Chemistry and Analysis of Radionuclides: Laboratory Techniques and Methodology

415 Pages·5.268 MB·English

by  Prof. Jukka Lehto, Dr. Xiaolin Hou(auth.)

Jukka Lehto and Xiaolin Hou
Chemistry and Analysis of
Radionuclides
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Jukka Lehto and Xiaolin Hou
Chemistry and Analysis of Radionuclides
Laboratory Techniques and Methodology
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ISBN:978-3-527-32658-7
V
Contents
Preface XVII
Acknowledgments XIX
1 RadionuclidesandtheirRadiometricMeasurement 1
1.1 Radionuclides 1
1.1.1 NaturalRadionuclides 1
1.1.2 ArtificialRadionuclides 4
1.2 ModesofRadioactiveDecay 6
1.2.1 Fission 6
1.2.2 AlphaDecay 8
1.2.3 BetaDecay 10
1.2.4 InternalTransition 12
1.3 DetectionandMeasurementofRadiation 14
1.3.1 GasIonizationDetectors 14
1.3.2 LiquidScintillationCounting 16
1.3.3 SolidScintillationDetectors 20
1.3.4 SemiconductorDetectors 20
1.3.5 SummaryofRadiometricMethods 22
2 SpecialFeaturesoftheChemistryofRadionuclides
andtheirSeparation 25
2.1 SmallQuantities 25
2.2 Adsorption 26
2.3 UseofCarriers 28
2.4 UtilizationofRadiationintheDeterminationofRadionuclides 31
2.5 ConsiderationofElapsedTime 31
2.6 ChangesintheSystemCausedbyRadiationandDecay 31
2.7 TheNeedforRadiochemicalSeparations 32
ChemistryandAnalysisofRadionuclides.JukkaLehtoandXiaolinHou
Copyright(cid:1)2011WILEY-VCHVerlagGmbH&Co.KGaA,Weinheim
ISBN:978-3-527-32658-7
VI Contents
3 FactorsAffectingChemicalFormsofRadionuclides
inAqueousSolutions 35
3.1 SolutionpH 35
3.2 RedoxPotential 38
3.3 DissolvedGases 42
3.3.1 Oxygen 42
3.3.2 CarbonDioxide 43
3.4 LigandsFormingComplexes
withMetals 46
3.5 HumicSubstances 48
3.6 ColloidalParticles 51
3.7 SourceandGenerationofRadionuclides 52
3.8 Appendix:ReagentsUsedtoAdjustOxidation
StatesofRadionuclides 54
3.8.1 Oxidants 54
3.8.2 Reductants 55
4 SeparationMethods 57
4.1 Precipitation 57
4.2 SolubilityProduct 58
4.2.1 Coprecipitation 59
4.2.2 ObjectivesofPrecipitation 60
4.2.2.1 PrecipitationsSpecificfortheInvestigated
Radionuclide 60
4.2.2.2 GroupPrecipitationsforthePreconcentration
oftheTargetRadionuclide 61
4.2.2.3 GroupPrecipitationsfortheRemovalofInterfering
RadionuclidesandStableElements 61
4.3 IonExchange 64
4.3.1 IonExchangeResins 64
4.3.2 DistributionCoefficientandSelectivity 65
4.3.3 CationExchangeorAnionExchange? 66
4.3.4 IonExchangeChromatography 67
4.3.5 IonExchangeinActinideSeparations 68
4.4 SolventExtraction 70
4.4.1 ExtractableComplexes 71
4.4.2 DistributionConstantandDistributionRatio 72
4.4.3 ExamplesoftheUseofSolventExtractionin
RadiochemicalSeparations 73
4.5 ExtractionChromatography 74
4.5.1 PrinciplesofExtractionChromatography 74
4.5.2 ExtractionChromatographyResins 74
4.5.3 PbandSrResins 75
4.5.4 UseofExtractionChromatographyinActinide
Separations 76
Contents VII
5 YieldDeterminationsandCountingSourcePreparation 81
5.1 TheDeterminationofChemicalYieldinRadiochemicalAnalyses 81
5.1.1 UseofStableIsotopicCarriersinYieldDeterminations 81
5.1.2 UseofRadioactiveTracersinYieldDeterminations 82
5.2 PreparationofSourcesforActivityCounting 85
5.2.1 PreparationofSourceforGammaEmitters 85
5.2.2 SamplePreparationforLSC 86
5.2.3 SourcePreparationforAlphaSpectrometrywithSemiconductor
DetectorsandforBetaCountingwithProportionalCounters 87
5.2.3.1 Electrodeposition 88
5.2.3.2 Micro-coprecipitation 88
5.2.3.3 SpontaneousDeposition 89
