Preface ................................................... XVII
Acknowledgments ............................................ XIX
1 Radionuclides and their Radiometric Measurement .............. 1
1.1 Radionuclides ........................................... 1
1.1.1 Natural Radionuclides ............................ 1
1.1.2 Artificial Radionuclides ......................... 4
1.2 Modes of Radioactive Decay .............................. 6
1.2.1 Fission .......................................... 6
1.2.2 Alpha Decay ...................................... 8
1.2.3 Beta Decay ...................................... 10
1.2.4 Internal Transition ............................. 12
1.3 Detection and Measurement of Radiation ................. 14
1.3.1 Gas Ionization Detectors ........................ 14
1.3.2 Liquid Scintillation Counting ................... 16
1.3.3 Solid Scintillation Detectors ................... 20
1.3.4 Semiconductor Detectors ......................... 20
1.3.5 Summary of Radiometric Methods .................. 22
2 Special Features of the Chemistry of Radionuclides and
their Separation ............................................ 25
2.1 Small Quantities ....................................... 25
2.2 Adsorption ............................................. 26
2.3 Use of Carriers ........................................ 28
2.4 Utilization of Radiation in the Determination of
Radionuclides
2.5 Consideration of Elapsed Time .......................... 31
2.6 Changes in the System Caused by Radiation and Decay .... 31
2.7 The Need for Radiochemical Separations ................. 32
3 Factors Affecting Chemical Forms of Radionuclides in
Aqueous Solutions ........................................... 35
3.1 Solution pH ............................................ 35
3.2 Redox Potential ........................................ 38
3.3 Dissolved Gases ........................................ 42
3.3.1 Oxygen .......................................... 42
3.3.2 Carbon Dioxide .................................. 43
3.4 Ligands Forming Complexes with Metals .................. 46
3.5 Humic Substances ....................................... 48
3.6 Colloidal Particles .................................... 51
3.7 Source and Generation of Radionuclides ................. 52
3.8 Appendix: Reagents Used to Adjust Oxidation States of
Radionuclides .......................................... 54
3.8.1 Oxidants ........................................ 54
3.8.2 Reductants ...................................... 55
4 Separation Methods .......................................... 57
4.1 Precipitation .......................................... 57
4.2 Solubility Product ..................................... 58
4.2.1 Coprecipitation ................................. 59
4.2.2 Objectives of Precipitation ..................... 60
4.3 Ion Exchange ........................................... 64
4.3.1 Ion Exchange Resins ............................. 64
4.3.2 Distribution Coefficient and Selectivity ........ 65
4.3.3 Cation Exchange or Anion Exchange? .............. 66
4.3.4 Ion Exchange Chromatography ..................... 67
4.3.5 Ion Exchange in Actinidc Separations ............ 68
4.4 Solvent Extraction ..................................... 70
4.4.1 Extractable Complexes ........................... 71
4.4.2 Distribution Constant and Distribution Ratio .... 72
4.4.3 Examples of the Use of Solvent Extraction in
Radiochemical Separations ....................... 73
4.5 Extraction Chromatography .............................. 74
4.5.1 Principles of Extraction Chromatography ......... 74
4.5.2 Extraction Chromatography Resins ................ 74
4.5.3 Pb and Sr Resins ................................ 75
4.5.4 Use of Extraction Chromatography in Actinide
Separations ..................................... 76
5 Yield Determinations and Counting Source Preparation ........ 81
5.1 The Determination of Chemical Yield in Radiochemical
Analyses ............................................... 81
5.1.1 Use of Stable Isotopic Carriers in Yield
Determinations .................................. 81
5.1.2 Use of Radioactive Tracers in Yield
Determinations .................................. 82
5.2 Preparation of Sources for Activity Counting ........... 85
5.2.1 Preparation of Source for Gamma Emitters ........ 85
5.2.2 Sample Preparation for LSC ...................... 86
5.2.3 Source Preparation for Alpha Spectrometry with
Semiconductor Detectors and for Beta Counting
with Proportional Counters ...................... 87
5.3 Essentials in Chemical Yield Determination and in
Counting Source Preparation ............................ 89
5.3.1 Yield Determination ............................. 89
