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Stable Isotope Forensics
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Stable Isotope
Forensics
Methods and Forensic Applications of
Stable Isotope Analysis
Second Edition
Wolfram Meier-Augenstein
RobertGordonUniversity
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Aberdeen,UK
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Thiseditionfirstpublished2018
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LibraryofCongressCataloging-in-PublicationData
Names:Meier-Augenstein,Wolfram.
Title:Stableisotopeforensics:methodsandforensicapplicationsofstable
isotopeanalysis/ProfessorDr.WolframMeier-Augenstein,RobertGordon
University,Aberdeen,UK.
Description:Secondedition.|Hoboken,NJ:Wiley,2018.|Series:
Developmentsinforensicscience|Includesbibliographicalreferencesand
index.|DescriptionbasedonprintversionrecordandCIPdataprovided
bypublisher;resourcenotviewed.
Identifiers:LCCN2017010492(print)|LCCN2017011764(ebook)|ISBN
9781119080220(pdf)|ISBN9781119080237(epub)|ISBN9781119080206
(cloth)
Subjects:LCSH:Chemistry,Forensic.|Stableisotopes.
Classification:LCCRA1057(ebook)|LCCRA1057.M452018(print)|DDC
614/.12–dc23
LCrecordavailableathttps://lccn.loc.gov/2017010492
CoverDesign:Wiley
CoverImages:(Background)©chokkicx/Gettyimages;
(Skull)StanleyKPatz/Gettyimages;
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Setin10.5/12.5ptTimesLTStdbySPiGlobal,Chennai,India
10 9 8 7 6 5 4 3 2 1
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Contents
SeriesForeword xi
Foreword:DameSueBlack xiii
Foreword:MarkHarrison xv
Forewordtothe1𝐬𝐭 Edition xvii
BookEndorsements xix
Prefacetothe2𝐧𝐝 Edition xxi
ListofAbbreviations xxv
AbouttheCompanionWebsite xxvii
Introduction: Stable Isotope ‘Profiling’ or Chemical ‘DNA’:
ANewDawnforForensicChemistry? xxix
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I HowitWorks 1
I.1 WhatareStableIsotopes? 2
I.2 NaturalAbundanceVariationofStableIsotopes 4
I.3 ChemicallyIdenticalandYetNottheSame 12
I.4 IsotopeEffects,MassDiscriminationandIsotopicFractionation 15
I.4.1 PhysicalChemistryBackground 15
I.4.2 FractionationFactor𝛼andEnrichmentFactor𝜀 17
I.4.3 IsotopicFractionationinRayleighProcesses 19
I.4.3.1 IsotopicFractionationSummary 20
I.5 StableIsotopicDistributionandIsotopicFractionationofLightElementsin
Nature 22
I.5.1 Hydrogen 22
I.5.2 Oxygen 26
I.5.3 Carbon 27
I.5.4 Nitrogen 30
I.5.5 Sulfur 32
I.5.6 Isoscapes 35
I.6 StableIsotopeForensicsinEverydayLife 40
I.6.1 “FoodForensics” 42
I.6.1.1 AuthenticityandProvenanceofSingle-Seed
VegetableOils 42
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vi CONTENTS
I.6.1.2 AuthenticityandProvenanceofBeverages 45
I.6.1.3 Caveats 49
I.6.2 AuthenticityandProvenanceofotherPremiumProducts 53
I.6.3 CounterfeitPharmaceuticals 54
I.6.4 EnvironmentalForensics 59
I.6.5 WildlifeForensics 61
I.6.6 Anti-DopingControl 62
I.7 SummaryofPartI 65
ReferencesPartI 67
II Instrumentation,AnalyticalTechniquesandDataQuality 81
II.1 MassSpectrometryversusIsotopeRatioMassSpectrometry 82
II.1.1 Stability,IsotopicLinearityandIsotopicCalibration 85
II.2 InstrumentationforStableIsotopeAnalysis 90
II.2.1 Dual-InletIRMSSystems 92
II.2.2 Continuous-FlowIRMSSystems 93
II.2.3 BulkMaterialStableIsotopeAnalysis 94
II.2.3.1 13C,15Nand34S 94
II.2.3.2 2Hand18O 96
II.2.4 Compound-SpecificStableIsotopeAnalysisofVolatileOrganic
Compounds 98
II.2.4.1 Compound-Specific13Cor15NAnalysisbyGC/C-IRMS 98
II.2.4.2 Compound-Specific2Hor18OAnalysisby