5.3 EssentialsinChemicalYieldDeterminationandinCounting
SourcePreparation 89
5.3.1 YieldDetermination 89
5.3.2 CountingSourcePreparation 90
6 RadiochemistryoftheAlkaliMetals 91
6.1 MostImportantRadionuclidesoftheAlkaliMetals 91
6.2 ChemicalPropertiesoftheAlkaliMetals 91
6.3 SeparationNeedsofAlkaliMetalRadionuclides 92
6.4 Potassium–40K 93
6.5 Cesium–134Cs,135Cs,and137Cs 94
6.5.1 SourcesandNuclearCharacteristics 94
6.5.2 PreconcentrationofCesiumNuclidesfromNaturalWaters 95
6.5.3 Determinationof135Cs 96
6.5.3.1 Determinationof135CsbyNeutronActivationAnalysis 96
6.5.3.2 Determinationof135CsbyMassSpectrometry 97
6.6 EssentialsintheRadiochemistryoftheAlkaliMetals 98
7 RadiochemistryoftheAlkalineEarthMetals 99
7.1 MostImportantRadionuclidesoftheAlkalineEarthMetals 99
7.2 ChemicalPropertiesoftheAlkalineEarthMetals 99
7.3 Beryllium–7Beand10Be 102
7.4 Calcium–41Caand45Ca 102
7.4.1 NuclearCharacteristicsandMeasurement 102
7.4.2 Determinationof45Caand41CainConcrete 103
7.5 Strontium–89Srand90Sr 106
7.5.1 NuclearCharacteristicsandSources 106
7.5.2 MeasurementofStrontiumIsotopes 107
7.5.2.1 Measurementof90SrActivity 107
7.5.2.2 SimultaneousDeterminationof89Srand90Sr 109
7.5.3 RadiochemicalSeparationsof90Srand89Sr 109
7.5.3.1 DeterminationofChemicalYieldinRadiostrontium
Separations 110
VIII Contents
7.5.3.2 SeparationofRadiostrontiumbytheNitratePrecipitation
Method 110
7.5.3.3 SeparationofRadiostrontiumbyaCa(OH) Precipitation
2
Method 113
7.5.3.4 SeparationofRadiostrontiumbyExtractionChromatography 114
7.6 Radium–226Raand228Ra 117
7.6.1 NuclearCharacteristicsofRadiumIsotopes 117
7.6.2 MeasurementoftheActivityofRadiumIsotopes 117
7.6.3 NeedforDeterminingtheActivityofRadiumIsotopes 119
7.6.4 RadiochemicalSeparationsofRadium 119
7.6.4.1 Separationof226RainRockSampleswithUseofIon
Exchange 120
7.6.4.2 Determinationof226Raand228RainWaterbyExtraction
Chromatography 121
7.7 EssentialsintheRadiochemistryoftheAlkalineEarthMetals 122
8 Radiochemistryofthe3d-TransitionMetals 123
8.1 TheMostImportantRadionuclidesofthe3d-TransitionMetals 123
8.2 ChemicalPropertiesofthe3d-TransitionMetals 124
8.3 Iron–55Fe 125
8.3.1 NuclearCharacteristicsandMeasurementof55Fe 125
8.3.2 ChemistryofIron 125
8.3.3 Separationof55Fe 128
8.3.3.1 Separationof55FebySolventExtraction 128
8.3.3.2 Separationof55FebyExtractionChromatography 129
8.4 Nickel–59Niand63Ni 130
8.4.1 NuclearCharacteristicsandMeasurementof59Niand63Ni 130
8.4.2 ChemistryofNickel 131
8.4.3 Separationof59Niand63Ni 132
8.4.3.1 SeparationofNickelbytheDMGPrecipitationMethod 132
8.4.3.2 Separationof63NibyNiResin 134
8.4.3.3 SeparationofNickelfortheMeasurementofNickelIsotopes
withAMS 135
8.4.3.4 SimultaneousDeterminationof55Feand63Ni 135
8.5 Essentialsin3-dTransitionMetalsRadiochemistry 137
9 Radiochemistryofthe4d-TransitionMetals 139
9.1 ImportantRadionuclidesofthe4d-TransitionMetals 139
9.2 Chemistryofthe4d-TransitionMetals 140
9.3 Technetium–99Tc 140
9.3.1 ChemistryofTechnetium 141
9.3.2 NuclearCharacteristicsandMeasurementof99Tc 141
9.3.3 Separationof99Tc 143
9.3.3.1 YieldDeterminationin99TcAnalyses 143
9.3.3.2 Enrichmentof99TcforWaterAnalyzes 144
Contents IX
9.3.3.3 Separationof99TcfromWaterbyPrecipitationandSolvent
Extraction 144
9.3.3.4 Separationof99TcbyExtractionChromatography 145
9.3.3.5 Separationof99TcbyDistillation 146
9.4 Zirconium–93Zr 146
