Stable Isotope Forensics: An Introduction to the Forensic Application of Stable Isotope Analysis

284 Pages·2010·13.397 MB·English

by  Dr Wolfram Meier?Augenstein(auth.)

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Stable Isotope Forensics
Stable Isotope Forensics: An Introduction to the Forensic Application of Stable Isotope Analysis Wolfram Meier-Augenstein
© 2010 John Wiley & Sons Ltd. ISBN: 978-0-470-51705-5
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Stable Isotope Forensics
An Introduction to the Forensic Application
of Stable Isotope Analysis
Wolfram Meier-Augenstein
Centre for Anatomy & Human Identification
University of Dundee, UK
SCRI, Invergowrie, Dundee, UK
A John Wiley & Sons, Ltd., Publication
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Thiseditionfirstpublished2010,(cid:1)c 2010byJohnWiley&SonsLtd.
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LibraryofCongressCataloguing-in-PublicationData
Meier-Augenstein,Wolfram.
Stableisotopeforensics:anintroductiontotheforensicapplicationofstableisotopeanalysis/Wolfram
Meier-Augenstein.
p.;cm.
Includesbibliographicalreferencesandindex.
ISBN978-0-470-51705-5
1.Chemistry,Forensic. 2.Stableisotopes. I.Title.
[DNLM: 1.ForensicSciences–methods. 2.Isotopes–analysis.W700M511s2010]
RA1057.M452010
363.25–dc22
2009041399
ISBN:978-0-470-51705-5
AcataloguerecordforthisbookisavailablefromtheBritishLibrary.
Typesetin10.5/12.5ptMinionbyAptaraInc.,NewDelhi,India.
PrintedinGreatBritainbyAntonyRoweLtd,Chippenham,Wiltshire.
FirstImpression 2010
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Contents
Series Foreword: Developments in Forensic Science Niamh Nic Dae´id ix
Foreword: Sean Doyle xi
List of Figures xiii
List of Tables xix
Introduction: Stable Isotope ‘Fingerprinting’ or Chemical ‘DNA’: A New
Dawn for Forensic Chemistry? xxi
I How It Works 1
I.1 WhatareStableIsotopes? 3
I.2 NaturalAbundanceVariationofStableIsotopes 5
I.3 ChemicallyIdenticalandYetNottheSame 8
I.4 IsotopeEffects,MassDiscriminationandIsotopicFractionation 10
I.4.1 PhysicalChemistryBackground 10
I.4.2 FractionationFactorαandEnrichmentFactorε 11
I.4.3 IsotopicFractionationinRayleighProcesses 13
I.4.4 IsotopicFractionationSummary 14
I.5 StableIsotopicDistributionandIsotopicFractionationofLightElementsinNature 16
I.5.1 Hydrogen 16
I.5.2 Oxygen 19
I.5.2.1 18OinBoneBio-apatiteandSourceWater 20
I.5.2.2 BoneRemodelling 23
I.5.2.3 BoneDiagenesis 24
I.5.2.3.1 DiageneticChangesofBio-apatite 24
I.5.3 Carbon 25
I.5.4 Nitrogen 27
I.5.4.1 FoodChainandTrophicLevelShift 29
I.5.4.2 DiageneticChangesofStructuralProteins 32
I.5.5 Sulfur 33
I.6 StableIsotopeForensicsinEverydayLife 36
I.6.1 ‘FoodForensics’ 37
I.6.1.1 AuthenticityandProvenanceofSingle-SeedVegetableOils 38
I.6.1.2 AuthenticityandProvenanceofBeverages 39
I.6.1.3 AuthenticityandProvenanceofotherPremiumFoods 41
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vi CONTENTS
I.6.2 CounterfeitPharmaceuticals 42
I.6.3 EnvironmentalForensics 43
I.6.4 WildlifeForensics 46
I.6.5 Anti-DopingControl 47
I.7 SummaryofPartI 49
I.8 Setproblems 50
References 51
II Instrumentation and Analytical Techniques 65
II.1 MassSpectrometryversusIsotopeRatioMassSpectrometry 67
II.2 InstrumentationandδNotation 72
II.2.1 Dual-InletIsotopeRatioMassSpectrometry 74
II.2.2 ContinuousFlowIsotopeRatioMassSpectrometry 74
II.2.3 BulkMaterialStableIsotopeAnalysis 77
II.2.4 Compound-SpecificStableIsotopeAnalysis 78
II.2.4.1 CSIAandCompoundIdentification 79
II.2.4.2 Position-SpecificIsotopeAnalysis 81
II.2.4.3 CSIAofPolar,Non-VolatileOrganicCompounds 83
II.3 IsotopicCalibrationandQualityControlinContinuousFlowIsotopeRatio
MassSpectrometry 85
II.3.1 Two-PointorEnd-memberScaleCorrection 86
II.3.1.1 ScaleCorrectionofMeasuredδ2HValues 87
II.3.1.2 ScaleCorrectionofMeasuredδ13CValues 88
II.4 StatisticalAnalysisofStableIsotopeDatawithinaForensicContext 91
II.4.1 ChemometricAnalysis 91
II.4.2 BayesianAnalysis 94
II.5 ForensicStableIsotopeAnalyticalProcedures 100
