, the collected
samples should be representative of the dissolved and particulate metals that are mobile in
ground-water systems. The Agency’s proposal to rely on low flow sampling and unfiltered
samples is a conservative approach that favors false positives over false negatives.
When the turbidity of the sample is high, the situation is different. In-line filtering provides
samples that retain their chemical integrity. Therefore, field filtering of properly collected
ground-water samples should be done when turbidity in the samples is higher than 5 NTU,
even after slow pumping has been utilized to obtain the sample.
They acknowledged, however, that differences in the way wells are installed, their packing
materials, and the techniques used to collect ground-water samples can lead to variability in
analytical results between wells and between individual samples. Filtering a sample can be a way
to remove suspended particles and some colloids that contain metals that would not normally be
in the ground water if the material were not disturbed during sampling. Here, a colloid is defined
as a particle that ranges in size from 0.003 to 10 µm (Puls et al., 1990; Puls and Powell, 1992).
The literature indicates that colloids as large as 2 µm can be mobile in porous media (Puls and
Powell, 1992). Saar (1997) presents a review of the industry practice of filtration of ground-water
samples. For some sites with low hydraulic conductivity the presence of an excess of colloids
presents numerous monitoring challenges and field filtration might be necessary.
The desire to disturb the aquifer as little as possible has led to the use of low-flow sampling of
wells—low-flow purging and sampling occurs typically at 0.1 to 0.3 L/min (Saar, 1997). The
low-flow technique maximizes representativeness by (EPA, 1997):
Minimizing disturbances that might suspend geochemical materials that are not usually
mobile;
Minimizing disturbances that might expose new reactive sites that could result in leaching or
adsorption of inorganic constituents of ground water;
Minimizing exposure of the ground water to the atmosphere or negative pressures, ensuring
that the rate of purging and sampling does not remove ground water from the well at a rate
much greater than the natural ground-water influx; and
Monitoring indicator parameters to identify when stagnant waters have been purged and the
optimum time for sample collection.
In summary, based on the ability of the low-flow sampling technique to collect representative
samples, EPA suggests that filtering of ground-water samples prior to metals analysis is usually
not required (EPA, 1997).
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10.3.2.2 Filters
The removal of suspended particles is commonly achieved by filtration. When filtration is
required, it should be done in the field or as soon as practicable. Field filtration permits acid
preservatives to be added soon after collection, which minimizes the adsorption of soluble
contaminants on the container walls and avoids the dissolution of particulate matter which may
not be part of the sample to be analyzed.
An arbitrary size of 0.45 µm has gained acceptance as the boundary between soluble and
insoluble matter (particularly for water in power plant boilers (ASTM D6301). It is the filter pore
size that is commonly recommended by laboratory protocols. Material that may be present in
colloidal form (a second phase in a liquid that is not in solution), can have particles that range
from 0.001 to 2 µm. Such particles may be problematic since they may or may not be filterable
(Maron and Lando, 1974). Thus, there can be no single standard for filter type or pore size, and
every project should establish its own filtration protocol based upon its needs.
The fact that small particles pass through membrane filters has been recognized for some time
(Kennedy et al., 1974). Conversely, as the filters clog, particles an order of magnitude smaller are
retained by these filters (Sheldon and Sutcliffe, 1969). It should be noted, however, that
manufacturers of filters usually specify only what will not pass through the filter; they make no
claims concerning what actually does pass through the filter. Laxen and Chandler (1982) present
a comprehensive discussion of some effects of different filter types. They refer to thin (5 to 10
µm) polycarbonate filters as “screen types,” and thick (100 to 150 µm) cellulose nitrate and
acetate filters as “depth type.” The screen-type filters (e.g., polycarbonate) clog much more
rapidly than the depth type (e.g., cellulose nitrate and acetate) filters. Once the filtration rate
drops, particles that would normally pass through the filter are trapped in the material already
retained. Also, filtering through screen-type filters may take considerable time and may require
suction or pressure to accomplish in a reasonable time. Hence, the use of screen-type filters,
because of their increased propensity to clog, generally is not recommended.
In addition to the difficulty of contending with clogging, Silva and Yee (1982) report adsorption
of dissolved radionuclides on membrane filters. Although these drawbacks cannot be completely
overcome, they are still less than the potential difficulties that arise from not filtering.
Finally, good laboratory practices must be used for field sampling. The most likely sources of
contamination for the filters are improperly cleaned tubing and filter holders and handling the
filters with contaminated fingers. Tubing and holders should be thoroughly cleaned and rinsed
between samples and the entire system should be rinsed several times with the water to be
sampled. Filters should be handled with clean rubber gloves.
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10.3.3 Field Preservation of Liquid Samples
Sample degradation may occur between the time of collection and analysis due to microbial
contaminants or chemical interactions. Although sample degradation cannot destroy or alter the
radiological properties of a contaminant, it can alter the radionuclide’s chemical properties and
its potential distribution within a sample. For example, microbial processes are known to affect
both the chemical state and the distribution of radioelements due to oxidation-reduction
reactions, complexation and solubilization by metabolic compounds, bioaccumulation,
biomylation, and production of gaseous substances such as CO 2, H 2, CH 4, and H2S (Francis,
1985; Pignolet et al., 1989).
The selected field preservation method also should take into account compatibility with the
radionuclides, analytical methods, analytical requirements, and container properties (see Section
10.2.3, “Selection of Sample Containers”). One example that illustrates compatibility with the
analytical method is the addition of HCl to water samples as a preservative for gross alpha and
gross beta analyses. The HCl will corrode stainless steel planchets used in the method. If
laboratory personnel are aware of this, they can include steps to prevent the corrosion. Other
preservation issues for liquid samples are discussed in Table 10.1 (page 10-25). Compatibility
issues should be evaluated during the planning phase and included in the field sampling plan.
10.3.3.1 Sample Acidification
Acidification is the method of choice for preserving most types of water samples. The principal
benefit of acidification is that it keeps many radionuclides in solution and minimizes their
potential for removal by chemical and physical adsorption or by ion exchange. The mode by
which a radionuclide is potentially removed from solution is strongly affected by the radionuclide
and the container material. For example, studies conducted by Bernabee et al. (1980) and Milkey
(1954) demonstrated that the removal of metal ions from solution is dominated by physical (i.e.,
van der Waals) adsorption. Milkey’s conclusion is based on: (1) the observation that the loss of
uranium, lead, and thorium ions from solution was significantly greater for containers made of
polyethylene than of borosilicate glass; and (2) the fact that while adsorption by glass may
potentially involve all three adsorption processes; with polyethylene plastic, there are no valence-
type attractive forces or ions to exchange, and only physical van der Waals adsorption is possible.
Similar observations were reported by: (1) Dyck (1968), who compared long-term adsorption of
silver ions by molded plastic to glass containers; (2) Jackson (1962), who showed that
polyethylene containers absorbed about five times as much 90Sr as glass containers at pH of about
seven; and (3) Martin and Hylko (1987a; 1987b), who reported that greater than 50 percent of
99Tc was adsorbed by polyethylene containers from non-acidified samples.
For sample acidification, either nitric or hydrochloric acid is commonly added until a pH of less
than two (APHA, 1998, Table 7010.1; EPA, 1980, Method 900.0). Other guidance for sample
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preservation by acidification is summarized below.
In instances of very low-activity samples where container adsorption poses a significant concern,
but where acidification of the sample interferes with the radioanalytical method, the choice of
sample container may be limited to glass or require alternative methods. For example, the use of
acids as a preservative is not recommended for the analysis of tritium (3H), carbon-14 (14C), or
radon in water, and precautions must be taken for the following reasons:
For radon, sample preservation offers no benefit and is therefore not required for analytical
accuracy. Adding acid also may cause the generation of CO2 in the sample, which could
purge radon gas.
The addition of acid to a sample containing 14C may result in the production of 14CO 2 and the
loss of 14C from the sample.
Acid does not have a direct effect on tritium. However, it may affect the cocktail used in
liquid scintillation analysis, or as with HCl, may add significant quench to the cocktail (see
Section 15.5.3, “Liquid Scintillation”).
Although acidification has been shown to effectively reduce the adsorption of technetium by
polyethylene, technetium in the TcO 4
!4 state has been observed to volatilize in strong acid
solutions during evaporation while preparing water samples for gross beta analysis (NAS, 1960).
To hasten evaporation, the planchet is commonly flamed. This dilemma can be resolved by either
precoating planchets with a film of detergent prior to the addition of the acidified water sample
or by passive evaporation of the acidified water sample that avoids the higher temperature
associated with flaming (Blanchard et al., 1993).
10.3.3.2 Non-Acid Preservation Techniques
If a sample contains significant organics, or if contaminants under investigation react with acids
that interfere with the radioanalytical methods, other methods of sample preparation should be
considered.
REFRIGERATION AND FREEZING
The effect of refrigeration or freezing temperatures to arrest microbial activity is a fundamental
concept. Temperatures near the freezing mark or below not only retard or block bacterial growth
but arrest essentially all other metabolic activity. It should, however, be noted that most bacteria
can survive even in extreme temperatures. (Indeed, if a suspension of bacterial cells is frozen
rapidly with no appreciable formation of ice crystals, it can be kept at temperatures as low as
-194 EC for indefinite periods of time with little loss of viability.)
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The choice between refrigeration and freezing is dictated by the potential impacts of ice
formation on sample constituents. Besides physical changes of organic constituents, the initial
formation of ice crystals and the exclusion of any solutes may concentrate the solutes to the point
of precipitation. Quick freezing methods that minimize ice crystal formation are beneficial for
preserving some organic constituents. Quick freezing is commonly done by packing sealed
samples in liquid nitrogen or dry ice. Care must be taken, however, to avoid container breakage
due to sample volume expansion. An air space of a least 10 percent and a container made of
plastic provide reasonable assurance for container integrity.
When refrigeration is employed, attempts should be made to avoid temperatures that could result
in slow freezing and the formation of ice crystals. Optimum refrigeration temperatures for sample
preservation at 4 ± 2 EC can be achieved by packing samples in ice or freeze packs within a
thermally insulated leak-proof container (ASTM D3856; ASTM D3370).
PAPER PULP
The addition of paper pulp, with its adsorptive property and large surface area, can avoid the
adsorption and loss of easily hydrolyzed radionuclides to the container wall over time (Bernabee
et al., 1980). About two grams of finely ground paper pulp are added per liter of acidified sample
at time of collection. The pH should be adjusted to one or less and vigorously shaken. The
sample may be stored in this condition for an extended period of time. To prepare for analysis,
the pulp is removed from solution by filtration and subjected to wet ashing using strong acids
(Chapter 12, Laboratory Sample Preparation). This ashed solution is commonly added to the
original filtrate to make a reconstituted sample solution.
The use of paper pulp and the need for wet ashing, however, pose problems for certain
radioanalytical laboratory protocols and must therefore be thoroughly evaluated.
SULFITE
To prevent the loss of radioiodine from solution, sodium bisulfite (NaHSO3), sodium thiosulfate
(Na2S2O3), or sodium metabisulfite (Na2S2O5) may be used. These compounds are strong
reducing agents and will convert volatile iodine (I2) to nonvolatile iodine (I-). If acid is also
employed to preserve samples for analysis of other radionuclides, it is important to note that acid
will counteract the effectiveness of the reducing agent. For this reason, samples collected for
iodine analyses typically are collected and preserved in a separate container. It should also be
noted that the reducing environment produced by the sulfite-type preservatives may convert iron,
uranium, and other reducible ions or their compounds to a different oxidation state. The
inadvertent change in oxidation state of other radionuclides will have an obvious adverse impact
on radioanalytical measurements that require chemical separation. Section 14.9 has additional
information on carriers and tracers.