GC/HTC-IRMS 100
II.2.4.3 Position-SpecificIsotopeAnalysis 101
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II.2.5 Compound-Specific13C/15NAnalysisofPolar,Non-Volatile
OrganicCompoundsbyLC-IRMS 101
II.2.6 Compound-SpecificIsotopeAnalysisandForensicCompound
Identification 103
II.3 QualityControlandQualityAssuranceinContinuous-FlowIsotopeRatioMass
Spectrometry 106
II.3.1 CompliancewithIUPACGuidelinesisaPrerequisitenotaLuxury 106
II.3.2 TheIdenticalTreatmentPrinciple 111
II.3.3 TheImportanceofScaleNormalization 112
II.3.3.1 ScaleNormalizationofMeasured𝛿2HValuesto
VSMOW 114
II.3.3.2 ScaleNormalizationofMeasured𝛿13CValuestoVPDB 120
II.3.3.3 ScaleNormalizationofMeasured𝛿18OValuesto
VSMOW 122
II.3.3.4 ScaleNormalizationofMeasured𝛿15NValuestoAir 126
II.3.3.5 ScaleNormalizationofMeasured𝛿34SValuestoVCDT 127
II.4 PointsofNoteforStableIsotopeAnalysis 128
II.4.1 PreparingforAnalysis 128
II.4.2 GenericConsiderationsforBSIA 131
II.4.2.1 ScaleNormalizationofBSIA 132
II.4.2.2 KeepingYourPowderDry 134
II.4.2.3 IsobaricInterference 135
II.4.2.4 IonizationQuenchEffect 137
II.4.3 ParticularConsiderationsforBSIA 140
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CONTENTS vii
II.4.3.1 Bulk15NAnalysisofNitrates 140
II.4.3.2 Bulk2HAnalysisofNitrogen-RichCompounds 141
II.4.3.3 Total𝛿2HversusTrue𝛿2HValues 141
II.4.3.4 OrganicCompoundswithExchangeableHydrogenand
Implicationsfor2HAbundanceAnalysis 144
II.4.3.4.1 ChemicalandBiochemicalConsiderations –
Example:Hair 152
II.4.3.5 2HAnalysisofHumanHair 158
II.4.3.5.1 Two-PointEquilibrationwithWaterat
AmbientTemperature 161
II.4.3.5.2 Two-PointEnd-MemberComparative
Equilibration 166
II.4.3.5.3 On-LineTwo-PointEnd-Member
ComparativeSteamEquilibration 170
II.4.4 PointsofNoteforCSIA 172
II.4.4.1 ScaleNormalizationofGC-IRMSAnalyses 172
II.4.4.2 IsotopeEffectsinGC-IRMSduringSampleInjection 175
II.4.4.3 TheChromatographicIsotopeEffectinGC-IRMS 176
II.4.4.4 DerivatizationofPolarCompoundsforGC-IRMS 178
II.4.4.5 Compound-Specific2HAnalysisofN-orCl-Rich
Compounds 181
II.5 StatisticalAnalysisofStableIsotopeDatawithinaForensicContext 183
II.5.1 ChemometricAnalysis 183
II.5.2 BayesianAnalysis 185
II.6 QualityControlandQualityAssuranceinForensicStableIsotopeAnalysis 194
(cid:2) II.6.1 AccreditationtoISO17025 195 (cid:2)
II.6.1.1 WhoAssessestheAssessors? 197
II.6.2 TheForensicIsotopeRatioMassSpectrometryNetwork 205
II.7 SummaryofPartII 207
II.A HowtoSetUpaLaboratoryforContinuous-FlowIsotopeRatioMass
Spectrometry 209
II.A.1 Pre-InstallationRequirements 210
II.A.2 LaboratoryLocation 210
II.A.3 TemperatureControl 211
II.A.4 PowerSupply 212
II.A.5 GasSupply 213
II.A.6 ForensicLaboratoryConsiderations 216
II.A.7 FinishingTouches 217
II.B SourcesofInternationalReferenceMaterialsandTertiaryStandards 219
II.C SelectedSamplePreparationProtocols 220
II.C.1 DerivatizationofAminoAcidsforCompoundSpecificIsotope
AnalysisbyGC-IRMS 220
II.C.2 AcidDigestofCarbonatefromBio-apatitefor13Cand18O
Analysis 223
II.C.3 PreparingSilverPhosphatefromBio-apatitefor18OAnalysis 225
II.C.4 Two-PointWaterEquilibrationProtocolforDeterminationof
Non-ex𝛿2HValuesofHumanHair 227
II.D InternetSourcesofGuidanceandPolicyDocuments 231
ReferencesPartII 233
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viii CONTENTS
III StableIsotopeForensics:CaseStudiesandCurrentResearch 247
III.1 ForensicContext 248
III.1.1 LegalContext 249
III.2 DistinguishingDrugs 255
III.2.1 NaturalandSemisyntheticDrugs 255
III.2.1.1 Marijuana 255