II.5.1 FIRMSNetwork 101
II.6 GenericConsiderationsforStableIsotopeAnalysis 102
II.6.1 GenericConsiderationsforSamplePreparation 102
II.6.2 GenericConsiderationsforBSIA 104
II.6.2.1 IsobaricInterference 104
II.6.3 ParticularConsiderationsfor2H-BSIA 105
II.6.3.1 KeepingYourPowderDry 105
II.6.3.2 Totalδ2HversusTrueδ2HValues 106
II.6.3.2.1 2HIsotopeAnalysisofHumanHair 108
II.6.3.3 IonizationQuenchEffect 113
II.6.4 GenericConsiderationsforCSIA 116
II.6.4.1 IsotopicCalibrationduringGC/C-IRMS 116
II.6.4.2 IsotopeEffectsinGC/C-IRMSduringSampleInjection 117
II.6.4.3 ChromatographicIsotopeEffectinGC/C-IRMS 118
II.7 SummaryofPartII 121
II.8 SetProblems 122
II.A HowtoSetUpaLaboratoryforContinuousFlowIsotopeRatio
MassSpectrometry 123
II.A.1 Pre-InstallationRequirements 124
II.A.2 LaboratoryLocation 124
II.A.3 TemperatureControl 125
II.A.4 PowerSupply 125
II.A.5 GasSupply 126
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CONTENTS vii
II.A.6 ForensicLaboratoryConsiderations 129
II.A.7 FinishingTouches 130
References 136
III Stable Isotope Forensics: Case Studies and Current Research 143
III.1 ForensicContext 145
III.2 DistinguishingDrugs 149
III.2.1 NaturalandSemisyntheticDrugs 149
III.2.1.1Marijuana 149
III.2.1.2MorphineandHeroin 150
III.2.1.3Cocaine 152
III.2.2 SyntheticDrugs 154
III.2.2.1Amphetamines 154
III.2.2.2MDMA:SynthesisandIsotopicSignature 157
III.2.2.2.1ThreeDifferentSyntheticRoutes–Controlled
Conditions 157
III.2.2.2.2OneSyntheticRoute–VariableConditions 164
III.2.2.3Methamphetamine:SynthesisandIsotopicSignature 164
III.2.3 Conclusions 167
III.3 ElucidatingExplosives 169
III.3.1 BulkIsotopeAnalysisofExplosivesandPrecursors 170
III.3.1.1AmmoniumNitrate 171
III.3.1.2Hexamine,RDXandSemtex 172
III.3.1.3HydrogenPeroxideandPeroxides 176
III.3.2 IsotopicProduct/PrecursorRelationship 179
III.3.3 PotentialPitfalls 182
III.3.4 Conclusions 183
III.4 MatchingMatchsticks 184
III.4.1 13C-BulkIsotopeAnalysis 185
III.4.2 18O-BulkIsotopeAnalysis 186
III.4.3 2H-BulkIsotopeAnalysis 187
III.4.4 MatchingMatchesfromFireScenes 188
III.4.5 Conclusions 189
III.5 ProvenancingPeople 190
III.5.1 StableIsotopeAbundanceVariationinHumanTissue 191
III.5.2 TheSkullfromtheSea 194
III.5.3 AHumanLifeRecordedinHair 197
III.5.4 FoundinNewfoundland 201
III.5.5 TheCaseof‘TheScissorSisters’ 207
III.5.6 Conclusions 211
III.6 StableIsotopeForensicsofotherPhysicalEvidence 214
III.6.1 MicrobialIsotopeForensics 214
III.6.2 Paper,Plastic(Bags)andParcelTape 215
III.6.2.1Paper 215
III.6.2.2PlasticandPlasticBags 216
III.6.2.3ParcelTape 218
III.6.3 Conclusions 221
III.7 Summary 222
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viii CONTENTS
III.A ‘PlayTrue?’:StableIsotopesinAnti-dopingControlorQuiscustodietipsos
custodes? 224
III.A.1 TestosteroneMetabolismand13CIsotopicComposition 226
III.A.2 AnalyticalMethodology:GasChromatographyandPeakIdentification 230
III.B SamplePreparationProcedures 236
III.B.1 PreparingSilverPhosphatefromBio-apatitefor18OIsotopeAnalysis 236
III.B.2 AcidDigestofCarbonatefromBio-apatitefor13Cand
18OIsotopeAnalysis 238
III.B.3 StandardProtocolforPreparingHairSamplesfor2HIsotopeAnalysis 240
References 242
Government Agencies and Institutes with Dedicated Stable
Isotope Laboratories 253
Acknowledgements 255
Recommended Reading 257
Author’s Biography 261
Index 263
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Series Foreword
Developments in Forensic Science
The world of forensic science is changing at a very fast pace. This is in terms of the
provisionofforensicscienceservices,thedevelopmentoftechnologiesandknowledge,
and the interpretation of analytical and other data as it is applied within forensic
practice. Practicing forensic scientists are constantly striving to deliver the very best
forthejudicialprocess,andassuchneedareliableandrobustknowledgebasewithin
theirdiversedisciplines.Itishopedthatthisbookserieswillbeavaluableresourcefor
forensicsciencepractitionersinthepursuitofsuchknowledge.