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OTHERS
Other methods that have been used to preserve liquid samples containing organics and biological
materials include chemical preservatives (e.g., formaldehyde and methanol). Table 10.1
summarizes the advantages and disadvantages of these and previously described preservation
methods.
TABLE 10.1—Summary of sample preservation techniques.
Preservation Technique Advantages Disadvantages
Addition of HNO3Reduces pH and inhibits plating of
metals on container walls.
Strong oxidizer that might react with organic
compounds, such as liquid scintillation
cocktails.
14C might be lost as 14CO2.
Addition of HCl Reduces pH and inhibits plating of
metals on container walls.
Chloride forms strong anionic
complexes with Iron and Uranium.
Causes quench in liquid scintillation cocktails.
14C might be lost as 14CO2.
Might cause corrosion of stainless steel
planchets on gross analyses.
Addition of Sulfite Forms a reducing environment to
prevent the volatilization of iodine.
May produce undesirable oxidation states of
iron or uranium.
Addition of
Formaldehyde
Preserves organic samples.
Prevents further biological activity.
May create disposal problems.
Cooling
(Ice at approximately 0
EC)
Preserves organic samples (i.e.,
water, foods).
Reduces dehydration and retains
moisture.
Reduces biological activity.
Ice melts, requiring replacement over time.
Freezing
(Dry Ice at approximately
-78 EC)
Preserves organic samples (i.e.,
water, plant, animal).
Suspends biological activity.
Dry ice sublimates and requires replacement.
May crack sample container if frozen too
quickly.
Addition of Paper Pulp Provides large surface area for
adsorption of metals, thus minimi-
zing adsorption on container walls.
Requires pH to be one or less.
Requires filtration and wet ashing of paper pulp
and combining liquids to make a new solution.
10.3.4 Liquid Samples: Special Cases
In some cases, liquid samples require special handling in order to preserve or retain a volatile or
gaseous radionuclide. The following are examples of specific methods used to recover or
preserve such samples of interest.
10.3.4.1 Radon-222 in Water
Waterborne radon is analyzed most commonly by liquid scintillation methods, although gamma-
ray spectrometry and other methods have been employed or proposed. Liquid scintillation has the
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obvious advantage of being designed for automated sample processing and is, therefore, less
labor intensive or costly. A key to consistency in analytical results is the zero headspace sampling
protocol such as the one described below.
Since radon is inert and nonpolar, it diffuses through plastic more rapidly than glass. The use of
plastic scintillation vials, therefore, leads to significant loss of radon in water (Whittaker, 1989;
Hess and Beasley, 1990). For this reason, it is recommended that the water sample is collected in
a 23 mL glass scintillation vial, capped with a Teflon or foil-lined cap.
Samples are collected from a nonaerated faucet or spigot, which has been allowed to flow for
sufficient time so that the sample is representative of the water in the distribution system or well.
The time will vary depending on the source.
10.3.4.1 Milk
Milk commonly is viewed as the food product of greatest potential dose significance for airborne
releases of radionuclides. Due to the animals’ metabolic discrimination, however, only a few
radionuclides have a significant dose impact via the milk pathway, notably 90Sr, 131I, and 137Cs.
To prevent milk from souring or curdling, samples should be refrigerated. Preservation of milk
may also be achieved through the addition of formaldehyde or methanol (DOE, 1987),
methimazole (Harrington et al., 1980), or Thimerosal (EPA, 1994). Analytical procedures for
select radionuclides in milk are well established and should be considered when deciding on a
sample preservation method. Adding formaldehyde to milk samples may require them to be
disposed of as hazardous or mixed wastes.
Due to the volatility and potential loss of 131I (as I2), a known amount of NaI dissolved in water
may be added to the milk sample at time of collection if iodine analysis is required. The NaI not
only serves as a carrier for the chemical separation of radioiodine, but also provides a
quantitative tool for determining any loss prior to analysis (DOE, 1990).
10.3.5 Nonaqueous Liquids and Mixtures
Nonaqueous liquids and mixtures include a wide range of organic fluids or solvents, organic
materials dissolved in water, oils, lubricants, etc. These liquids are not likely to represent
contaminated environmental media or matrices, but most likely represent waste streams that must
be sampled. Nonaqueous waste streams are generated as part of normal operations by nuclear
utilities, medical facilities, academic and research facilities, state and federal agencies, radio-
pharmaceutical manufacturers, DOE weapons complexes, mining and fuel fabrication facilities,
etc. Examples of these nonaqueous liquids and mixtures include waste oils and other lubricants
that are generated routinely from maintenance of equipment associated with nuclear power plant
operations or the production of nuclear fuel and nuclear weapon components; and organic and
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inorganic solvents, acids, and bases that are used in a variety of medical, research, and industrial
applications.
In addition to the production of nonaqueous liquid wastes from routine operations by these
facilities, large quantities of nonaqueous liquids containing radionuclide contaminants are also
generated by routine facility decontamination efforts and final decontamination associated with
facility decommissioning. For decontamination and decommissioning activities, a wide range of
processes have been developed that employ halogenated organic compounds, such as Freon®,
chloroform, or trichloroethane. Other aggressive chemical decontamination processes involve
dissolution and removal of metal and oxide layers from surfaces using acid solutions (e.g.,
sulfuric acid, nitric acid, phosphoric acids, and oxalic acid). Chemical decontamination also may
use chelating agents in concentrated processes (5 to 25 percent by weight chemical in solution)
and dilute processes (one percent wt. or less chemicals in solution). Examples of chemical
processes that can be used in both concentrated and dilute forms include the low oxidation-state
transition-metal ion (LOMI) and LOMI-nitric permanganate, developed by Dow Chemical
Company and AP/Citron. The reagents used in both the concentrated and dilute processes include
chelating and complexing agents such as ethylene diamine tetraacetic acid (EDTA), diethylene
triamine pentaacetic acid (DTPA), citric acid, oxalic acid, picolinic acid, and formic acid.
Chelating agents and organic acids are used in decontamination formulas because they form
strong complexes with actinides, lanthanides, heavy metals, and transition metals and assist in
keeping these elements in solution.
Generally, these chemical decontamination solutions, once used, are treated with ion-exchange
resins to extract the soluble activity. The ion-exchange decontamination solutions must be
sampled, nevertheless, to assess the amount of residual radioactivity.
The radionuclides that may be encountered with nonaqueous liquids and mixtures depend on
both the nature of the liquid and its usage. The following listing of radionuclides and liquids are
based on published data collected by NRC (1992) and the State of Illinois (Klebe 1998; IDNS
1993-1997), but are not intended to represent a comprehensive list:
Toluene/xylene/scintillation fluids used by research and clinical institutions: 3H, 14C, 32/33P,
35S, 45Ca, 63Ni, 67Ga, 125/131I, 99Tc, 90Sr, 111In, 123/125I, 147Pm, 201/202Tl, 226/228Ra, 228/230/232Th,
232/234/235/238U, 238/239/241/242Pu, 241Am.
Waste oils and lubricants from operation of motors, pumps, and other equipment: 3H, 54Mn,
65Zn, 60Co, 134/137Cs, 228/230/232Th.
Halogenated organic and solvents from refrigeration, degreasing, and decontamination: 3H,
14C, 32/33P, 35S, 54Mn, 58/60Co, 63Ni, 90Sr, 125/129I, 134/137Cs, 226/228Ra, 228/230/232Th, 232/234/235/238U,
238/239/241Pu.
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Other organic solvents from laboratory and industrial operations and cleaning: 3H, 32/33P, 35S,
45Ca, 125I, U-natural.
Inorganic and organic acids and bases from extraction processes and decontamination: 3H,
14C, 32/33P, 35S, 54Mn, 67Ga, 125/131I, 60Co, 137Cs, and U-natural.
Due to the large number of potential nonaqueous liquids and the complex mixtures of radionuc-
lide contaminants that may require radiochemical analysis, a comprehensive discussion of sample
preparation and preservation is beyond the scope of this discussion. In most instances, however,
these samples are not likely to require refrigeration or chemical preservatives that protect against
sample degradation.
Some organic solvents and highly acidic or basic liquids may react with plastic containers,
causing brittleness or breakage. In selecting sample containers for these nonaqueous samples, it
is important to assess the manufacturers product specifications, which typically provide
information regarding the container’s resistance to chemical and physical agents. When
nonaqueous samples are stored for long periods of time, containers should be checked routinely.
10.4 Solids
Solid samples consist of a wide variety of materials that include soil and sediment, plant and
animal tissue, metal, concrete, asphalt, trash, etc. In general, most solid samples do not require
preservation, but require specific processing in the field before transporting to the laboratory for
analysis. For example, soil sample field processing may require sieving in order to establish
sample homogeneity. These and other specific handling requirements are described below in the
section on each type of solid sample.
The most critical aspect is the collection of a sufficient amount of a representative sample. One
purpose of soil processing is to bring back only that sample needed for the laboratory. Unless
instructed otherwise, samples received by the laboratory are typically analyzed exactly as they are
received. This means that extraneous material should be removed at the time of sample
collection, if indicated in the appropriate plan document.
In many instances, sample moisture content at the time of collection is an important factor. Thus,
the weights of solid samples should be recorded at the time a sample is collected. This allows one
to track changes in wet weight from field to laboratory. Dry and ash weights generally are
determined at the laboratory.
Unlike liquid samples that may be introduced or removed from a container by simple pouring,
solid samples may require a container that is designed for easy sample placement and removal.
For this reason, large-mouth plastic containers with screw caps or individual boxes with sealable
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plastic liners are commonly used. The containers also minimize the risk for breakage and sample
cross-contamination.
10.4.1 Soils
ASTM D653 defines soil as: “Sediments or other unconsolidated accumulations of solid particles
produced by the physical and chemical degradation of rocks, and that might or might not contain
organic matter.” ASTM C999 provides generic guidance for soil sample preparation for the
determination of radionuclides. ASTM D4914 and D4943 provide additional information on soil
and rock.
The distribution of radionuclides in soil should be assumed to be heterogeneous. The degree of
heterogeneity is dictated by the radionuclide’s mode of entry into the environment and soil, the
chemical characteristics of the radionuclide contaminant, soil composition, meteorological and
environmental conditions, and land use. For example, soil contamination from an airborne
release of a radionuclide with strong affinity for clay or other mineral constituents of soil likely
will exhibit a gradient with rapidly diminishing concentrations as a function of soil depth (the
parameter associated with this affinity is KD, which is the concentration of the solid phase
divided by the concentration of the liquid phase). Moreover, contamination may be differentially
distributed among soil particles of different sizes. In most cases, because the contaminant is
adsorbed at the surface of soil particles and since the surface-to-volume ratio favors smaller
particles, smaller soil particles will exhibit a higher specific activity when compared to larger
particles. If land areas include areas of farming, tilling of soil will clearly impact the distribution
of surface contamination.
10.4.1.1 Soil Sample Preparation
Extraneous material should be removed at the time of sample collection, if indicated in the
appropriate plan document. The material may have to be saved and analyzed separately,
depending on the project requirements and MQOs. If rocks, debris, and roots are removed from a
soil sample after it arrives at the laboratory, there may be insufficient material to complete all the
requested analyses (see Section 12.3.1.1 “Exclusion of Material”). A sufficient amount of sample
should be collected to provide the net quantity necessary for the analysis. Subsequent drying at
the laboratory may remove a large percentage of the sample weight that is available for analysis.