III.2.1.2 MorphineandHeroin 257
III.2.1.3 Cocaine 259
III.2.2 SyntheticDrugs 263
III.2.2.1 Amphetamines 263
III.2.2.2 Methamphetamine:SynthesisandIsotopicSignature 264
III.2.2.2.1 TwoDifferentSyntheticRoutes –
ClandestineConditions 268
III.2.2.3 MDMA:SynthesisandIsotopicSignature 270
III.2.2.3.1 ThreeDifferentSyntheticRoutes –
ControlledConditions 273
III.2.2.3.2 OneSyntheticRoute – VariableConditions 279
III.2.3 “LegalHighs”and“DesignerDrugs” 284
III.2.3.1 Mephedrone 284
III.2.3.2 Piperazines 287
III.2.4 Excipients 291
III.2.5 Conclusions 293
III.3 ElucidatingExplosives 296
III.3.1 StableIsotopeAnalysisofExplosivesandPrecursors 297
III.3.1.1 AmmoniumNitrate(AN) 298
(cid:2) III.3.1.2 Hexamine,RDX,C4andSemtex 300 (cid:2)
III.3.1.3 IsotopicProduct/PrecursorRelationship 305
III.3.1.3.1 RDXandHMX 305
III.3.1.3.2 HMTDandTATP 309
III.3.1.4 HydrogenPeroxide 315
III.3.2 PotentialPitfalls 321
III.3.3 Conclusions 323
III.4 MatchingMatchsticks 324
III.4.1 13C-BulkIsotopeAnalysis 325
III.4.2 18O-BulkIsotopeAnalysis 326
III.4.3 2H-BulkIsotopeAnalysis 328
III.4.4 MatchingMatchesfromFireScenes 330
III.4.5 Conclusions 331
III.5 ProvenancingPeople 333
III.5.1 StableIsotopeAbundanceVariationinHumanTissue 336
III.5.1.1 HairandNails 338
III.5.1.1.1 CharacteristicsofHair 340
III.5.1.1.2 CharacteristicsofNails 342
III.5.1.1.3 DiageneticChangesofKeratin 342
III.5.1.1.4 2HIsotopicRecordinHairandNail 343
III.5.1.1.5 18OIsotopicRecordinHairandNail 345
III.5.1.1.6 13CIsotopicRecordinHairandNail 346
III.5.1.1.7 15NIsotopicRecordinHairandNail 347
III.5.1.2 BoneandTeeth 350
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CONTENTS ix
III.5.1.2.1 ChemicalCompositionofBoneandTeeth 351
III.5.1.2.2 StaticversusRemodellingTissue
Compartments 352
III.5.1.2.3 DiageneticChangesofBoneandTeeth
Mineral 354
III.5.1.2.4 DiageneticChangesofTypeICollagen 356
III.5.1.2.5 18OIsotopicRecordinCarbonateand
PhosphatefromBio-apatite 357
III.5.1.2.6 13CIsotopicRecordinCarbonatefrom
Bio-apatite 363
III.5.1.2.7 IsotopicRecordinTypeICollagen 364
III.5.1.3 TrophicLevelShiftEffectonStableIsotopeAbundance
ValuesinHumanTissue 365
III.5.2 CaseExamples 370
III.5.2.1 TheSkullfromtheSea 371
III.5.2.2 AHumanLifeRecordedinHair 375
III.5.2.3 FoundinNewfoundland 379
III.5.2.4 TheCaseof“TheScissorSisters” 384
III.5.2.5 TooShortaLife 390
III.5.2.6 SaltairSally 393
III.5.2.7 ATaleofTwoCultures 394
III.5.3 ConclusionsandCaveats 397
III.6 StableIsotopeForensicsofOtherPhysicalEvidence 401
III.6.1 MicrobialIsotopeForensics 402
III.6.2 ToxinsandPoisons 404
(cid:2) III.6.3 Paper,Plastic(Bags)andParcelTape 404 (cid:2)
III.6.3.1 Paper 404
III.6.3.2 PlasticandPlasticBags 407
III.6.3.3 ParcelTape 408
III.6.4 Conclusions 412
III.7 EvaluativeInterpretationofForensicStableIsotopeData 413
III.7.1 NotScaleReferenced𝛿-Values 415
III.7.2 UnresolvedContradictoryData 418
III.7.2.1 Example:“GeographicProvenanceofaMurderVictim” 418
III.7.2.2 Example:“ManslaughterduetoNegligence” 420
III.7.3 ForegoneConclusions 422
III.7.4 LogicalFallacies 424
III.7.5 UntestedAssumptions 426
III.7.6 Conclusion 428
III.8 SummaryofPartIII 430
III.A AnAbridgedListofForensicStableIsotopeLaboratoriesWorldwide 432
ReferencesPartIII 434
RecommendedReading 453
Author’sBiography 459
Acknowledgements 461
Index 463
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Series Foreword
Theworldofforensicscienceischangingataveryfastpaceintermsoftheprovision
offorensicscienceservices,thedevelopmentoftechnologiesandknowledgeandthe