5.3.2 Counting Source Preparation ..................... 90
6 Radiochemistry of the Alkali Metals ......................... 91
6.1 Most Important Radionuclides of the Alkali Metals ...... 91
6.2 Chemical Properties of the Alkali Metals ............... 91
6.3 Separation Needs of Alkali Metal Radionuclides ......... 92
6.4 Potassium - 40K ........................................ 93
6.5 Cesium - 134Cs, 135Cs, and 137Cs ......................... 94
6.5.1 Sources and Nuclear Characteristics ............. 94
6.5.2 Preconcentration of Cesium Nuclides from
Natural Waters .................................. 95
6.5.3 Determination of 135Cs .......................... 96
7 Radiochemistry of the Alkaline Earth Metals ................. 99
7.1 Most Important Radionuclides of the Alkaline Earth
Metals ................................................. 99
7.2 Chemical Properties of the Alkaline Earth Metals ....... 99
7.3 Beryllium - 7Be and 10Be ............................... 102
7.4 Calcium-41Ca and 45Ca .................................. 102
7.4.1 Nuclear Characteristics and Measurement ........ 102
7.4.2 Determination of 45Ca and 41Ca in Concrete ...... 103
7.5 Strontium - 89Sr and 90Sr .............................. 106
7.5.1 Nuclear Characteristics and Sources ............ 106
7.5.2 Measurement of Strontium Isotopes .............. 107
7.5.3 Radiochemical Separations of 90Sr and 89Sr ...... 109
7.6 Radium - 226Ra and 228Ra ............................... 127
7.6.1 Nuclear Characteristics of Radium Isotopes ..... 117
7.6.2 Measurement of the Activity of Radium
Isotopes ....................................... 117
7.6.3 Need for Determining the Activity of Radium
Isotopes ....................................... 119
7.6.4 Radiochemical Separations of Radium ............ 119
7.7 Essentials in the Radiochemistry of the Alkaline
Earth Metals .......................................... 122
8 Radiochemistry of the 3d-Transition Metals ................. 123
8.1 The Most Important Radionuclides of the 3d-
Transition Metals ..................................... 123
8.2 Chemical Properties of the 3d-Transition Metals ....... 124
8.3 Iron-55Fe ............................................. 125
8.3.1 Nuclear Characteristics and Measurement of
55Fe ........................................... 125
8.3.2 Chemistry of Iron .............................. 125
8.3.3 Separation of 55Fe ............................. 128
8.4 Nickel - 59Ni and 63Ni ................................. 130
8.4.1 Nuclear Characteristics and Measurement of
59Ni and 63Ni ................................... 230
8.4.2 Chemistry of Nickel ............................ 231
8.4.3 Separation of 59Ni and 63Ni ..................... 132
8.5 Essentials in 3-d Transition Metals Radiochemistry .... 137
9 Radiochemistry of the 4d-Transition Metals ................. 139
9.1 Important Radionuclides of the 4d-Transition Metals ... 139
9.2 Chemistry of the 4d-Transition Metals ................. 140
9.3 Technetium - 99Tc ..................................... 140
9.3.1 Chemistry of Technetium ........................ 141
9.3.2 Nuclear Characteristics and Measurement of
99Tc ........................................... 141
9.3.3 Separation of 99Тс ............................. 143
9.4 Zirconium - 93Zr ...................................... 146
9.4.1 Chemistry of Zirconium ......................... 147
9.4.2 Nuclear Characteristics and Measurement of
93Zr ........................................... 148
9.4.3 Separation of 93Zr ............................. 148
9.5 Molybdenum - 93Mo ..................................... 151
9.5.1 Chemistry of Molybdenum ........................ 151
9.5.2 Nuclear Characteristics and Measurement of
93Mo ........................................... 153
9.5.3 Separation of 93Mo ............................. 154
9.6 Niobium - 94Nb ........................................ 156
9.6.1 Chemistry of Niobium ........................... 156
9.6.2 Nuclear Characteristics and Measurement of
Niobium Radionuclides .......................... 157
9.6.3 Separation of 94Nb ............................. 157
9.7 Essentials in the Radiochemistry of 4-d Transition
Metals ................................................ 159
10 Radiochemistry of the Lanthanides .......................... 163
10.1 Important Lanthanide Radionuclides .................... 163
10.2 Chemical Properties of the Lanthanides ................ 163
10.3 Separation of Lanthanides from Actinides .............. 165
10.4 Lanthanides as Actinide Analogs ....................... 165
10.5 147Pm and 151Sm ........................................ 167
10.5.1 Nuclear Characteristics and Measurement of
147Pm and 151Sm ................................. 167