Field-portable balances or scales may be used to weigh samples as they are collected, further
ensuring sufficient sample weights are obtained. For certain types of samples, the project DQOs
may require maintaining the configuration of the sample, such as core samples where
concentration verses depth will be analyzed.
The project plan should address the impact of heterogeneity of radionuclide distribution in soil.
Some factors to consider that may impact radionuclide distribution are: determining sampling
depth, the need for removal of vegetative matter, rocks, and debris, and the homogenation of soil
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particulates. For example, soil sampling of the top 5 cm is recommended for soils contaminated
by recent airborne releases (ASTM C998); soil depth to 15 cm may be appropriate when
exposure involves the need to monitor the root zone of food crops (MARSSIM, 2000; NRC,
1990). The need for sample field QC, such as splitting, should be evaluated. Some types of field
QC can be used to evaluate the extent of radionuclide homogeneity. In general, no special
preservation measures are required for soil samples; however, preliminary soil sample
preparation involving drying, sieving, homogenizing, and splitting may be performed by a field
laboratory prior to sample shipment to the analytical laboratory.
If volatile elements are suspected to be present with other nonvolatile contaminants, samples
must be split before drying to avoid loss of the contaminant of interest. Dried samples are
homogenized by mortar and pestle, jaw crusher, ball mill, parallel plate grinder, blender, or a
combination of these techniques and sieved to obtain a uniform sample. Sieve sizes from 35 to
200 mesh generally are recommended for wet chemistry procedures. ASTM C999 correlates
various mesh sizes with alternative designations, inclusive of physical dimensions expressed in
inches or in the metric system. In addition, samples for chemical separations are usually ashed in
a muffle furnace to remove any remaining organic materials that may interfere with the
procedures.
10.4.1.2 Sample Ashing
Soil samples that require chemical separation for radionuclide analysis may also be ashed by the
field laboratory. The use of the term “field laboratory” can cause confusion, since no single
definition is possible. It is used here to define a laboratory that is close to the point of sample
collection. It does not imply that there is a distinction in requirements or specifications that
impact quality. For soil samples, ashing is performed in a muffle furnace to remove any organic
materials that may interfere with radiochemical procedures.
10.4.2 Sediments
Sediments of lakes, reservoirs, cooling ponds, settling basins, and flowing bodies of surface
water may become contaminated as a result of direct liquid discharges, wet surface deposition, or
from runoffs associated with contaminated soils. Because of various chemically and physically
binding interactions with radionuclides, sediments serve as integrating media that are important
to environmental monitoring. An understanding of the behavior of radionuclides in the aquatic
environment is critical to designing a sampling plan, because their behavior dictates their
distribution and sampling locations.
In most cases, sediment is separated from water by simple decanting, but samples also may be
obtained by filtering a slurry or through passive evaporation. As noted previously, care must be
taken to avoid cross contamination from sampling by decontaminating or replacing tools and also
from avoiding contact between successive samples. Suitable sample containers include glass or
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plastic jars with screw caps. The presence of volatile or semi-volatile organic and micro-
organisms may impact the radionuclide concentration, therefore, samples should be kept on ice
while in the field and refrigerated while awaiting radioanalysis. Sediment cores may be sampled,
frozen, and then sectioned.
10.4.3 Other Solids
10.4.3.1 Structural Materials
In some cases, a project plan requires sample analysis of structural materials such as concrete or
steel. Concrete from floors, walls, sidewalks or road surfaces is typically collected by scabbling,
coring, drilling, or chiseling. Depending on the radionuclides of interest and detection methods,
these sample preparations may require crushing, pulverization, and sieving.
Metal associated with structures (e.g., I-beams, rebar) or machines may be contaminated on
exterior or interior surfaces or through activation may become volumetrically contaminated.
Surface contamination may be assessed by swipe samples that provide a measure of removable
contamination (Section 10.6) or by scraping, sandblasting, or other abrasive techniques.
Volumetric contamination is frequently assessed by nondestructive field measurements that rely
on gamma-emitting activation products. However, drill shavings or pieces cut by means of a
plasma arc torch may be collected for further analysis in a laboratory where they can be analyzed
in a low-background environment. In general, these materials require no preservation but, based
on activity/dose-rate levels and sample size and weight, may require proper shielding, engineered
packaging, and shipping by a licensed carrier.
10.4.3.2 Biota: Samples of Plant and Animal Products
The release of radionuclides to the environment from normal facility operations or as the result of
an accident requires the sampling of a wide variety of terrestrial and aquatic biota. For most
biota, sample preservation usually is achieved by icing samples in the field and refrigeration until
receipt by the analytical laboratory. The field sampling plan should describe the type of
processing and preservation required.
Foods may be categorized according to the U.S. Department of Agriculture scheme as leafy
vegetables, grains, tree-grown fruits, etc., and representative samples from each group may be
selected for analysis.
MEAT, PRODUCE, AND DAIRY PRODUCTS
Samples of meat, poultry, eggs, fresh produce, and other food should be placed in sealed plastic
bags and appropriately labeled and preserved by means of ice in the field and refrigeration during
interim storage prior to delivery to the analytical laboratory. All food samples may be reduced to
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edible portions (depending on study objective) for analysis in a manner similar to that for human
consumption (i.e., remove cores, bones, seeds, other nonedible parts) and weighed as received
from the field (i.e., wet weight) within 24 hours. Wet weights are desired, since consumption
data are generally on this basis.
ANIMAL FEED AND VEGETATION
Animal feeds also provide important data for determining radionuclide concentrations in the food
chain. Crops raised for animal feed and vegetation consumed by grazing farm animals may be
sampled. Depending upon radionuclides under investigation and their associated MQOs,
kilogram quantities of vegetative matter may be needed.
As in all terrestrial samples, naturally occurring 40K and the uranium and thorium series
radionuclides contribute to the radiation observed. Deposition of such cosmic-ray-produced
nuclides as 7Be and fallout from nuclear tests also may be present. Properly selected processed
items from commercial sources may be helpful in providing natural and anthropogenic
background data.
TERRESTRIAL WILDLIFE
Wild animals that are hunted and eaten may be of interest for potential dose estimates and
therefore may require sampling. Examples of wildlife that have been used are deer, rabbits, and
rodents that may feed or live in a contaminated site. An estimate of the radionuclide intake of the
animal just before its death may be provided by analyzing the stomach content, especially the
rumen in deer.
AQUATIC ENVIRONMENTAL SAMPLES
In addition to natural radionuclides and natural radionuclides enhanced by human activity, there
are numerous man-made radionuclides that have the potential for contaminating surface and
ground water. The most common of these are fission and activation products associated with
reactor operation and fuel cycle facilities. Radioanalysis of aquatic samples may therefore
include 54Mn, 58Co, 60Co, 65Zn, 95Zr, 90Sr, 134Cs, 137Cs, and transuranics, such as 239Pu.
When surface and ground waters are contaminated, radionuclides may be transferred through a
complex food web consisting of aquatic plants and animals. Aquatic plants and animals, as
discussed here, are any species which derive all or substantial portions of their nourishment from
the aquatic ecosystem, are part of the human food chain, and show significant accumulation of a
radionuclide relative to its concentration in water. Although fish, aquatic mammals, and
waterfowl provide a direct link to human exposure, lower members of the food chain also may be
sampled.
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FLORA
Aquatic biota such as algae, seaweed, and benthic organisms are indicators and concentrators of
radionuclides—especially 59Fe, 60Co, 65Zn, 90Sr, 137Cs, and the actinides—and can be vectors in
the water-fish-human food chain. As such, they may be sampled upstream and downstream at
locations similar to those described for sediment. Because of their high water content, several
kilograms (wet weight) should be collected per sample. The wet weight of the sample should be
recorded. Enough of the wet sample should be processed so that sufficient sample remains
following the drying process. Both algae (obtained by filtering water or by scraping submerged
substrates) and rooted aquatic plants should be sampled.
FISH AND SHELLFISH
Several kilograms of each fish sample are usually required; this may be one large fish, but
preferably a composite of a number of small ones. Analysis of the edible portions of food fish as
prepared for human consumption is of major interest. Fish may be de-boned, if specified in the
sampling plan. The whole fish is analyzed if it is used for the preparation of a fish meal for
consumption or if only trend indication is required. In a program where fish are the critical
pathway, fish are analyzed by species; if less detail is required, several species with similar
feeding habits (such as bottom feeders, insectivores, or predators) may be collected and the data
grouped. Some species of commercial fish, though purchased locally, may have been caught
elsewhere. Thus, the presence or absence of a radionuclide in a specific fish may not permit any
definite conclusion concerning the presence of the radionuclide in water at that location.
Shellfish, such as clams, oysters, and crabs, are collected for the same reasons as fish, but have
the advantage as indicators of being relatively stationary. Their restricted mobility contributes
substantially to the interpretation and application of analytical results to environmental
surveillance. Edible and inedible portions of these organisms can be prepared separately.
WATERFOWL
Waterfowl, such as ducks and geese, may also concentrate radionuclides from their food sources
in the aquatic environment and serve as important food sources to humans. The migratory
patterns and feeding habits of waterfowl vary widely. Some species are bottom feeders and, as
such, tend to concentrate those radionuclides associated with sediments such as 60Co, 65Zn, and
137Cs. Others feed predominantly on surface plants, insects, or fish.
An important consideration in obtaining a sample from waterfowl is that their exterior surfaces,
especially feathers, may be contaminated. It is important to avoid contaminating the “flesh”
sample during handling. As with other biota samples, analyses may be limited to the edible
portions and should be reported on a wet weight basis.
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10.5 Air Sampling
The measurement of airborne radionuclides as gases or particulates provides a means of
evaluating internal exposure through the inhalation pathways. The types of airborne radioactivity
that may require air sampling are normally categorized as: (1) airborne particulates; (2) noble
gases; (3) volatilized halogens (principally radioiodines); and (4) tritiated water. Depending upon
the source term and the objectives of the investigation, air sampling may be conducted outdoors
as well as indoors on behalf of a variety of human receptors. For example, routine outdoor air
samples may be taken for large population groups living within a specified radius of a nuclear
facility. On the other end of the spectrum, air samples may be taken for a single person or small
group of persons exposed occupationally to a highly localized source of airborne radioactivity.
The purpose of the samples being collected must, therefore, be well defined in terms of sampling
location, field sampling equipment, and required sample volumes. Due to the wide range of
conditions that may mandate air sampling, and the limited scope of this section, only generic
topics of air sampling will be discussed.
10.5.1 Sampler Components and Operation
Common components of air sampling equipment include a sample collector (i.e., filter), a sample
collector holder, an air mover, and a flow-rate measuring device.
The sample holder should provide adequate structural support while not damaging the filter,
should prevent sampled air from bypassing the filter, should facilitate changing the filter, and
should facilitate decontamination. A backup support that produces negligible pressure drop
should be used behind the filter to prevent filter distortion or deterioration. If rubber gaskets are
used to seal the filter to the backing plate, the gasket should be in contact with the filter along the
entire circumference to ensure a good fit.
Air movers or vacuum systems should provide the required flow through the filter and minimize
air flow reduction due to filter loading. Consideration should be given to the use of air movers
that compensate for pressure drop. Other factors to consider should include size, power
consumption, noise, durability, and maintenance requirements.
