Analytical Chemistry of Uranium: Environmental, Forensic, Nuclear, and Toxicological Applications

318 Pages·2014·14.81 MB·English

by  Zeev Karpas

CHEMISTRY
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ANALYTICAL
R ANALYTICAL
P
A
CHEMISTRY
S
CHEMISTRY
OF URANIUM
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OF URANIUM
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Environmental, Forensic, Nuclear,
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and Toxicological Applications
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Accurate uranium analysis, particularly for isotope measurements, is essential I
C Environmental, Forensic, Nuclear,
in many fields, including environmental studies, geology, hydrogeology, the
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nuclear industry, health physics, and homeland security. Nevertheless, only a
and Toxicological Applications
few scientific books are dedicated to uranium in general and analytical chemistry L
aspects in particular. Analytical Chemistry of Uranium: Environmental, Forensic,
C
Nuclear, and Toxicological Applications covers the fascinating advances in the
field of analytical chemistry of uranium. H
E
Exploring a broad range of topics, the book focuses on the analytical aspects
of industrial processes that involve uranium, its presence in the environment, M
health and biological implications of exposure to uranium compounds, and
I
nuclear forensics. S
Topics include T
• Examples of procedures used to characterize uranium in environmental R
samples of soil, sediments, vegetation, water, and air Y
• Analytical methods used to examine the rigorous specifications of uranium

and its compounds deployed in the nuclear fuel cycle O
• Health aspects of exposure to uranium and the bioassays used for F
exposure assessment

• Up-to-date analytical techniques used in nuclear forensics for safeguards U
in support of non-proliferation, including single particle characterization
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Each chapter includes an overview of the topic and several examples to
demonstrate the analytical procedures. This is followed by sample preparation, N
separation and purification techniques where necessary. The book supplies
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readers with a solid understanding of the analytical chemistry approach used U
today for characterizing the different facets of uranium, providing a good
M
starting point for further investigation into this important element.
K22209
ISBN: 978-1-4822-2058-2
90000
ZEEV KARPAS
9 781482 220582
K22209_Cover_PubGr.indd All Pages 10/16/14 12:36 PM

ANALYTICAL
CHEMISTRY
OF URANIUM
Environmental, Forensic, Nuclear,
and Toxicological Applications