interpretation of analytical and other data as it is applied within forensic practice.
Practicingforensicscientistsareconstantlystrivingtodelivertheverybestforthe
judicialprocessandassuchneedareliableandrobustknowledgebasewithintheir
diversedisciplines.Itishopedthatthisbookserieswillprovidearesourcebywhich
suchknowledgecanbeunderpinnedforbothstudentsandpractitionersofforensic
sciencealike.
It is the objective of this book series to provide a valuable resource for forensic
sciencepractitioners,educatorsandothersinthatregard.Thebooksdevelopedand
published within this series come from some of the leading researchers and prac-
titioners in their fields and will provide essential and relevant information to the
reader.
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ProfessorNiamhNicDaéid
SeriesEditor
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Foreword by Dame Sue Black
I am so delighted to be asked to write the foreword for a text where I understand
so little of the background science. A reasonable question might be, then why ask
aforensicanthropologisttodothiswhenshebarelypassedHigherChemistryand
has absolutely no experience in the field of stable isotope analysis? One of the
most important aspects of working within a forensic team is to know the limits of
one’s own ability and to recognize and utilize the strengths of others. It has been
my pleasure to work with Wolfram for many years and when forensic casework
comestome,itiswithoutsecondthoughtthatIpassitontohimknowingthatthe
investigativeauthoritieswillnotbehoodwinkedbyapseudoscientist.
A single-author text in these days is rare and the value of this book lies in the
dedication and experience of the author, which is evident in the clarity of prose,
the honest illustration of evidence and the realistic practical application of the
subject–itmakesthisatextofgenuinescientificvalue.Thatasecondeditionhas
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been requested is a clear indication that the field is still progressing and that new
research is still being reported. In the current world of forensic science flux, it is
vitalthatrobustscientificresearchendeavourscontinue andthatitbereportednot
only in published peer-reviewed papers but collocated in scholarly tomes for easy
reference.
In my early discussions with Wolfram I admit to having been a bit of a sceptic,
but over time I have been educated and fully persuaded of the value of stable
isotope analysis to the world of provenancing and human identification. There
havebeenseveralinstanceswhereconclusionsdrawnregardingethnicoriginbased
on forensic anthropological examination of skeletal remains were corroborated
independently by results from stable isotope analysis of bone and teeth. One need
onlyreadthecasehistoriesincludedinthetexttoappreciatethepracticalvalueof
thisapproachtoforensicinvestigationsand,inparticular,whenattemptingtoestab-
lish the identity of the deceased, which is a pivotal component of any successful
investigation.
Forme,oneofthemostimportantandreassuringaspectsofthistextisitsbrutal
openness, honesty and transparency. Without apology it identifies equally where
are the strengths and limitations of the science and its interpretation for forensic
purposes. Whilst this book will challenge those who are not chemically literate, it
willquicklybecomeestablishedasthe“go-to”textforallpractitionersandendusers
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