Each air sampler should be equipped with a calibrated air-flow measuring device with specified
accuracy. To calculate the concentrations of any radionuclide in air collected, it is necessary to
determine the total volume of air sampled and the associated uncertainties. The planning
documents should state who is responsible for making volume corrections. Also, the information
needed for half-life corrections for short-lived radionuclides needs to be recorded. If the mean
flow during a collection period can be determined, the total volume of air sampled can be readily
calculated.
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Accurate flow measurements and the total integrated sample volume of air can be obtained using
a mass flow meter and a totalizer. This direct technique of air flow measurement becomes
impractical at remote field locations, due to cost and exposure of the flow meter to harsh
environments. Other procedures for the measurement of air flow in sampling systems are
reviewed by Lippmann (1989a). The sample parameters (flow rate, volume, associated
uncertainties, etc.) should be recorded by the sample collector.
The collection medium or filter used depends on the physical and chemical properties of the
materials to be collected and counted. A variety of particulate filters (cellulose, cellulose-
asbestos, glass fiber, membrane, polypropylene, etc.) is available. The type of filter is selected
according to needs, such as high collection efficiency, particle-size selectivity, retention of alpha
emitters on the filter surface, and the compatibility with radiochemical analysis. The criteria for
filter selection are good collection efficiency for submicron particles at the range of face
velocities used, high particle and mass loading capacity, low-flow resistance, low cost, high
mechanical strength, low-background activity, compressibility, low-ash content, solubility in
organic solvents, nonhygroscopicity, temperature stability, and availability in a variety of sizes
and in large quantities. The manufacturer’s specifications and literature should provide a source
for filter collection efficiency. In the selection of a filter material, a compromise must be made
among the above-cited criteria that best satisfies the sampling requirements. An excellent review
of air filter material used to monitor radioactivity was published by Lockhart and Anderson
(1964). Lippmann (1989b) also provides information on the selection of filter materials for
sampling aerosols by filtration. See ANSI HPS N13.1, Annex D and Table D.1, for criteria for
the selection of filters for sampling airborne radioactive particles.
In order to select a filter medium with adequate collection efficiency, it may be necessary to first
determine the distribution of size of airborne particulates. Several methods, including impactors
(e.g., multistage cascade impactor) and electrostatic precipitators, can be used to classify particle
size. Waite and Nees (1973) and Kotrappa et al. (1974) discuss techniques for particle sizing
based on the flow discharge perturbation method and the HASL cyclone, respectively. These
techniques are not recommended for routine environmental surveillance of airborne particulates,
although their use for special studies or for the evaluation of effluent releases should not be
overlooked. Specific data on various filter materials, especially retention efficiencies, have been
reported by several authors (Lockhart and Anderson, 1964; Denham, 1972; Stafford, 1973;
ASTM STP555) and additional information is available from manufacturers.
10.5.2 Filter Selection Based on Destructive Versus Nondestructive Analysis
Pure cellulose papers are useful for samples to be dissolved and analyzed radiochemically, but
the analytical filter papers used to filter solutions are inefficient collectors for aerosols and clog
easily. Cellulose-asbestos filter papers combine fairly high efficiency, high flow rates, high
mechanical strength, and low pressure drops when loaded. They are very useful for collecting
large samples but present difficulties in dissolution, and their manufacture is diminishing because
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of the asbestos. Fiberglass filters can function efficiently at high flow rates, but require fluoride
treatment for dissolution and generally contain sufficient radioactive nuclides to complicate low-
activity analysis. Polystyrene filters are efficient and capable of sustaining high air flow rates
without clogging. They are readily destroyed for analysis by ignition (300 EC) or by wet washing
with oxidizing agents, and also are soluble in many organic liquids. They have the disadvantage
of low mechanical and tensile strength, and they must be handled carefully. Membrane filters are
excellent for surface collection efficiency and can be used for direct alpha spectrometry on the
filter. However, they are fragile and suffer from environmental dust loading. An alternative
choice for radionuclides in the environment is the polypropylene fiber filter. Teflon fiber filters
can be efficient, but they should be used with care because of their high ashing temperatures and
difficulties with digestion.
10.5.3 Sample Preservation and Storage
Since particulate air samples are generally dry samples that are chemically and physically stable,
they require no preservation. However, care must be exercised to avoid loss of sample from the
filter medium and the cross contamination among individual samples. Two common methods are
to fold filters symmetrically so that the two halves of the collection surface are in contact, or to
insert the filter into glassine envelopes. Filters should be stored in individual envelopes that have
been properly labeled. Filters may also be stored in special holders that attach on the filter’s edge
outside of the collection surface.
Since background levels of 222Rn and 220Rn progeny interfere with evaluating alpha air samples, a
holdup time of several hours to several days may be required before samples are counted.
Corrections or determinations can also be made for the contribution of radon or thoron progeny
present on a filter (Setter and Coats, 1961).
10.5.4 Special Cases: Collection of Gaseous and Volatile Air Contaminants
Prominent radionuclides that may exist in gaseous states include noble gases (e.g., 131/133Xe, 85Kr),
14C as carbon dioxide or methane, 3H as water vapor, gaseous hydrogen, or combined in volatile
organic compounds and volatilized radioiodines.
10.5.4.1 Radioiodines
The monitoring of airborne iodine, such as 129I and 131I, may be complicated by the probable
existence of several species, including particulate iodine or iodine bound to foreign particles,
gaseous elemental iodine, and gaseous non-elemental compounds of iodine. A well-designed
sampling program should be capable of distinguishing all possible iodine forms. While it may
not always be necessary to differentiate between the various species, care should be taken so that
no bias can result by missing one or more of the possible species. See ANSI HPS N13.1 (Annex
C.3) for information on collection media for radioiodine.
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In addition to the problems noted above, charcoal cartridges (canisters) for the collection of
radioiodine in air are subject to channeling. Several should be mounted in series to prevent loss
of iodine. Too high a sampling rate reduces both the collection efficiency and retention time of
charcoal filters, especially for the non-elemental forms of iodine (Keller et al., 1973; Bellamy,
1974). The retention of iodine in charcoal is dependent not only on charcoal volume, but also the
length of the charcoal bed. Typical air flow rates for particulate sampling of 30 to 90 L/min (1 to
3 ft3/min) are normally acceptable for environmental concentrations of radioiodine. The method
proposed by the Intersociety Committee (APHA, 1972) for 131I concentrations in the atmosphere
involves collecting iodine in its solid and gaseous states with an “absolute” particulate filter in
series with an activated charcoal cartridge followed by gamma spectrometric analysis of the filter
and cartridge. The Intersociety-recommended charcoal cartridges are e inch (16 mm) diameter
by 1½ inch (38 mm) deep containing 3 g of 12-to-30-mesh KI-activated charcoal. The minimum
detectable level using the Intersociety method is 3.7×10-3 Bq/m3 (0.1 pCi/m3). Larger cartridges
will improve retention, permitting longer sampling periods. A more sensitive system has been
described by Baratta et al. (1968), in which concentrations as low as 0.037 Bq/m3 (0.01 pCi/mL)
of air are attainable.
For the short-lived radioiodines (mass numbers 132, 133, 135), environmental sampling is
complicated by the need to obtain a sufficient volume for analysis, while at the same time,
retrieving the sample soon enough to minimize decay (with half-lives ranging from two hours to
21 hours). Short-period (grab) sampling with charcoal cartridges is possible, with direct counting
of the charcoal as soon as possible for gamma emissions.
Because of the extremely long half-life and normally low environmental concentrations,
129I
determinations must usually be performed by neutron activation or mass spectrometry analysis
after chemical isolation of the iodine. For concentrations of about 0.11 Bq/L (3×10-10 µCi/mL),
liquid scintillation counting can be used after solvent extraction (Gabay et al., 1974).
10.5.4.2 Gases
Sampling for radioactive gases is either done by a grab sample that employs an evacuated
chamber or by airflow through a medium, such as charcoal, water, or a variety of chemical
absorbers. For example, radioactive CO2 is most commonly extracted by passing a known
volume of air through columns filled with 3 M NaOH solution. After the NaOH is neutralized
with sulfuric acid, the CO2 is precipitated in the form of BaCO3, which then can be analyzed in a
liquid scintillation counter (NCRP, 1985). An alternative method for collecting noble gases by
compression into high-pressure canisters is described in Section 15.3.5.1, “Radioactive Gases.”
Because noble gases have no metabolic significance, and concern is principally limited to
external exposure, surveillance for noble gases is commonly performed by ambient dose rate
measurements. However, the noble gases xenon and krypton may be extracted from air by
adsorption on activated charcoal (Scarpitta and Harley, 1990). However, depending upon the
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analytical method and instrumentation employed, significant interference may result from the
presence of naturally occurring radioactive gases of 222Rn and 220Rn.
10.5.4.3 Tritium Air Sampling
In air, tritium occurs primarily in two forms: as water vapor (HOT) and as hydrogen gas (HT).
However, if tritiated hydrogen (HT) is a suspected component of an air sample (e.g., from a vent
or stack), the sampling must take place in the emission point of the gas. This is because the high
escape velocity of hydrogen gas causes rapid, isotropic dispersion immediately beyond the
discharge point. Tritiated organic compounds in the vapor phase or attached to particulate matter
occur only occasionally. To measure tritium as HT or in tritiated organic, the gas phase can be
oxidized, converting the tritium to HOT before desiccation and counting. For dosimetric
purposes, the fraction present as HT can usually be neglected, since the relative dose for a given
activity concentration of HOT is 400 times that for HT (NCRP, 1978). However, if HT analysis
is required, it can be removed from the atmosphere by oxidation to water (HOT) using
CuO/MnO2 at 600 EC (Pelto et al., 1975), or with air passed over platinum alumina catalyst
(Bixel and Kershner 1974). These methods also oxidize volatile tritiated organic compounds to
yield tritiated water (ANSI HPS N13.1, Annex H).
A basic system for sampling HOT consists of a pump, a sample collector, and a flow-measuring
or flow-recording device. Air is drawn through the collector for a measured time period at a
monitored flow rate to determine the total volume of air sampled. The total amount of HOT
recovered from the collector is divided by the total volume of air sampled to determine the
average HOT-in-air concentration of the air sampled. In some sampler types, the specific activity
of the water collected is measured and the air concentration is determined from the known or
measured humidity. Some common collectors are cold traps, tritium-free water, and solid
desiccants, such as silica gel, DRIERITE, or molecular sieve.
Cold traps are usually made of glass and consist of cooled collection traps through which sample
air flows. The trap is cooled well below the freezing point of water, usually with liquid nitrogen.
The water vapor collected is then prepared for analysis, usually by liquid scintillation counting.
Phillips and Easterly (1982) have shown that more than 95 percent HOT collection efficiency can
be obtained using a single cold trap. Often a pair of cold traps is used in series, resulting in a
collection efficiency in excess of 99 percent.
Gas-washing bottles (i.e., “bubblers”) filled with an appropriate collecting liquid (usually tritium-
free water) are used quite extensively for collecting HOT from air. HOT in the sample gas stream
“dissolves” in the collecting liquid. For the effective collection rate to remain the same as the
sample flow rate, the specific activity of the bubbler water must be negligible with respect to the
specific activity of the water vapor. Thus, the volume of air that can be sampled is ultimately
limited by the volume of water in the bubbler. However, except when sampling under conditions
of very high humidity, sample loss (dryout) from the bubbler usually limits collection time rather
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than the attainment of specific-activity equilibrium. Osborne (1973) carried out a thorough
theoretical and experimental evaluation of the HOT collection efficiency of water bubblers over a
wide range of conditions.