ANALYTICAL
CHEMISTRY
OF URANIUM
Environmental, Forensic, Nuclear,
and Toxicological Applications
ZEEV KARPAS
CRC Press
Taylor & Francis Group
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Boca Raton, FL 33487-2742
© 2015 by Taylor & Francis Group, LLC
CRC Press is an imprint of Taylor & Francis Group, an Informa business
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Version Date: 20140703
International Standard Book Number-13: 978-1-4822-2060-5 (eBook - PDF)
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Contents
Preface.......................................................................................................................ix
Acknowledgments .....................................................................................................xi
Acronyms ...............................................................................................................xiii
Chapter 1 Introduction: Fundamental Properties of Uranium and Its
Compounds, the Nuclear Fuel Cycle, and Analytical Methods
Used for Characterizing Uranium ........................................................1
1.1 Introduction ...............................................................................1
1.2 Fundamentals of Uranium and Its Chemistry ...........................3
1.2.1 History and Properties of the Element .........................3
1.2.1.1 Discovery and History ..................................3
1.2.1.2 Occurrence ....................................................4
1.2.1.3 Physical Properties .......................................4
1.2.1.4 Nuclear Properties and Isotopes ...................5
1.2.1.5 Radioactive Decay Chains ............................9
1.2.1.6 Fission of U-235 by Neutrons .....................12
1.2.1.7 Alloys ..........................................................14
1.2.1.8 Chemical Properties ...................................14
1.2.2 Mineralogy of Uranium .............................................14
1.2.3 Major Uranium Compounds .......................................16
1.2.3.1 Binary Oxides of Uranium .........................17
1.2.3.2 Binary Fluorides of Uranium .....................19
1.2.3.3 Oxyfluorides of Uranium ............................23
1.2.3.4 Other Uranyl Compounds ...........................23
1.2.3.5 Other Uranium Compounds in the
Nuclear Industry .........................................25
1.3 Uranium in the NFC ................................................................25
1.3.1 Uranium Mining .........................................................27
1.3.2 Uranium Milling ........................................................28
1.3.3 Uranium Conversion Facility .....................................29
1.3.4 Isotope Enrichment ....................................................31
1.3.5 Fabrication of Nuclear Fuel and Irradiation ...............34
1.3.6 Treatment and Disposal of Irradiated Fuel ................35
1.3.7 Types of NFCs ............................................................36
1.3.8 Reactor Fuel and Fuel Elements .................................37
1.3.8.1 Reactor Types, Moderators, and Coolants ...38
1.3.8.2 Type of Fuel ................................................39
1.4 Modern Analytical Techniques in a Nutshell ..........................39
1.4.1 Photon Counting Techniques .....................................41
1.4.1.1 Atomic Absorption Spectrometry ..............41
v
vi Contents
1.4.1.2 Atomic Emission Spectrometry
or Optical Emission Spectrometry .............43
1.4.1.3 X-Ray Fluorescence Spectrometry .............45
1.4.1.4 Neutron Activation Analysis .......................45
1.4.1.5 Gamma Spectrometry .................................47
1.4.1.6 Electron Microscopy ...................................49
1.4.1.7 Other Spectroscopic Techniques ................50
1.4.2 Ion Counting Techniques ...........................................51
1.4.2.1 Mass Spectrometry (MS) ............................51
1.4.2.2 Alpha Spectrometry ....................................56
1.4.2.3 Other Ion Counting Techniques ..................58
1.4.3 Generic Sample Preparation and Uranium
Separation Techniques................................................59
1.5 Summary .................................................................................60
References ..........................................................................................60
Chapter 2 Industrial Applications .......................................................................63
2.1 Industrial Considerations .........................................................63
2.1.1 Introduction ................................................................63
2.1.2 World Resources and Production of Uranium............66
2.2 Analytical Chemistry of Uranium Ores ..................................68
2.2.1 Prospecting Methods ..................................................68
2.2.1.1 Aerial and Ground-Level
Gamma-Ray Surveys ..................................69
2.2.1.2 Geophysical Methods .................................71
2.2.1.3 Other Prospecting Strategies ......................72
2.2.2 Assay of Minerals and Uranium Ores ........................73
2.3 Analytical Chemistry in the NFC ...........................................77
2.3.1 Analytical Characterization of UF
6
for Enrichment Facilities ............................................80
2.3.1.1 Sampling of Uranium Hexafluoride ............80
2.3.1.2 Isotopic Analysis of Uranium Hexafluoride ...83
2.3.1.3 Determination of Impurities in
Uranium Hexafluoride ................................86
2.3.2 Analytical Characterization of UO Fuel ...................87
2
2.3.3 Analytical Characterization of Uranium
and Uranium Alloys ...................................................93
2.3.4 Analytical Characterization of Fuel Elements ...........94
2.3.5 Analysis at the Back End of the NFC ........................95
2.3.5.1 Characterizing SNF ....................................97
2.3.6 Reprocessing SNF ....................................................103
2.3.7 Analysis of Waste in the NFC ..................................105
2.4 Depleted Uranium and Its Characterization ..........................107
2.5 Summary ...............................................................................110