10.5.2 Separation of 147Pm and 151Sm ................... 168
10.6 Essentials of Lanthanide Radiochemistry ............... 173
11 Radiochemistry of the Halogens ............................. 175
11.1 Important Halogen Radionuclides ....................... 175
11.2 Physical and Chemical Properties of the Halogens ...... 176
11.3 Chlorine - 36C1 ....................................... 178
11.3.1 Sources and Nuclear Characteristics of 36Cl .... 178
11.3.2 Determination of 36Cl .......................... 178
11.4 Iodine- 129I .......................................... 181
11.4.1 Sources and Nuclear Characteristics of 129I .... 181
11.4.2 Measurement of 129I ............................ 182
11.4.3 Radiochemical Separations of 129I .............. 185
11.5 Essentials of Halogen Radiochemistry .................. 190
12 Radiochemistry of the Noble Cases .......................... 193
12.1 Important Radionuclides of the Noble Gases ............ 193
12.2 Physical and Chemical Characteristics of the Noble
Gases ................................................. 193
12.3 Measurement of Xe Isotopes in Air ..................... 194
12.4 Determination of 85Kr in Air .......................... 194
12.5 Radon and its Determination ........................... 196
12.5.1 Determination of Radon in Outdoor Air and
Soil Pore Spaces ............................... 197
12.5.2 Determination of Radon in Indoor Air ........... 197
12.5.3 Determination of Radon in Water ................ 197
12.6 Essentials of Noble Gas Radiochemistry ................ 198
13 Radiochemistry of Tritium and Radiocarbon .................. 201
13.1 Tritium - 3Н .......................................... 201
13.1.1 Nuclear Properties of Tritium .................. 201
13.1.2 Environmental Sources of Tritium ............... 202
13.1.3 Determination of Tritium in Water .............. 203
13.1.4 Electrolytic Enrichment of Tritium ............. 203
13.1.5 Determination of Tritium in Organic Material ... 204
13.1.6 Determination of Tritium from Urine ............ 204
13.1.7 Determination of Tritium after Conversion
into Benzene ................................... 205
13.1.8 Determination of Tritium using Mass
Spectrometry ................................... 205
13.1.9 Determination of Tritium in Nuclear Waste
Samples ........................................ 206
13.2 Radiocarbon - 14C ..................................... 207
13.2.1 Nuclear Properties of Radiocarbon .............. 207
13.2.2 Sources of Radiocarbon ......................... 207
13.2.3 Chemistry of Inorganic Carbon .................. 209
13.2.4 Carbon Dating of Carbonaceous Samples .......... 209
13.2.5 Separation and Determination of 14С ............ 210
13.3 Essentials of Tritium and Radiocarbon
Radiochemistry ........................................ 215
14 Radiochemistry of Lead, Polonium, Tin, and Selenium ........ 217
14.1 Polonium - 210Po ...................................... 218
14.1.1 Nuclear Characteristics of 210Po ............... 218
14.1.2 Chemistry of Polonium .......................... 219
14.1.3 Determination of 210Po ......................... 220
14.2 Lead-210Pb ............................................ 221
14.2.1 Nuclear Characteristics and Measurement of
210Pb .......................................... 221
14.2.2 Chemistry of Lead .............................. 223
14.2.3 Determination of 210Pb ......................... 224
14.3 Tin-126Sn ............................................. 228
14.3.1 Nuclear Characteristics and Measurement of
126Sn .......................................... 228
14.3.2 Chemistry of Tin ............................... 229
14.3.3 Determination of 126Sn ......................... 230
14.4 Selenium - 79Se ....................................... 233
14.4.1 Nuclear Characteristics and Measurement of
79Se ........................................... 233
14.4.2 Chemistry of Selenium .......................... 233
14.4.3 Determination of 79Se .......................... 235
14.5 Essentials of Polonium, Lead, Tin, and Selenium
Radiochemistry ........................................ 236
15 Radiochemistry of the Actinides ............................ 239
15.1 Important Actinide Isotopes ........................... 239
15.2 Generation and Origin of the Actinides ................ 239
15.3 Electronic Structures of the Actinides ................ 244
15.4 Oxidation States of the Actinides ..................... 245
15.5 Ionic Radii of the Actinides .......................... 246
15.6 Major Chemical Forms of the Actinides ................. 247
15.7 Disproportionation .................................... 247
15.8 Hydrolysis and Polymerization of the Actinides ........ 249