9.4.1 ChemistryofZirconium 147
9.4.2 NuclearCharacteristicsandMeasurementof93Zr 148
9.4.3 Separationof93Zr 148
9.4.3.1 Determinationof93ZrbyTTAExtractionandMeasurement
byLSC 149
9.4.3.2 Separationof93ZrbyCoprecipitationandSolventExtraction
fortheZrMeasurementbyICP-MS 149
9.5 Molybdenum–93Mo 151
9.5.1 ChemistryofMolybdenum 151
9.5.2 NuclearCharacteristicsandMeasurementof93Mo 153
9.5.3 Separationof93Mo 154
9.5.3.1 SeparationofRadioactiveMolybdenumbyAluminumOxide 154
9.5.3.2 Separationof93MobySolventExtraction 154
9.6 Niobium–94Nb 156
9.6.1 ChemistryofNiobium 156
9.6.2 NuclearCharacteristicsandMeasurementofNiobium
Radionuclides 157
9.6.3 Separationof94Nb 157
9.6.3.1 Separationof94NbbyPrecipitationasNb2O5 158
9.6.3.2 Separationof94NbbyPrecipitationasNb O andby
2 5
AnionExchange 158
9.6.3.3 Separationof94NbbySolventExtraction 159
9.7 EssentialsintheRadiochemistryof4-dTransitionMetals 159
10 RadiochemistryoftheLanthanides 163
10.1 ImportantLanthanideRadionuclides 163
10.2 ChemicalPropertiesoftheLanthanides 163
10.3 SeparationofLanthanidesfromActinides 165
10.4 LanthanidesasActinideAnalogs 165
10.5 147Pmand151Sm 167
10.5.1 NuclearCharacteristicsandMeasurementof147Pm
and151Sm 167
10.5.2 Separationof147Pmand151Sm 168
10.5.2.1 SeparationwithLnResin 168
10.5.2.2 Determinationof147PmfromUrineUsingIonExchange
Chromatography 170
10.5.2.3 Separationof147PmfromIrradiatedFuelbyIonExchange
Chromatography 170
10.5.2.4 Determinationof147Pmand151SminRocks 171
10.6 EssentialsofLanthanideRadiochemistry 173
X Contents
11 RadiochemistryoftheHalogens 175
11.1 ImportantHalogenRadionuclides 175
11.2 PhysicalandChemicalPropertiesoftheHalogens 176
11.3 Chlorine–36Cl 178
11.3.1 SourcesandNuclearCharacteristicsof36Cl 178
11.3.2 Determinationof36Cl 178
11.3.2.1 Determinationof36ClfromSteel,Graphite,andConcrete
bySolventExtractionandIonExchange 179
11.4 Iodine–129I 181
11.4.1 SourcesandNuclearCharacteristicsof129I 181
11.4.2 Measurementof129I 182
11.4.2.1 Determinationof129IbyNeutronActivationAnalysis 182
11.4.2.2 Determinationof129IbyAcceleratorMassSpectrometry 184
11.4.3 RadiochemicalSeparationsof129I 185
11.4.3.1 Separationof129IbySolventExtraction 185
11.4.3.2 PretreatmentofSamplesfor129IAnalyses 188
11.4.3.3 SpeciationofIodineSpeciesinWater 188
11.5 EssentialsofHalogenRadiochemistry 190
12 RadiochemistryoftheNobleGases 193
12.1 ImportantRadionuclidesoftheNobleGases 193
12.2 PhysicalandChemicalCharacteristicsoftheNobleGases 193
12.3 MeasurementofXeIsotopesinAir 194
12.4 Determinationof85KrinAir 194
12.5 RadonanditsDetermination 196
12.5.1 DeterminationofRadoninOutdoorAirandSoilPoreSpaces 197
12.5.2 DeterminationofRadoninIndoorAir 197
12.5.3 DeterminationofRadoninWater 197
12.6 EssentialsofNobleGasRadiochemistry 198
13 RadiochemistryofTritiumandRadiocarbon 201
13.1 Tritium–3H 201
13.1.1 NuclearPropertiesofTritium 201
13.1.2 EnvironmentalSourcesofTritium 202
13.1.3 DeterminationofTritiuminWater 203
13.1.4 ElectrolyticEnrichmentofTritium 203
13.1.5 DeterminationofTritiuminOrganicMaterial 204
13.1.6 DeterminationofTritiumfromUrine 204
13.1.7 DeterminationofTritiumafterConversionintoBenzene 205
13.1.8 DeterminationofTritiumusingMassSpectrometry 205
13.1.9 DeterminationofTritiuminNuclearWasteSamples 206
13.2 Radiocarbon–14C 207
13.2.1 NuclearPropertiesofRadiocarbon 207
13.2.2 SourcesofRadiocarbon 207
13.2.3 ChemistryofInorganicCarbon 209