References ........................................................................................111
Contents vii
Chapter 3 Determination of Uranium in Environmental Samples ...................119
3.1 Introduction and General Overview ......................................119
3.1.1 Transport of Uranium in the Environment ...............120
3.1.2 Analytical Procedures for the Determination
of Uranium in Environmental Samples ....................122
3.1.3 Analytical Methods for the Determination
of Uranium ...............................................................125
3.2 Uranium Content in Soil ........................................................126
3.2.1 Digestion and Sample Preparation ...........................126
3.2.2 Soil Sample Preparation for Methods
That Do Not Require Extensive Treatment ..............135
3.3 Uranium Content in Plants and Vegetation ...........................139
3.4 Soil-to-Plant Transfer Factors ................................................144
3.5 Uranium Content in Natural Freshwater Sources
and Oceans ............................................................................147
3.5.1 Preconcentration of Uranium from Aqueous
Samples ....................................................................148
3.5.2 Uranium in Ocean Water and Seawater ...................151
3.5.3 Uranium in Surface Waters ......................................152
3.6 Uranium Content in Air and Other Environmental Samples .....154
3.7 Summary ...............................................................................158
References ........................................................................................161
Chapter 4 Exposure, Toxicity, and Biomonitoring of Uranium Exposure ........167
4.1 Introduction ...........................................................................167
4.2 Exposure Pathways ................................................................167
4.2.1 Sources of Environmental and Occupational
Exposures .................................................................167
4.2.1.1 Daily Intake of Uranium through
Ingestion....................................................168
4.2.1.2 Daily Intake of Uranium through
Inhalation ..................................................174
4.2.1.3 Exposure to Uranium through
Skin and Injury .........................................175
4.2.1.4 Analytical Methods for the Determination
of Uranium in Drinking Water ........................177
4.2.1.5 Analytical Methods for the Determination
of Uranium in Food Products ..........................179
4.2.2 Distribution of Uranium in the Body
(Biokinetic Models) ..................................................182
4.3 Toxicity ..................................................................................188
4.3.1 Toxicity of Uranium .................................................188
4.3.2 Chemical Toxicity ....................................................192
4.3.3 Radiological Toxicity ...............................................195
4.3.4 Other Health Effects .................................................195
viii Contents
4.4 Bioassays for Uranium Exposure ..........................................197
4.4.1 Analytical Methods for the Determination
of Uranium in Urine .................................................201
4.4.2 Urinalysis for Special Populations ...........................212
4.4.3 Blood and Feces Analysis ........................................216
4.4.4 Uranium Content Analysis in Hair and Nails ..........218
4.4.5 Uranium Content Analysis in Other Bioassays ........225
4.5 Dose Assessment and Treatment of Exposed People ............226
4.6 Summary ...............................................................................227
References ........................................................................................228
Chapter 5 Trace Analysis and Nuclear Forensics .............................................237
5.1 Introduction ...........................................................................237
5.1.1 Nuclear Forensics .....................................................237
5.1.2 Adaptation of Analytical Techniques
for Trace Analysis ....................................................240
5.1.3 Thermal Ionization Mass Spectrometry...................242
5.1.4 Secondary Ion Mass Spectrometry ..........................244
5.1.5 Inductively Coupled Plasma Mass Spectrometry .....245
5.2 Nuclear Fingerprints ..............................................................246
5.2.1 Standards and Certified Reference Materials ..........248
5.2.2 Fingerprinting of Uranium Ores ..............................248
5.2.3 Uranium Conversion Facilities
and Enrichment Plants .............................................253
5.2.4 Fingerprinting Operations with UF ........................253
6
5.2.5 Nuclear Fuel Fabrication and Spent Fuel .................258
5.2.5.1 Uranium Oxide .........................................258
5.2.6 Postdetonation Fingerprints .....................................260
5.3 Bulk Analysis and Single Particle Analysis ..........................261
5.3.1 Bulk Analysis for Safeguards Purposes ...................261
5.3.2 Single Particle Analysis............................................263
5.3.3 Locating Uranium in Single Particles ......................273
5.3.4 Characterization of Uranium in Single Particles .....274
5.4 Trace Analysis and Safeguards .............................................274
5.4.1 Principles of Age Determination ..............................275
5.4.2 Analytical Procedures Used for Uranium-Based
Age Dating ...............................................................278
5.5 Nuclear Forensics ..................................................................284
5.5.1 Databases for Nuclear Forensic Investigations .........284
5.5.2 Case Studies .............................................................284
5.6 Summary ...............................................................................286
References ........................................................................................289
Chapter 6 Summary ..........................................................................................295