15.9 Complex Formation of the Actinides .................... 250
15.10 Oxides of the Actinides .............................. 250
15.11 Actinium ............................................. 251
15.11.1 Isotopes of Actinium .......................... 251
15.11.2 Chemistry of Actinium ......................... 252
15.11.3 Separation of Actinium ........................ 253
15.11.4 Essentials of Actinium Radiochemistry ......... 254
15.12 Thorium .............................................. 255
15.12.1 Occurrence of Thorium ......................... 255
15.12.2 Thorium Isotopes and their Measurement ........ 255
15.12.3 Chemistry of Thorium .......................... 256
15.12.4 Separation of Thorium ......................... 258
15.12.5 Essentials of Thorium Radiochemistry .......... 259
15.13 Protactinium ......................................... 260
15.13.1 Isotopes of Protactinium ...................... 260
15.13.2 Chemistry of Protactinium ..................... 261
15.13.3 Separation of Protactinium .................... 262
15.13.4 Essentials of Protactinium Radiochemistry ..... 263
15.14 Uranium .............................................. 264
15.14.1 The Most Important Uranium Isotopes ........... 264
15.14.2 Occurrence of Uranium ......................... 266
15.14.3 Chemistry of Uranium .......................... 267
15.14.4 Hydrolysis of Uranium ......................... 269
15.14.5 Formation of Uranium Complexes ................ 269
15.14.6 Uranium Oxides ................................ 271
15.14.7 From Ore to Uranium Fuel ...................... 271
15.14.8 Measurement of Uranium ........................ 272
15.14.9 Reasons for Determining Uranium Isotopes ...... 273
15.14.10 Separation of Uranium ........................ 274
15.14.11 Essentials of Uranium Radiochemistry ......... 275
15.15 Neptunium ............................................ 277
15.15.1 Sources of Neptunium .......................... 277
15.15.2 Nuclear Characteristics and Measurement of
237Np ......................................... 278
15.15.3 Chemistry of Neptunium ........................ 278
15.15.4 Separation of 237Np ........................... 280
15.15.5 Essentials of Neptunium Radiochemistry ........ 283
15.16 Plutonium ............................................ 284
15.16.1 Isotopes of Plutonium ......................... 284
15.16.2 Sources of Plutonium .......................... 286
15.16.3 Measurement of Plutonium Isotopes ............. 287
15.16.4 The Chemistry of Plutonium .................... 289
15.16.5 Separation of Plutonium ....................... 293
15.16.6 Tracers Used in the Determination of Pu
Isotopes ...................................... 294
15.16.7 Separation by Solvent Extraction .............. 295
15.16.8 Separation of Pu by Anion Exchange
Chromatography ................................ 296
15.16.9 Separation of Pu by Extraction
Chromatography ................................ 297
15.16.10 Separation of Pu from Large Volumes of
Water ......................................... 298
15.16.11 Automated and Rapid Separation Methods for
Pu Determination .............................. 300
15.16.12 Essentials of Plutonium Radiochemistry ....... 301
15.17 Americium and Curium ................................. 302
15.17.1 Sources of Americium and Curium ............... 302
15.17.2 Nuclear Characteristics and Measurement of
241Am, 242Cm, 243Cm, and 244Cm ................... 303
15.17.3 Chemistry of Americium and Curium ............. 304
15.17.4 Separation of Americium and Curium ............ 306
15.17.5 Essentials of Americium and Curium
Radiochemistry ................................ 309
16 Speciation Analysis ........................................ 311
16.1 Considerations Relevant to Speciation ................. 311
16.2 Significance of Speciation ............................ 312
16.3 Categorization of Speciation Analyzes ................. 313
16.4 Fractionation Techniques for Environmental Samples .... 314
16.4.1 Particle Fractionation in Water ................ 314
16.4.2 Fractionation of Aerosol Particles ............. 316
16.4.3 Fractionation of Soil and Sediments ............ 317
16.5 Analysis of Radionuclide and Isotope Compositions ..... 317
16.6 Spectroscopic Speciation Methods ...................... 318
16.7 Wet Chemical Methods .................................. 321
16.7.1 Coprecipitation ................................ 321
16.7.2 Solvent Extraction ............................. 322
16.7.3 Ion Exchange Chromatography .................... 323
16.8 Sequential Extractions ................................ 324
16.9 Computational Speciation Methods ...................... 326