The use of silica gel as a desiccant to remove moisture from air is a common technique for
extracting HOT. The advantage of using silica gel is that lower HOT-in-air concentrations can be
measured, since the sample to be analyzed is not significantly diluted by an initial water volume,
which occurs when a liquid-sampling sink is used. Correcting for dilution is discussed in Rosson
et al. (2000).
10.5.4.4 Radon Sampling in Air
There are three isotopes of radon in nature: 222Rn is a member of the 238U decay chain; 220Rn is a
member of the 232Th decay chain; and 219Rn is a member of the 235U decay chain. Because of the
small relative abundance of the parent nuclides and the short half-lives of 220Rn (55 seconds) and
219Rn (4 seconds), the term “radon” generally refers to the isotope 222Rn. Owing to its ubiquitous
presence in soils, uranium mill tailings, underground mines, etc., and the health risks to large
populations and occupational groups, radon is perhaps the most studied radionuclide.
Consequently, many reports and articles have been published in the scientific literature dealing
with the detection methods and health risks from radon exposures. Many of them appear in
publications issued by the EPA, DOE, NCRP, NAS, and in radiation-related journals, such as
Health Physics and Radiation Research. Given the voluminous amount of existing information,
only a brief overview of the sampling issues that impact laboratory measurements can be
presented here.
Quantitative measurements of radon gas and its short-lived decay products can be obtained by
several techniques that are broadly categorized as grab sampling, continuous radon monitoring,
and integrative sampling. Each method imposes unique requirements that should be followed
carefully. Continuous monitors are not discussed further, since they are less likely to be used by
laboratory analysts. Guidance for radon sample collection was published by EPA’s Radon
Proficiency Program, which was discontinued in October 1998 (EPA 1992; 1993). Additional
sampling methods and materials are also presented in EPA (1994) and Cohen (1989).
In general, EPA’s protocols specify that radon sampling and measurements be made under
standardized conditions when radon and its progeny are likely to be at their highest concentra-
tions and maximum equilibrium. For indoor radon measurement, this implies minimum building
ventilation through restrictions on doors, windows, HVAC systems, etc. Also sampling should
not take place during radical changes in weather conditions. Both high winds and rapid changes
in barometric pressure can dramatically alter a building’s natural ventilation rate. Although
recommended measurements are likely to generate higher than actual average concentrations, the
benefit of a standardized sampling condition is that it is reproducible, least variable, and
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moderately conservative.
The choice among sampling methods depends on whether the measurement is intended as a
short-term, quick-screening measurement or as a long-term measurement that determines average
exposure or integration. In practice, the choice of a measurement system often is dictated by
availability. If alternative systems are available, the cost or duration of the measurement may
become the deciding factor. Each system has its own advantages and disadvantages, and the
investigator must exercise some judgment in selecting the system best suited to the objectives of
the investigation. Brief descriptions of several basic techniques used to sample air for radon and
its progeny are provided below.
GRAB SAMPLING
The term “grab sampling” refers to very short-term sampling. This method consists of evaluating
a small volume of air for either radon or radon decay product concentration. In the radon grab
sampling method, a sample of air is drawn into and subsequently sealed in a flask or cell that has
a zinc sulfide phosphor coating on its interior surfaces. One surface of the cell is fitted with a
window that is put in contact with a photomultiplier tube to count light pulses (scintillations)
caused by alpha disintegrations from the sample interacting with the zinc sulfide coating. The
general terms “flask” or “cell” are used in this discussion. Sometimes they are referred to as
“Lucas cells” (Lucas, 1982). The Lucas cell—or alpha scintillation counter—has specific
attributes, and not all radon cells are Lucas cells.
Several methods for performing such measurements have been developed. However, two
procedures that have been most widely used with good results are the Kusnetz procedure and the
modified Tsivogiou procedure. In brief, the Kusnetz procedure (Kusnetz, 1956; ANSI N13.8)
may be used to obtain results in working levels when the concentration of individual decay
products is not important. Decay products in up to 100 liters of air are collected on a filter in a
five-minute sampling period. The total alpha activity on the filter is counted any time between 40
and 90 minutes after sampling is completed. Counting can be done using a scintillation-type
counter to obtain gross alpha counts for a selected counting time. Counts from the filter are
converted to disintegrations using the appropriate counter efficiency. The disintegrations from
the decay products may be converted into working levels using the appropriate “Kusnetz factor”
for the counting time used.
The Tsivogiou procedure may be used to determine both working level and the concentration of
the individual radon decay products. Sampling is the same as in the Kusnetz procedure.
However, the filter is counted three separate times following collection. The filter is counted
between 2 and 5 minutes, 6 and 20 minutes, and 21 and 30 minutes after sampling is complete.
Count results are interpreted by a series of equations that calculate concentrations of the three
radon decay products and working levels.
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INTEGRATING SAMPLING DEVICES
By far, the most common technique for measuring radon is by means of integrating devices.
Integrating devices, like charcoal canister and the Electret-Passive Environmental Radon Monitor
(E-PERM®), are commonly employed as short-term integrating devices (two to seven days), while
alpha-track detectors are commonly used to provide measurements of average radon levels over
periods of weeks to months. Only charcoal canisters are discussed below, since they are more
likely to be used by laboratory analysts than electrets and alpha-track detectors.
CHARCOAL CANISTERS
Charcoal canisters are passive devices requiring no power to function. The passive nature of the
activated charcoal allows continual adsorption and desorption of radon. During the measurement
period, the adsorbed radon undergoes radioactive decay. Therefore, the technique does not
uniformly integrate radon concentrations during the exposure period. As with all devices that
store radon, the average concentration calculated using the mid-exposure time is subject to error
if the ambient radon concentration adsorbed during the first half of the sampling period is
substantially higher or lower than the average over the period. The ability of charcoal canisters to
concentrate noble gases or other materials may be affected by the presence of moisture,
temperature, or other gaseous or particulate materials that may foul the adsorption surface of the
charcoal.
10.6 Wipe Sampling for Assessing Surface Contamination
Surface contamination falls into two categories: fixed and loose. The wipe test (also referred to
as “swipes” or “smears”) is the universally accepted technique for detecting removable
radioactive contamination on surfaces (Section 12.5, “Wipe Samples”). It is often a stipulation of
radioactive materials licenses and is widely used by laboratory personnel to monitor their work
areas, especially for low-energy radionuclides that are otherwise difficult to detect with hand-
held survey instruments.” Frame and Abelquist (1999) provide a comprehensive history of using
smears for assessing removable contamination.
The purpose of the wipe test, organizational requirements or regulations, the nature of the
contamination, the surface characteristics, and the radionuclide all influence the conditions for
the actual wipe-test process. The wipe-test process should be standardized to ensure that the
sampling process is consistent. Since surfaces and wipe materials vary considerably, wipe-test
results provide qualitative indication of removable contamination. Fixed contamination will, by
definition, not be removed. Therefore, direct measurements may be necessary to determine the
extent on contamination.
The U.S. Nuclear Regulatory Commission (NRC, 1981) suggests that 100 cm2 areas be wiped
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and lists acceptable levels for surface contamination. However, NRC neither recommends the
collection device nor the manner in which to conduct such surveys, relying instead on
suggestions by the National Committee on Radiation Protection (1964) and the National Council
on Radiation Protection and Measurements (1978).
To maintain constant geometry in an automatic proportional counter, it is important that the wipe
remain flat during counting. Additionally, material that will curl can jam the automatic counter
and cause cross contamination or even destroy the instrument window. When it is necessary to do
destructive analysis on the wipe, it is critical that the wipe can easily be destroyed during the
sample preparation step, and that the residue not cause interference problems.
When wipes are put directly into liquid scintillation cocktail, it is important that the wipe not add
color or react with the cocktail. For maximum counting efficiency, as well as reproducibility, the
wipe either should dissolve in the cocktail or become transparent to the counting system.
10.6.1 Sample Collection Methods
10.6.1.1 Dry Wipes
Dry wipes (smears) for removable surface activity usually are obtained by wiping an area of 100
cm2 using a dry filter paper of medium hardness while applying moderate pressure. A 47 mm
diameter filter typically is used. This filter can be placed into a proportional counter for direct
counting. Smaller filters may be advantageous when the wipe is to be counted using liquid
scintillation counter for low energy beta-emitting radionuclides, such as tritium, 14C, and 63Ni.
The choice of wipe-test media and cocktail is critical when counting low-energy beta-emitting
radionuclides in liquid scintillation counters, because the liquid scintillation counting process
depends on the detection of light produced by the interaction of the radiation with the cocktail.
The filter may absorb energy from the radiation (see “Quench” under Section 15.5.3.3). A filter
that is in the cocktail can prevent light from being seen by both detectors at the same time. If
light is produced and seen by only one of the two detectors typical in liquid scintillation counting
systems, then the count will be rejected as noise. A filter/cocktail combination that produces a
sample that is transparent to the counting system is the best combination for liquid scintillation
counting. Background produced by the filter may also be a consideration.
For surveys of small penetrations, such as cracks or anchor-bolt holes, cotton swabs are used to
wipe the area of concern. The choice of material for wipe-testing for special applications is
critical (Hogue, 2002), and the material selected can significantly affect the efficiency of the
removal of surface radioactivity. Usually, switching wipe test material should be avoided during
a project, when possible. Samples (dry wipes or swabs) are placed into envelopes or other
individual containers to prevent cross-contamination while awaiting analysis. Dry wipes for
alpha and medium- or high-energy beta activity can be evaluated in the field by counting them on
an integrating scaler unit with appropriate detectors; the same detectors utilized for direct
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measurements may be used for this purpose. However, the more common practice is to return the
dry wipes to the laboratory, where analysis can be conducted using more sensitive techniques.
The most common method for analyzing wipe samples is to use a proportional counter. For very
low-energy beta emissions, wipe samples are commonly analyzed by liquid scintillation
counting.
Additional information on wipe-test counting can be found in ISO (7503-1; 7503-2; 7503-3),
which apply to surfaces of equipment and facilities, containers of radioactive materials, and
sealed sources. Abelquist (1998) discusses using smears to assess the quantity of removable
contamination as it applies to radiological surveys in support of decommissioning, compliance
with DOT shipping criteria, and operational radiological protection programs.
10.6.1.2 Wet Wipes
Although dry wipes are more convenient to handle, and there are fewer chances of cross
contamination, a general limitation of dry wipes is their low recovery of surface contamination.
The low recovery using dry wipes is due to the higher affinity for the surface by the contaminant
than for the filter paper. Several studies have shown that for maximum sensitivity, a wipe
material moistened with a suitable solvent may be indicated. For example, Ho and Shearer
(1992) found that alcohol-saturated swabs were 100 times more efficient at removing
radioactivity than dry swabs.
In another study, Kline et al. (1992) assessed the collection efficiency of wipes from various
surfaces that included vinyl floor tile, plate glass, and lead foil. Two different collection devices,
cotton swabs and 2.5 cm diameter glass fiber filter disks, were evaluated under various collection
conditions. Dry wipes were compared to collections made with the devices dampened with
different amounts of either distilled H2O, 70 percent ethanol, or a working-strength solution of a
multipurpose laboratory detergent known to be effective for removing contaminants from
laboratory glassware (Manske et al., 1990).
The entire area of each square was manually wiped in a circular, inwardly-moving motion with
consistent force. The collection capacity of each device was estimated by wiping progressively
larger areas (multiple grids) and comparing the measured amounts of radioactivity with the
amounts placed on the grids.
