gc×gc-ms and bayesian testing in forensics … · gc×gc-ms and bayesian testing in forensics ......

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GC×GC-MS AND BAYESIAN TESTING IN FORENSICS: TOWARDS THE IDENTIFICATION OF SUSPECTS THROUGH THEIR ODOR Isabelle RIVALS 1 , Vincent CUZUEL 2 , Guillaume COGNON 2 , Roman Lecon Didier THIEBAUT 3 , Charles SAULEAU 2 , Jérôme VIAL 3 – GCxGC 2018, Riva Del Garda, Italy Équipe de StaSsSque Appliquée, UMRS 1158, ESPCI Paris, France InsStut de Recherche Criminelle de la Gendarmerie NaSonale, Cergy-Pontoise, France UMR CBI 8231 - Laboratoire Sciences AnalySques, BioanalySques et MiniaturisaSon – ESPCI Paris – PSL Research University

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Page 1: GC×GC-MS AND BAYESIAN TESTING IN FORENSICS … · GC×GC-MS AND BAYESIAN TESTING IN FORENSICS ... development and opmizaon in view of human hand odor analysis by thermal desorpon

GC×GC-MSANDBAYESIANTESTINGINFORENSICS:TOWARDSTHEIDENTIFICATIONOFSUSPECTSTHROUGH

THEIRODORIsabelleRIVALS1,VincentCUZUEL2,GuillaumeCOGNON2,RomanLeconte2

DidierTHIEBAUT3,CharlesSAULEAU2,JérômeVIAL3

ISCC–GCxGC2018,RivaDelGarda,Italy

1-ÉquipedeStaSsSqueAppliquée,UMRS1158,ESPCIParis,France2-InsStutdeRechercheCriminelledelaGendarmerieNaSonale,Cergy-Pontoise,France3-UMRCBI8231-LaboratoireSciencesAnalySques,BioanalySquesetMiniaturisaSon–ESPCIParis–PSLResearchUniversity

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CONTEXT

PopularizaConofthetechniquesusedbythe

police

CriminalsaremoreaLenCveandcauCous!

Humanodor

GCxGC-ISCCRivadelgarda2018

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USEOFTRAINEDDOGS

•  SufficientforidenCficaConofaperson•  LimitedprobaCvevalueincourtsofjusCce

•  NeedforcorroboraCveevidencebyanalyCcaltools:•  SupporttheinformaSonprovidedbydogs•  ProbaSvevaluetoevidenceincourtsofjusCce

GCxGC-ISCCRivadelgarda2018

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OBJECTIVES•  DevelopaglobalstrategytocharacterizetheolfactoryfingerprintsofindividualsusinganalyScalandstaSsScaltools•  VolaClecompoundsattracelevels:preconcentraConsteprequired•  Complexmixtures:mulCdimensionalseparaCon(GC×GC-MS)

•  QuesContobeanswered•  Isthecomparisonofan“odor”referencechromatogramtoachromatogramobtainedusinganodorsamplefromasuspect(crimescene…)sufficienttoprovethattheodorbelongstothesameperson?

GCxGC-ISCCRivadelgarda2018

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GLOBALSTRATEGY

SAMPLING/PANEL SEPARATIONANDDETECTION DATAPROCESSING

GCxGC-ISCCRivadelgarda2018

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PRECONCENTRATIONANDANALYSIS:PURGEANDTRAP-GCXGC

ThermodesorpSoncoupledwith

GC×GC-MS

VSP4000,AcConEurope(Sausheim,France)

Sampletemperature=190°CPurgeflow=20mL/minPurgeSme=20minSplit=0mL/min

DesorpConopCmizaConDOE:•  syntheScmixtureofhuman

odor(80compounds1)•  fullfactorialdesign24

1-Cuzueletal.,Areview:Origin,analyScalcharacterizaSonanduseofhumanhandsodorinforensics,2017,JournalofForensicSciences

Directsampling

Indirectsampling

DB1MS-DB17012°C/min–modulaSon8s

GCxGC-ISCCRivadelgarda2018

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CHROMATOGRAMOFAREALSAMPLE8s

0 86min

2nddimen

sion:DB1

7-01(m

id-polar)

1stdimension:DB1-MS(apolar)

•  ShimadzuGC×GC/MSQ2010Plus•  Gradient:2.5°C/min40°Cà250°C

NonanalDecanal

5-hepten-2-one,6methyl

α-pinene

5,9-undecadien-2-one,6,10-dimethyl(E)1,7-octanediol,3,7-dimethyl

Ethanol,2-phenoxy

Phenol,p-tert-butyl

TerSaryodor

Primaryandsecondaryodor

GCxGC-ISCCRivadelgarda2018

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COMPARISONOFREALSAMPLES?