16.10 Characterization of Radioactive Particles ............ 329
16.10.1 Identification and Isolation of the
Particles ..................................... 330
16.10.2 Scanning Electron Microscopic Analysis of
the Particles ................................. 330
16.10.3 Gamma and X-ray Analysis of the Particles ..... 331
16.10.4 Secondary Ion Mass Spectrometry Analysis of
Radioactive Particles ......................... 332
16.10.5 Synchrotron-Based X-ray Microanalyses ......... 332
16.10.6 Post-Dissolution Analysis of Particles 334
Further Reading ............................................ 335
17 Measurement of Radionuclides by Mass Spectrometry .......... 337
17.1 Introduction .......................................... 337
17.2 Inductively Coupled Plasma Mass Spectrometry
(ICP-MS) .............................................. 338
17.2.1 Components and Operation Principles of ICP-MS
Systems ........................................ 339
17.2.2 Resolution and Abundance Sensitivity ........... 342
17.2.3 Dynamic Collision/Reaction Cells ............... 343
17.2.4 Detectors ...................................... 344
17.2.5 Detection Limits ............................... 345
17.2.6 90Sr Measurement by ICP-MS ..................... 346
17.2.7 90Tc Measurement by ICP-MS ..................... 348
17.2.8 Measurement of Uranium and Thorium Isotopes
by ICP-MS ...................................... 348
17.2.9 237Np Measurement by ICP-MS .................... 349
17.2.10 Measurement of Plutonium Isotopes by
ICP-MS ........................................ 349
17.3 Accelerator Mass Spectrometry (AMS) ................... 350
17.3.1 Components and Operation of AMS ................ 350
17.3.2 14C Measurement by AMS ......................... 352
17.3.3 36Cl Measurement by AMS ........................ 353
17.3.4 41Ca Measurement by AMS ........................ 353
17.3.5 63Ni and S9Ni Measurement by AMS ............... 353
17.3.6 99Tc Measurement by AMS ........................ 354
17.3.7 129I Measurement by AMS ........................ 355
17.3.8 Measurement of Plutonium Isotopes by AMS ....... 355
17.4 Thermal Ionization Mass Spectrometry (TIMS) ........... 356
17.5 Resonance Ionization Mass Spectrometry (RIMS) ......... 358
17.6 Essentials of the Measurement of Radionuclides by
Mass Spectrometry ..................................... 359
Further Reading ............................................ 360
18 Sampling and Sample Pretreatment for the Determination
of Radionuclides ........................................... 361
18.1 Introduction .......................................... 361
18.2 Air Sampling and Pretreatment ......................... 362
18.2.1 Sampling Aerosol Particles ..................... 362
18.3 Sampling Gaseous Components ........................... 366
18.4 Atmospheric Deposition Sampling ....................... 369
18.4.1 Dry/Wet Deposition Sampling .................... 369
18.4.2 Ion Exchange Collector ......................... 370
18.5 Water Sampling ........................................ 371
18.5.1 Surface Water Sampling ......................... 371
18.5.2 Water Core (Depth Profile) ..................... 372
18.5.3 Preconcentration of Radionuclides from
Natural Waters ................................. 375
18.6 Sediment Sampling and Pretreatment .................... 377
18.6.1 Surface Sediment Sampling ...................... 377
18.6.2 Sediment Core Sampling ......................... 379
18.6.3 Sediment Pore Water Sampling ................... 381
18.6.4 Pretreatment of Sediments - Storage, Drying,
Homogenizing ................................... 383
18.7 Soil Sampling and Pretreatment ........................ 384
18.7.1 Planning the Sampling .......................... 384
18.7.2 Soil Core Sampling ............................. 385
18.7.3 Template Method ................................ 387
18.7.4 Trench Method .................................. 387
18.7.5 Pretreatment of Soil Samples ........................ 388
18.8 Essentials in Sampling and Sample Pretreatment for
Radionuclides ......................................... 388
19 Chemical Changes Induced by Radioactive Decay .............. 391
19.1 Autoradiolysis ........................................ 391
19.1.1 Dissolved Gases ................................ 392
19.1.2 Water Solutions ................................ 392
19.1.3 Organic Compounds Labeled with Radionuclides ... 392
19.1.4 Solid Compounds ................................ 393
19.2 Transmutation and Subsequent Chemical Changes ......... 393
19.3 Recoil - Hot Atom Chemistry ........................... 394
Index ...................................................... 397
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