TheForensicScienceSocietyistheprofessionalbodyforforensicpractitionersinthe
UnitedKingdom.TheSocietywasfoundedin1959andgainedprofessionalbodystatus
in2006.TheSocietyiscommittedtothedevelopmentoftheforensicsciencesinallof
itsmanyfacets,andinparticulartothedeliveryofhighlyprofessionalandworthwhile
publicationswithinthesedisciplinesthroughventuressuchasthisbookseries.
DrNiamhNicDae´id
SeriesEditor
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Foreword
I am delighted to be able to write the foreword for this, the first textbook of stable
isotopeforensics.
Thebreadthofmaterialcoverediswide,rangingfromfundamentalstopolicyissues,
andthereforethistextwillbeofbenefittopractitioners,researchersandinvestigators,
indeedtoanyonewhohasaninterestinthisnewforensicdiscipline.
Theyear2001sawtheformationoftheForensicIsotopeRatioMassSpectrometry
(FIRMS) Network. Since then much has been achieved in terms of advancing the
forensicapplicationofstableisotopeanalysis,thistextbookbeingthelatestsignificant
step.
Theseadvanceshavebeenmadeinthefaceofconsiderablechallengesresultingfrom
the novelty and complexity of the technique. Isotope forensics has already proved a
powerful tool in the investigation and prosecution of high-profile crimes, including
terrorism.Stableisotopeanalysisenablesquestionsregardingthesourceandhistoryof
illicitandotherforensicmaterialstobeaddressed–questionswhichmightotherwise
remainunanswered.
Isotope forensics is now being widely adopted for profiling illicit materials and
humanprovenancing.Stableisotopeanalysishasalreadybeenusedsuccessfullyintwo
majorterroristtrialsintheUnitedKingdom,andinavarietyofinvestigationsandtrials
intheUnitedKingdom,EuropeandtheUnitedStates.
DrMeier-Augensteinistobecommendedforhisvisioninrecognizingtheforensic
potentialofstableisotopes,forhisenergyindevelopingandoptimizingthemethod-
ology,andin promotingthetechniqueto end-users.Heis alsowellawareoftherisk
of contributing to a miscarriage of justice and recognizes that only an appropriate
regulatoryframeworkcansignificantlymitigatethatrisk.
Thedevelopmentofsuitabledatabasesofreferencematerialsandappropriatetools
forevaluationremainsignificanttasks;oncecompletethenextdecadeshouldseeisotope
forensicstakingadeservedplaceinmainstreamforensicscienceand,toagreaterextent,
contributingtotheefficientandeffectivedeliveryofjustice.
SeanDoyle
PastChairoftheFIRMSNetwork
PrincipalScientist,ForensicExplosivesLaboratory,DefenceScience
andTechnologyLaboratory
September2009
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List of Figures
PartI
FigureI.1 δ2Handδ18Ovaluesofwholewoodandplantsugars(beetand
canesugar)intheframeworkoftheglobalmeteoricwaterline 18
FigureI.2 Correlationplotofsourcewaterδ2Hvaluesversusδ2Hvaluesof
freshsoftfruitwater 19
FigureI.3 CorrelationgraphsaccordingtoDauxetal.,Longinelli,andLuz
andKolodnyforδ18O versusδ18O andtheresulting
phosphate water
differentsolutionsofδ18O forthesameδ18O 23
water phosphate
FigureI.4 Bivariategraphplottingδ15Nversusδ13Cvaluesofscalphair
samplesvolunteeredbyresidentsindifferentcountries
reflectingtheirregionallydifferentdiet 26
FigureI.5 Schematicrepresentationoftypicalδ15Nvaluesinrelationto
trophiclevel 28
FigureI.6 13Cisotopiccompositionofvariousfoodandanimaltissue 29
FigureI.7 Bivariategraphplottingδ15Nversusδ13Cvaluesfromscalphair
ofaveganandanomnivorewhohasarelativelystrongmeat
componentintheirdiet 31
FigureI.8 Approximateδ13Cvaluesfor13Cisotopiccompositionof
variousbodypoolsandtissue 32
FigureI.9 Naturalvariationin13Cisotopiccompositionofsingle-seed
vegetableoilsandselectedfattyacidsisolatedfromtheseoils 39
FigureI.10 Bivariateplotofδ2Handδ13Cvaluesofethanolfroma
selectionofEuropeanwhitewines,includingonesuspect
sampleofwinelabelledasvintageAustrianwine 41
FigureI.11 Isotopicbivariateplotofδ13Candδ15NvaluesoftheAPIfolic
acidfromthreedifferentmanufacturersatthreedifferent
locations 44