•  Complexsamples

•  Comparisonisnottrivial

•  Alotofdatatoprocess

•  NeedforanautomateddataprocessingtoextractrelevantinformaSon•  Needforapanelofpersonstoevaluatethestrategy

GCxGC-ISCCRivadelgarda2018

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Panelof119persons

•  Phototype1-skinissunsensiCveanddoesnotburn•  Phototype2-intermediateskin•  Phototype3–welltanningskin•  4directsamplingsofhands/person(Sorb-star®)

•  15minutes•  Blank(samplingroom)

•  TD*-GC×GC-MS**•  3chromatograms/person*Cuzueletal.,SamplingmethoddevelopmentandopSmizaSoninviewofhumanhandodoranalysisbythermaldesorpSoncoupledwithgaschromatographyandmassspectrometry,2017,Anal.Bioanal.Chem.

**Cuzueletal.,Humanodorandforensics.OpSmizaSonofacomprehensivegaschromatographymethodbasedonorthogonality:hownottochoosebetweencriteria.,2017,JournalofChromatographyA

gender age(years) phototype

total ♂ ♀ 10-23 24-36 37-81 1 2 3

119 61 58 39 39 41 25 79 15

CHROMATOGRAMSOFREALSAMPLES:PANEL

GCxGC-ISCCRivadelgarda2018

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DATAPROCESSING/BAYESIANAPPROACH

GCxGC-ISCCRivadelgarda2018

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•  FrequenCstApproach

•  BayesianApproach

ü

ü

ü

ü

CHROMATOGRAPHICDATAPROCESSINGWITHMATLAB

Conversionoffiles Pre-treatment DetecSonofpeaks

Transferofdatainthelibrairies

TreatmentusingstaSsScs

•  DetecConoflocalmaxima

•  ExtracConofassociatedinformaCons

•  BaselinecorrecCon

•  SelecConofinvesCgatedzones

ExportincompaCbleformat

(mzXML)

ImportofdatatoMatlab

•  DetecConoflocalmaxima

•  ExtracConofassociatedinformaCons

(alkanes,1t,2t,LRI,MSspectrum,name)

•  ImporttoNISTandownlibrary(3persons)

(>600compounds)

•  Libraryupdate(knownodorcompounds*)

•  IdenCficaConandpeakassignaCon

*Cuzueletal.,Origin,analyScalcharacterizaSonanduseofhumanodorinforensics,2017,J.ForensicSci.

1chromatogram 1vectorcorrespondingto600compoundspeakintensityGCxGC-ISCCRivadelgarda2018

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H0:thetwochromatogramsareobtainedfromthesamepersonH1:thetwochromatogramsareNOTobtainedfromthesamepersonIfDrepresenttheobserveddata(thetwochromatograms),Bayesformulagives:

Protocole:

•DefiniConofadistancedbetween2chromatograms(D≡d)

•Panelofchromatogramsofindividuals(119personssampled4Cmes)spliLedinindependentcalibraSonandtestgroups

•CalibraCongroupèesCmaConofdistribuSonsofdforcouplesofchromatogramsfromthesamepersonf(d|H0)andfromdifferentpersonsf(d|H1)

•TestgroupèesCmaConofperformance(AUC,sensiCvity,spécificity)

P(H0 |D) =f(D |H0)P(H0)

f(D |H0)P(H0)+ f(D |H1)P(H1)

BAYESIANAPPROACH(APOSTERIORI)

GCxGC-ISCCRivadelgarda2018

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EsSmaSonofthestaSsScallikelihoodOpSons:d:distancesbetween600-vectorsofintensiCes:

a)euclidiandistanceb)1– PearsoncorrelaSoncoefficientc)1– SpearmancorrelaSoncoefficient