Collection efficiency varied with both the wipe method and the surface wipe. Contamination was
removed most readily from unwaxed floor tile and glass; lead foil released only about one-half
the radioactivity. Stainless steel, another common laboratory surface, has contamination retention
properties similar to those of glass.
In most cases, collection was enhanced by at least a factor of two after dampening either the
swabs or filter disks with water. Dampening with ethanol or the detergent produced removals that
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were statistically indistinguishable from samples dampened with an equal amount of water.
The filter disks had a higher collection capacity for removable contaminants than cotton swabs,
nearly doubling the radioactivity removed for each doubling of surface area wiped. Variability
within all methods was high, with coefficients of variation ranging from 2 to 30 percent.
For the moistened wipes, wipe efficiency depended on three factors, including the polarity of the
solvent, the polarity of the contaminant being measured, and the affinity of the compound for the
contaminated surface. For a solvent to readily dissolve a compound (i.e., remove it from the
surface), the solvent and the compound must have similar polarities. Nonpolar solvents include
ethyl acetate and petroleum ether; for polar solvents, water or methanol may be used (Campbell
et al., 1993). There are other factors that influence the affinity of a compound for a surface,
including porosity of the surface and available binding sites on the surface. One important factor
that influences binding capacity is the type of treatment that a surface has received. When
working with a surface treated with a nonpolar wax, such as that used on floor tile, a nonpolar
compound will be adsorbed to the surface, which further limits recovery. Recovery from
absorbent surfaces, such as laboratory bench paper or untreated wood, also may be poor due to
the porous nature of the surface.
10.6.2 Sample Handling
Filter paper or other materials used for wipe tests in the field should be placed in separate
containers that prevent cross contamination during transport and allow for labeling of each
sample. Plastic bags, paper or glassine envelopes, and disposable plastic petri dishes are typically
used to store and transport wipe samples. Field workers can use plastic or rubber gloves and
forceps when applying the wipe material to a surface and during handling as each wipe is placed
into a container. Protection of the sample wipe surface is the main concern when a wipe must be
placed in a container for transport. If a scintillation vial or planchet will be used in the laboratory,
then a field worker may put wipes directly into them. Planchets containing loose or self-sticking
wipes can also be put into self-sealing plastic bags to separate and protect the integrity of the
sample’s surface. Excessive dust and dirt can cause self adsorption or quenching, and therefore
should be minimized.
10.6.3 Analytical Considerations for Wipe Material Selection
Some analytical considerations for selecting wipe materials are included here, because field
sample collection and subsequent sample counting usually occur without such intervening steps
as sample preparation, sample dissolution, or separation. It is critical, therefore, to ensure that the
wipe material used for collection and the actual counting process are compatible. The following
paragraphs offer some general guidance for proportional and liquid scintillation counting. The
final paragraph discusses some key issues that impact dissolution of wipes.
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The wipe should remain flat during counting in order to maintain optimum counting geometry in
an automatic proportional counter. Wipe material that can curl may jam an automatic counter and
destroy the detector window of the counter, become a source of cross-contamination of samples,
or contaminate the counting system. Most proportional counting systems use two-inch (5 cm)
planchets, and the wipe should fit into the planchet. If not, a subsample will need to be taken, and
subsampling adds additional uncertainty due to sample homogeneity considerations.
When wipes are put directly into a liquid scintillation cocktail, the wipe should not add color or
react with the cocktail. For maximum counting efficiency and reproducibility, the wipe either
should dissolve or become transparent to the counting system. When wipes that have an adhesive
backing are put directly in a liquid scintillation cocktail, the adhesive may not dissolve
completely. Compatibility should be checked before use to prevent problems during actual
sample analysis. Special cocktails are available to dissolve filters, but they may cause a waste-
disposal problem. Since the possible combination of cocktails and filters is large, only general
guidance is provided here. Consult the manufacturer’s specifications for specific guidance.
When it is necessary to do destructive analysis on a wipe, select a wipe that can be destroyed
easily or dissolved during the sample preparation steps, and the residue will not cause
interference problems in the subsequent counting. Some wipes have adhesive backing; the wipe
materials may dissolve easily but the adhesive backing may not. Additional steps would then be
necessary to destroy the adhesive backing. Dissolving glass-fiber wipes may require the use of
hydrofluoric acid. These extra processes can add time or cost to the analysis. See Section 10.5.2
(“Filter Selection Based on Destructive Versus Nondestructive Analysis”), Section 12.5 (“Wipe
Samples”) and Chapter 13 (Sample Dissolution) for additional information.
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Maron, S.H. and J. B. Lando. 1974. Fundamentals of Physical Chemistry. New York: Macmillan
Publishing Company.
MARSSIM. 2000. Multi-Agency Radiation Survey and Site Investigation Manual, Revision 1.
NUREG-1575 Rev 1, EPA 402-R-97-016 Rev1, DOE/EH-0624 Rev1. August. Available
from www.epa.gov/radiation/marssim/.
Martin, J.E. and J.M. Hylko. 1987a. “Formation of Tc-99 in Low-Level Radioactive Waste
Samples from Nuclear Plants,” Radiation Protection Management, 4:6, pp. 67-71.
Martin, J.E. and J.M. Hylko. 1987b. “Measurement of 99Tc in Low-Level Radioactive Waste
from Reactors Using 99Tc as a Tracer,” Applied Radiation and Isotopes, 38:6, pp. 447-450.
Milkey, R.G. 1954. “Stability of Dilute Solutions of Uranium, Lead, and Thorium Ions,” Anal.
Chem. 26:11, pp. 1800-1803.
National Academy of Sciences (NAS). 1960. The Radiochemistry of Technetium. Office of
Technical Services, Washington, DC.
National Committee on Radiation Protection. 1964. Safe Handling of Radioactive Materials.
NCRP Report 30, Washington, DC.
National Council on Radiation Protection and Measurements (NCRP). 1978. Instrumentation
and Monitoring Methods for Radiation Protection. NCRP Report 57.
National Council on Radiation Protection and Measurements (NCRP). 1985. A Handbook of
Radioactivity Measurements Procedures. NCRP Report 81.
National Council on Radiation Protection and Measurements (NCRP). 1987. Use of Bioassay
Field and Sampling Issues That Affect Laboratory Measurements
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Procedures for Assessment of Internal Radionuclides Deposition. NCRP Report No. 87.
National Institute for Occupational Safety and Health (NIOSH). 1983. Industrial Hygiene
Laboratory Quality Control-587. NIOSH, Cincinnati, Ohio.
Naval Sea Systems Command (NAVSEA), 1997. Navy Environmental Compliance Sampling
and Field Testing Procedures Manual, NAVSEA T0300-AZ-PRO-010, 10 June 1997
U.S. Nuclear Regulatory Commission (NRC). Acceptable Concepts, Models, Equations, and
Assumptions for a Bioassay Program. NRC Regulatory Guide 8.9. Revision 1, September
1993.
U.S. Nuclear Regulatory Commission (NRC). Applications of Bioassay for Uranium. NRC
Regulatory Guide 8.11. June 1974.
U.S. Nuclear Regulatory Commission (NRC). 1977. Estimating Aquatic dispersion of Effluents
from Accidental and Routine Reactor Releases for the Purpose of Implementing Appendix I.
NRC Regulatory Guide 1.113.
U.S. Nuclear Regulatory Commission (NRC). Applications of Bioassay for I-125 and I-131.
NRC Regulatory Guide 8.20. Revision 1, September 1979.
U.S. Nuclear Regulatory Commission (NRC). Applications of Bioassay for Fission and
Activation Products. NRC Regulatory Guide 8.26. September 1980.
U.S. Nuclear Regulatory Commission (NRC). Bioassays at Uranium Mills. NRC Regulatory
Guide 8.22. Revisoin 1, August 1988.
U.S. Nuclear Regulatory Commission (NRC). Criteria for Establishing a Tritium Bioassay
Program. NRC Regulatory Guide 8.32. July 1988.
U.S. Nuclear Regulatory Commission (NRC). 1981. Radiation Safety Surveys at Medical
Institutions. NRC Regulatory Guide 8.23.
U.S. Nuclear Regulatory Commission (NRC). 1990. Model Feasibility Study of Radioactive
Pathways From Atmosphere to Surface Water. NUREG/CR-5475, Washington, DC.
U.S. Nuclear Regulatory Commission (NRC). 1992. National Profile on Commercially
generated Low-Level Radioactive Mixed Waste. NUREG/CR-5938, Washington, DC.
Osborne, R.V. 1973. “Sampling for Tritiated Water Vapor,” in Proceedings of the 3rd
International Congress. International Radiation Protection Association, CONF-730907-P2,
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1973:1428-1433.
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Experience in the Release of Low-Level Waste to Rivers and Lakes,” in Proceedings of the
Third United National International Symposium on the Peaceful Uses of Atomic Energy Vol.
14:62-71.
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75-50, p. 35 (Argonne National Laboratory, Lemont, IL).
Phillips, J.E. and C.E. Easterly. 1982. “Cold Trapping Efficiencies for Collecting Tritiated Water
Entrained in a Gaseous Stream,” Rev. Sci. Instrum., 53:1.
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11 SAMPLE RECEIPT, INSPECTION, AND TRACKING
11.1 Introduction
This chapter provides guidance on laboratory sample receiving and surveying, inspecting,
documenting custody, and assigning laboratory tracking identifiers (IDs). These topics are
presented sequentially in this chapter, but they may be performed in a different order. The
chapter is directed primarily at laboratory personnel (as are all of the Part II chapters), although
the project manager and field personnel need to be aware of the steps involved in sample receipt,
inspection, and tracking. Within MARLAP, the “sample receipt” process includes the surveying
of the package and sample containers for radiological contamination and radiation levels.
“Sample inspection” means checking the physical integrity of the package and samples,
confirming the identity of the sample, confirming field preservation (if necessary), and recording
and communicating the presence of hazardous materials. “Laboratory sample tracking” is a
process starting with logging in the sample and assigning a unique laboratory tracking identifier
(numbers and/or letters) to be used to account for the sample through analyses, storage, and
shipment. Laboratory tracking continues the tracking that was initiated in the field during sample
collection (see Section 10.2, “Field Sampling Plan: Non-Matrix-Specific Issues”).
This chapter focuses on sample receipt, inspection, and tracking of samples in the laboratory
because these are the three modes of initial control and accountability (Figure 11.1). Sample
receipt and inspection activities need to be done in a timely manner to allow the laboratory and
field personnel to resolve any problems (e.g., insufficient material collected, lack of field
preservation, etc.) with the samples received by the laboratory as soon as is practical. Effective
communications between field personnel and the laboratory not only facilitates problem
resolution but also prevents unnecessary delays in the analytical process.
Other relevant issues, including the laboratory’s radioactive materials license conditions and
proper operating procedures, are also discussed because these topics are linked to receipt,
inspection, and tracking activities. The result of the sample receipt and inspection activities is to
accept the samples as received or to perform the necessary corrective action (which may include
rejecting samples). Health and safety information on radiological issues can be found in NRC
(1998a; 1998b).