•intensiCesnormalized/binarized(b=c)CalibraCongroup(260chromatograms/75persons)-341couplesofchromatogramsforH0(sameperson)-33329couplesdechromatogramsforH1(différentpersons)èhistogramsofdvaluesforH0andH1Ajustmentofhistogramsusingseveralgaussiancurvesè f(d|H0)andf(d|H1)

BAYESIANAPPROACH:CHOICEOFDISTANCEBETWEENCHROM

GCxGC-ISCCRivadelgarda2018

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•ProbabiliCesapriori:P(H0)=P(H1)=0.5•FicCCousexamplesofstaCsCcallikelihood

P(H0 | d) =f(d |H0)P(H0)

f(d |H0)P(H0)+ f(d |H1)P(H1)

BAYESIANAPPROACH:EXPECTEDRESULTS

Distancebetweenchromatograms Distancebetweenchromatograms

GCxGC-ISCCRivadelgarda2018

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BAYESIANAPPROACH:RESULTSUSING600COMPOUNDS

distanceintensiSes euclidian 1–ρPearson 1–ρSpearman

normalized 62.7%/64.6% 74.6%/74.7% 92.4%/93.6%

binarized 88.4%/91.6% 89.6%/91.7%

N.B.usingthetestgroup,thereare173/9418couplesforH0/H1respecCvely

2modes!

GCxGC-ISCCRivadelgarda2018

(%AUCcalibraCon/%AUCtest)

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•DiscriminaCngcompoundsforH0andH1:thosewhich intensitydifferences|∆i|aresignificantlylowerforH0thanH1• QuanCficaCon :p-value usingunilateral Fisher test (binarized intensiCes) orWilcoxon(normalizedintensiCes)on|∆i|•Examples:

BAYESIANAPPROACH:DISCRIMINATINGCOMPOUNDS

GCxGC-ISCCRivadelgarda2018

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Binarized

Normalized

BAYESIANAPPROACH:RESULTSUSINGDISCRIMINATINGCOMPOUNDS

GCxGC-ISCCRivadelgarda2018

(%AUCcalibraCon/%AUCtest)

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BAYESIANAPPROACH:RESULTSUSINGDISCRIMINATINGCOMPOUNDS

•Thresholdπ value–log10(p)ofFishertest(binarizedintensiCes)orWilcoxon(normalized intensiCes) :opCmizedvalueobtainedusingcrossvalidaSon (K=3)oncalibraSongroup

distanceintensiSes euclidian 1–ρPearson 1–ρSpearman

normalizedπ =12/61comp.

76.2%/73.9%

π =13/54comp.

78.1%/75.2%

π =7/146comp.

97.5%/98.2%

binarizedπ =18/82comp.

93.1%/94.8%

π =18/82comp.97.4%/98.1%

(%AUCcalibraCon/%AUCtest)

GCxGC-ISCCRivadelgarda2018

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Discussion

Performances• Adequate distanceèquanStaSve exploitaCon of compounds intensiCes despite theanalyCcalvariability•SelecSonèsecondmodesoff(d|H0)etf(d|H1)arestronglydecreasedèbeLerresults•Binarized:moreparsimonious(82/146compoundstobeused)•67commoncompoundsforbothclassifiersNotabene•samedirectsamples•nopolluConbyotherodors

intensiSes AUC sensiSvity specificity nb.compounds

binarized 97.4%/98.1% 89.4%/90.0% 94.9%/92.5% 82

normalized 97.5%/98.2% 89.1%/85.9% 93.7%/95.0% 146

(%AUCcalibraCon/%AUCtest)

GCxGC-ISCCRivadelgarda2018

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CONCLUSIONANDPERSPECTIVES

ü Direct/nondirectsamplingproceduresforhuman(hand)odoranalysesü ComprehensiveGC×GC-MSmethodanddata(ToF)ü ValidaConofproceduresinthefieldwithdoghandlersü LargePanelofindividualstotestthemodelü Storageofsamples:standardizedprocedureü DataprocessinginprogressforrealapplicaCon

ü Differentsamples(directornot…)andsamplingcondiSonsü StudyofdiscriminaCngcompoundsü NormalizaConondiscriminaCngcompounds,morecomplexdistance…

ü ThefinalanswertothequesSonmustbeYESorNOnot98.2%GCxGC-ISCCRivadelgarda2018

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ACKNOWLEDGEMENTS

THANKYOUFORYOURATTENTION!Dino

GCxGC-ISCCRivadelgarda2018