11.2 General Considerations
11.2.1 Communication Before Sample
Receipt
Before the samples are received, the laboratory
should know the approximate number of
samples that will be received within a specific
Contents
11.1 Introduction .......................... 11-1
11.2 General Considerations ................. 11-1
11.3 Sample Receipt ....................... 11-5
11.4 Sample Inspection ..................... 11-8
11.5 Laboratory Sample Tracking ............ 11-11
11.6 References .......................... 11-13
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Field Sample Shipment
(see Chapter 10)
Tracking Documents
 Number and type of samples along
with field sample number
 Field processing and preservation
 Analysis requested
Sample received in designated area
 Authorized user notified for radiological
screening of package
 Check for evidence of breakage or
leakage of exterior of shipping
package, then shipping containers.
If found, radiologically survey and
decontaminate if necessary
 Radiological survey
 License requirements
 Chain-of-custody procedures if
required
Sample Receipt
Sample Inspection
In designated rad receiving/prep area:
 Check container labels against sample
 Check radionuclides requested
against tracking documents
 Check tamper seals
 Verify preservation against tracking
documents
 Check field preparation against
tracking documents
Any discrepancies in the following will
result in corrective action:
 Survey limits
 Expected radionuclides
 Number and type of samples
 Tracking Documents
SAMPLE
REJECTED
SAMPLE
ACCEPTED
Laboratory
Tracking
Check with client
relative to sample
disposition
Short-term
sample storage
or sample
prep/analysis
laboratory
FIGURE 11.1 — Overview of sample receipt, inspection, and tracking
period of time and the types of analyses that are expected for the samples. Laboratory personnel
should be provided with a contact in the field and with means of contacting the person
(telephone, FAX, e-mail). The information about the client, points of contact, number of samples,
and types of analyses can be entered into the laboratory information management system (LIMS)
to facilitate communication between the laboratory—in both the sample receipt area and the
project management area—and the project manager. Communication between laboratory
personnel and project staff in the field allows the parties to coordinate activities, schedules, and
sample receipt. In particular, the project manager should provide to the laboratory any special
instructions regarding the samples before shipment of samples. This information serves to notify
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the laboratory of health and safety concerns and provides details that will affect analytical
procedures, sample disposition, etc. For example, without this communication, a laboratory
might receive a partial shipment and not realize that samples are missing. Furthermore, advance
communications allow laboratory staff to arrange for special handling or extra storage space
should the need arise.
Planning for the samples to be received at the laboratory starts during the development of the
appropriate plan document and the statement of work (SOW) and continues through the
communication between the project staff in the field and the laboratory. For example, the
laboratory could use its LIMS to generate labels and bar-codes for the appropriate containers to
be used in the field. This process would assist in assigning appropriate sample IDs for the
laboratory tracking system, which starts with sample receipt. The laboratory should instruct the
field staff to place the tracking documents on the inside of the cooler lid for easy access and to
include any other pertinent information (field documentation, field surveying information, etc.).
11.2.2 Standard Operating Procedures
A laboratory should have standard operating procedures (SOPs) for activities related to sample
receipt, inspection, and tracking. Some typical topics that might be addressed in laboratory SOPs
are presented in Table 11.1. For example, the laboratory should have an SOP that describes what
information should be included in the laboratory sample tracking system. Laboratory SOPs
should describe chain-of-custody procedures giving a comprehensive list of the elements in the
program such as signing the appropriate custody forms, storing samples in a secure area, etc.
(ASTM D4840; ASTM D5172; EPA, 1995).
TABLE 11.1 — Typical topics addressed in standard operating procedures related to
sample receipt, inspection, and tracking
Sample
Receipt:
Order and details for activities associated with receiving shipments of samples
Surveying methods
Inspection: Check physical integrity
Confirm sample identification
Identify/manage hazardous materials
pH measurement instructions
Use the laboratory information management system (LIMS) to assign laboratory sample IDs
Tracking: Maintain chain of custody and document sample handling during transfer from the field to
the laboratory, then within the laboratory
Ensure proper identification of samples throughout process
Procedures to quickly determine location and status of samples within laboratory
Custodian: Execution of responsibilities of the sample custodian
Forms/Labels: Examples of forms and labels used to maintain sample custody and document sample
handling in the laboratory
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The laboratory needs to establish corrective action guidelines (Section 11.3.3) as part of every
SOP for those instances when a nonconformance is noted. Early recognition of a nonconfor-
mance will allow the project manager and the laboratory more options for a quick resolution.
11.2.3 Laboratory License
Laboratories that handle radioactive materials are required (with few exceptions, such as certain
U.S. Department of Energy National Laboratories and Department of Defense laboratories) to
have a radioactive materials license issued by the NRC or the Agreement State in which the
laboratory operates. The radioactive materials license lists the radionuclides that the laboratory
can possess, handle, and store. In addition, the license limits the total activity of specific
radionuclides that can be in the possession of the laboratory at a given time.
The client must have a copy of the current radioactive materials license for the facility to which
the samples are being shipped. The laboratory staff and the project manager all need to be aware
of the type of radionuclide(s) in the samples and the total number of samples to be sent to the
laboratory. This information should be included in the appropriate plan document and SOW prior
to sampling.
The laboratory is required by the license to maintain a current inventory of certain radioactive
materials present in the facility. The radioactive materials license also requires the laboratory to
develop and maintain a radiation protection plan (NRC, 1998b) that states how radioactive
samples will be received, stored, and disposed. The laboratory will designate an authorized user
(NRC, 1998b) to receive the samples. A Radiation Safety Officer (RSO) may be an authorized
user, but not always. NRC (1998b) gives procedures for the receipt of radioactive samples during
working hours and non-working hours.
11.2.4 Sample Chain-of-Custody
Sample chain-of-custody (COC) is defined as a process whereby a sample is maintained under
physical possession or control during its entire life cycle, that is, from collection to disposal
(ASTM D4840—see Section 10.2.7). The purpose of COC is to ensure the security of the sample
throughout the process. COC procedures dictate the documentation needed to demonstrate that
COC is maintained. When a sample is accepted by the laboratory it is said to be in the physical
possession or control of the laboratory. ASTM D4840 states that a sample is under “custody” if it
is in possession or under control so as to prevent tampering or alteration of its characteristics.
If the samples are transferred under COC, the relinquisher and the receiver should sign the
appropriate parts of the COC form with the date and time of transfer (see Figure 10.1). After
receipt and inspection the samples should be kept in a locked area or in an area with controlled
access.
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COC is not a requirement for all samples. COC is most often required when the sample data may
be used as legal evidence. The project plan should state whether COC will be required. The
paperwork received with the samples should also indicate whether COC has been maintained
from the time of collection and must be maintained in the laboratory. If the laboratory has been
informed that COC procedures should be followed, but it appears that appropriate COC
procedures have not been followed (before or after sample receipt at the laboratory) or there are
signs of possible sample tampering when the samples arrive, the project manager should be
contacted. The problem and resolution should be documented. Additional information on COC
can be found in EPA (1985).
11.3 Sample Receipt
Laboratory sample receipt occurs when a package containing samples is accepted, the package
and sample containers are surveyed for external surface radiological contamination and radiation
level, and the physical integrity of the package and samples is checked. Packages include the
shipping parcel that holds the smaller sample containers with the individual samples (see Section
11.3.2 on radiological surveying). Also note that topics and activities covered in Section 11.3
appear in a sequence but, in many cases, these activities are performed simultaneously during
initial receiving activities (i.e., package surveying and observation of its physical integrity).
11.3.1 Package Receipt
Some laboratories require arriving samples to go through a security inspection process at a
central receiving area before routing them to the appropriate laboratory area(s). In addition, if
samples are shipped by an air transport carrier, the shipping containers may be subject to airport
security. In these cases, the container housing the samples may be opened and the samples
inspected and reinserted in an order not consistent with the original packaging. In these cases, it
is imperative that each individual sample container have a permanent identifier either in indelible
ink or as a label affixed on the side of the sample container (see Section 10.2.4, “Container Label
and Sample Identification Code”). Within each shipping container, a separate sample packing
slip or tracking documents that lists the samples (by sample ID) for the container should be
included.
Packages should be accepted only at designated receiving areas. Packages brought to any other
location by a carrier should be redirected to the appropriate receiving area. All packages labeled
RADIOACTIVE I, II, or III require immediate notification of the appropriate authorized user (NRC,
1998b).
A sample packing slip or tracking documents is required and must be presented at the time of
receipt, and the approximate activity of the shipment should be compared to a list of acceptable
quantities. If known, the activity of each radionuclide contained in the shipment must be
Sample Receipt, Inspection, and Tracking
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reviewed relative to the total amount of that radionuclide currently on site to ensure that the
additional activity will not exceed that authorized by the NRC or Agreement State in the
laboratory’s license.
Surveying measures described in Section 11.3.2 may indicate that the samples are more
radioactive than expected and that the radiation license limit may be exceeded. The laboratory
should take extra precautions with these samples, but the survey results should be verified. The
federal, state, or local agency should be contacted immediately when verified license limits are
exceeded. The laboratory must respond quickly to stay in compliance with its license.
If the package is not accepted by the laboratory, the laboratory should follow corrective-action
procedures prescribed in the radiation materials license, the appropriate plan document (if this is
a reasonable possibility for the project), and the laboratory’s SOPs. The project manager should
be contacted about possible disposition of any samples.
11.3.2 Radiological Surveying
In addition to ensuring compliance with the laboratory’s license and verifying estimates of radio-
nuclide activity (Section 11.3.1), the radiological surveying of packages during sample receipt
serves to identify and prevent the spread of external contamination. All packages containing
samples for analysis received by the laboratory should be surveyed for external contamination
using a wipe (sometimes referred to as a “swipe”) and for surface exposure rate using the approp-
riate radiation survey meter. Exceptions may include known materials intended for analysis as:
well-characterized samples, bioassays, or radon and associated decay products in charcoal media
(exceptions should be listed in the laboratory SOP). Surveying of packages and sample
containers received in the laboratory should be conducted in accordance with the laboratory’s
established, documented procedures and the laboratory radiation protection and health and safety
plan. The exterior of the package is surveyed first; if there is no evidence of contamination or that
the laboratory licence would be exceeded, the package is opened up and the sample containers
surveyed individually. These procedures should include the action level and appropriate action as
established by the facility. Personnel performing surveying procedures should be proficient in the
use of portable radiation surveying instruments and knowledgeable in radiological contamination
control procedures. Health and safety considerations are affected by the suspected or known
concentrations of radionuclides in a sample or the total activity of a sample.
Radiation surveying is normally conducted using Geiger-Mueller (GM) detectors, ionization
chambers, micro-R meters, or alpha scintillation probes, as appropriate. The laboratory should
refer to any information they obtained before receipt of samples or with the samples, especially
concerning the identity and concentration of radioactive and chemical constituents in the
samples. Radiological surveying needs to be performed as soon as practical after receipt of the
package, but not later than three hours (10 CFR 20.1906) after the package is received at the
licensee’s facility for packages received during normal working hours. For packages received
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outside of normal working hours, the surveying must be performed no later than three hours from
the beginning of the next workday.
Survey the exterior of a labeled package for radioactive contamination (10 CFR 20.1906). If the
package is small (less than 100 cm2), the whole package should be wiped (swiped). Wipes are not
always used, but if there is reason to believe that something has leaked, then wipes should be
used. This survey is performed to detect possible violations of Department of Transportation
(DOT) packaging and labeling regulations, as well as to determine the possible presence of
gamma- and some beta-emitting radionuclides that may require special handling. Also, such a
survey can help to avoid introducing a high-activity sample into a low-activity area. NRC
(1998b) gives the following sample model for opening packages containing radioactive material:
Wear gloves to prevent hand contamination.
Visually inspect the package for any sign of damage (e.g. crushed, punctured). If damage is
noted, stop and notify the RSO.
Check DOT White I, Yellow II, or Yellow III label or packing slip for activity of contents, so
shipment does not exceed license possession limits.
Monitor the external surfaces of a labeled package according to specifications in Table 8.4,
Section 13.14, Item 10 [of NRC, 1998b].
Open the outer package (following supplier’s directions if provided) and remove packing
slip. Open inner package to verify contents (compare requisition, packing slip and label on
the bottle or other container). Check integrity of the final source container (e.g., inspecting
for breakage of seals or vials, loss of liquid, discoloration of packaging material, high count
rate on smear). Again check that the shipment does not exceed license possession limits. If
you find anything other than expected, stop and notify the RSO.
Survey the packing material and packages for contamination before discarding. If contamina-
tion is found, treat them as radioactive waste. If no contamination is found, obliterate the
radiation labels prior to discarding in the regular trash.
Maintain records of receipt, package survey, and wipe test results.
Notify the final carrier and by telephone, telegram, mailgram, or facsimile, the administrator
of the appropriate NRC Regional Office listed in 10 CFR 20, Appendix D when removable
radioactive surface contamination exceeds the limits of 10 CFR 71.87(i); or external radiation
levels exceed the limits of 10 CFR 71.47.
In addition to these, laboratories may have additional internal notifications or procedures.
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11.3.3 Corrective Action
The laboratory’s SOPs should specify corrective actions for routine and non-routine sample
problems, including deficiency in sample volume, leaking samples, and labeling errors. The
appropriate corrective action may require consulting the project manager and other laboratory
personnel. Timely response can allow for a broader range of options and minimize the impact of
the sample problem on the project. The laboratory should document the problem, the cause (if
known), the corrective action taken, and the resolution of each problem that requires corrective
action. The documentation should be included in the project files.
11.4 Sample Inspection
After sample receipt, the next steps are to confirm that the correct sample has been sent, to check
that the appropriate field preservation and processing have been performed, and to identify any
hazardous chemicals.
Documents accompanying the samples should be reviewed upon receipt of the samples at the
laboratory. If the proper paperwork is not present, the project manager should be notified. Data
recorded on the paperwork, such as collection dates, sample descriptions, requested analyses, and
field staff personnel, should be compared to data on the sample containers and other documen-
tation. Any deficiencies or discrepancies should be recorded by the laboratory and reported to the
project manager. The documents can provide data useful for health and safety surveying,
tracking, and handling or processing of critical short-lived radionuclides.
11.4.1 Physical Integrity of Package and Sample Containers
Sample containers should be thoroughly inspected for evidence of sample leakage. Leakage can
result from a loose lid, sample container puncture, or container breakage. Packages suspected to
contain leaking sample containers should be placed in plastic bags. The authorized user or alter-
nate authorized user must be notified immediately for assistance. If leakage has occurred, approp-
riate radiological and chemical contamination controls should be implemented. Sample materials
that have leaked or spilled are normally not suitable for analysis and should be properly disposed.
In all cases, the laboratory’s management and project manager should be notified of leaks,
breakage, spills, and the condition of sample materials that remain in the original containers.
Sample containers that have leaked (from a loose lid or puncture) may still hold enough sample
for the requested analyses, so the laboratory should first determine whether sufficient representa-
tive sample remains. The sample is not usually analyzed if its integrity was compromised or is in
doubt. Unless appropriate information is provided in the project plan or SOW, the project
manager should determine whether or not the sample materials can be used for analysis or if new
samples are required.
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Packages, cooler chests, or individual sample containers may arrive at the laboratory bearing
custody seals. These seals provide a means to detect unauthorized tampering. When packages or
samples arrive with custody seals, they should be closely inspected for evidence of tampering.
Custody seals are made from material that cannot be removed without tearing. If a custody seal is
torn or absent, sample tampering may have occurred. This evidence of possible tampering is
generally sufficient to preclude use of the sample for laboratory analyses. The project manager
should be notified of the condition of the custody seal to determine if new samples are needed.
Observations regarding the condition of the custody seals should be recorded according to the
laboratory’s standard procedures.
11.4.2 Sample Identity Confirmation
Visual inspection is the means to confirm that the correct sample has been received. Verifying
the identity of a sample is a simple process where the appearance, sample container label, and
chain-of-custody record or tracking documents are compared. If all three sources of information
identify the same sample, then the sample is ready for the next step. If the sample label indicates
the sample is a liquid and the container is full of soil, this discrepancy would indicate nonconfor-
mance. If the sample label states that there is 1,000 mL of liquid and there only appears to be 200
mL in the container, there may be nonconformance. Visual inspection can be used to:
Verify identity of samples by matching container label IDs and tracking documents;
Verify that the samples are as described by matrix and quantity;
Check the tamper seal (if used);
Verify field preparation (e.g., filtering, removing extraneous material ), if indicated; and
Note any changes to samples’ physical characteristics that are different than those in the
tracking documents.
11.4.3 Confirmation of Field Preservation
For those liquid samples requiring acid preservation, pH measurements may be performed on all
or selected representative liquid samples to determine if acid has been added. The temperature of
the sample may also be part of field preservation and the actual measured temperature should be
compared to the specified requirements in the documentation.
11.4.4 Presence of Hazardous Materials
The presence of hazardous materials in a sample typically creates the need for additional health
and safety precautions when handling, preparing, analyzing, and disposing samples. If there is
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documentation on the presence of non-radiological hazardous constituents, the project manager
should notify the laboratory about the presence of these chemicals. These chemical contaminants
should be evaluated by the laboratory to determine the need for special precautions. The
laboratory can also perform preliminary sample surveying for chemical contaminants using
surveying devices such as a photoionization detector for volatile components. The presence of
suspected or known hazardous materials in a sample should be identified, if possible, during
project planning and documented in the plan document and SOW. Visual inspection can also be
used such as checking the color of the sample (e.g., a green-colored water sample may indicate
the presence of high chromium levels). The presence of suspected or known hazardous materials
determined in the field should be communicated to the laboratory prior to the arrival of samples
and noted on documentation accompanying the samples to the laboratory. If no documentation on
non-radiological hazardous constituents is available, the laboratory should review previous
experience concerning samples from the site to assess the likelihood of receiving samples with
chemical contaminants. The laboratory’s chemical hygiene officer and the project manager
should be notified about the presence of potentially hazardous chemical contaminants.
11.4.5 Corrective Action
Visual inspection can also verify whether field sample preparation was performed as stated in
accompanying documentation. Samples that were not filtered in the field or that reacted with the
preservative to form a precipitate may represent a significant problem to the laboratory. If it
appears that the sample was filtered in the field (e.g., there is no corresponding filter or there are
obviously solid particles in a liquid sample), the liquid generally will be analyzed as originally
specified. Laboratory personnel should check the project plan or SOW to see if the filter and
filtered materials require analyses along with the filtered sample. If it appears that the sample was
not filtered in the field (i.e., there is no corresponding filter or there are obviously solid particles
in a liquid sample), sample documentation should be reviewed to determine if a deviation from
the project plan was documented for the sample. It may be appropriate to filter the sample in the
laboratory. The project manager should be notified immediately to discuss possible options such
as filtering the sample at the laboratory or collecting additional samples.
One example of a corrective action for inspection is, if the pH is out of conformance, it may be
possible to obtain a new sample. If it is not possible or practical to obtain a new sample, it may
be possible to acidify the sample in the laboratory.
Visual inspection can serve to check certain aspects of sample collection. For example, if the
SOP states that a soil sample is supposed to have twigs, grass, leaves, and stones larger than a
certain size removed during sample collection and some of this foreign material is still included
as part of the sample, this discrepancy results in a nonconformance.
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11.5 Laboratory Sample Tracking
Sample tracking should be done to ensure that analytical results are reported for the “correct”
sample. Sample tracking is a process by which the location and status of a sample can be
identified and documented. The laboratory is responsible for sample tracking starting with receipt
(at which time a unique laboratory sample ID is assigned), during sample preparation, and after
the performance of analytical procedures until final sample disposition. The process of sample
tracking begins the moment a field worker assigns an identification number (based on the
information provided in the appropriate plan document) and documents how materials are
collected. The way samples are transported from the field to the laboratory should be
documented. The sample receipt procedures and documentation should be consistent when
applicable with 10 CFR Part 20 Subpart J, and the client’s requirements as stated in the
appropriate plan document or statement of work.
11.5.1 Sample Log-In
Laboratory sample IDs should be assigned to each sample in accordance with the laboratory’s
SOP on sample codes. Each sample should receive a unique sample ID by which it can be logged
into the LIMS, scheduled for analysis, tracked, and disposed. Information to be recorded during
sample log-in should include the field sample identification number, laboratory sample ID, date
and time samples were collected and received, reference date for decay calculations, method of
shipment, shipping numbers, condition of samples, requested analyses, number and type of each
sample, quality control requirements, special instructions, and other information relevant to the
analysis (e.g., analytical requirements or MQOs) and tracking of samples at the laboratory.
Laboratory sample tracking is a continuation of field sample tracking. Some of this information
may have been entered into the LIMS during the planning phase.
Documents generated for laboratory sample tracking must be sufficient to verify the sample
identity, that the sample may be reliably located, and that the right sample is analyzed for the
right analyte. The documentation should include sample log-in records, the analysis request form,
names of staff responsible for the work, when procedures are completed, and details concerning
sample disposal. The documentation must conform to the laboratory’s SOPs.
During sample log-in, laboratory quality control (QC) samples may be scheduled for the analyses
requested. The type and frequency of QC samples should be provided by the plan document or
SOW and consistent with the laboratory’s SOPs.
11.5.2 Sample Tracking During Analyses
At this point, samples are introduced into the laboratory’s analytical processing system. The
information gathered during surveying, along with the assigned tracking identification, passes to
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the laboratory where specific preparation and analyses are performed. The sample may be further
subsampled. Each subsample, along with the original sample, requires tracking to account for all
materials handled and processed in the laboratory.
Each set of samples received by the laboratory should be accompanied by documents identifying
the analytes required for each sample. These documents should be reviewed against the project
plan documents or the SOW, which should identify the analytes, matrices, and analytical
requirements and be part of the project documentation prior to the samples being received by the
laboratory. Laboratory management personnel should be notified of any discrepancies. The
requested analyses should be entered into the laboratory’s tracking system. Typically, only one
sample container of sufficient volume or quantity will be provided for a single or multiple set of
different analyses. Each aliquant removed from the original container may require tracking (and
perhaps a different laboratory sample ID).
Aliquants used during the analytical process can be tracked using analysis laboratory notebooks,
forms, or bench sheets that record laboratory sample IDs, analyte, reference date for decay
correction, aliquant size, and designated quality control samples. Bench sheets are loose-leaf or
bound pages used to record information during laboratory work and are used to assist in sample
tracking. Each sheet is helpful for identifying and processing samples in batches that include
designated QC samples. The bench sheet, along with the laboratory log book, can later be used to
record analytical information for use during the data review process. Bench sheets can also be
used to indicate that sample aliquants were in the custody of authorized personnel during the
analytical process.
After receipt, verification of sample information and requested analyses, and assignment of
laboratory sample IDs, the requested analyses can be scheduled for performance in accordance
with laboratory procedures. Using this system, the laboratory can formulate a work schedule, and
completion dates can be projected.
11.5.3 Storage of Samples
If samples are to be stored and analyzed at a later date, they should be p