gc×gc-ms and bayesian testing in forensics … · gc×gc-ms and bayesian testing in forensics ......
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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
CONTEXT
PopularizaConofthetechniquesusedbythe
police
CriminalsaremoreaLenCveandcauCous!
Humanodor
GCxGC-ISCCRivadelgarda2018
USEOFTRAINEDDOGS
• SufficientforidenCficaConofaperson• LimitedprobaCvevalueincourtsofjusCce
• NeedforcorroboraCveevidencebyanalyCcaltools:• SupporttheinformaSonprovidedbydogs• ProbaSvevaluetoevidenceincourtsofjusCce
GCxGC-ISCCRivadelgarda2018
OBJECTIVES• DevelopaglobalstrategytocharacterizetheolfactoryfingerprintsofindividualsusinganalyScalandstaSsScaltools• VolaClecompoundsattracelevels:preconcentraConsteprequired• Complexmixtures:mulCdimensionalseparaCon(GC×GC-MS)
• QuesContobeanswered• Isthecomparisonofan“odor”referencechromatogramtoachromatogramobtainedusinganodorsamplefromasuspect(crimescene…)sufficienttoprovethattheodorbelongstothesameperson?
GCxGC-ISCCRivadelgarda2018
GLOBALSTRATEGY
SAMPLING/PANEL SEPARATIONANDDETECTION DATAPROCESSING
GCxGC-ISCCRivadelgarda2018
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
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
COMPARISONOFREALSAMPLES?
• Complexsamples
• Comparisonisnottrivial
• Alotofdatatoprocess
• NeedforanautomateddataprocessingtoextractrelevantinformaSon• Needforapanelofpersonstoevaluatethestrategy
GCxGC-ISCCRivadelgarda2018
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
DATAPROCESSING/BAYESIANAPPROACH
GCxGC-ISCCRivadelgarda2018
• 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
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
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
•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
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)
•DiscriminaCngcompoundsforH0andH1:thosewhich intensitydifferences|∆i|aresignificantlylowerforH0thanH1• QuanCficaCon :p-value usingunilateral Fisher test (binarized intensiCes) orWilcoxon(normalizedintensiCes)on|∆i|•Examples:
BAYESIANAPPROACH:DISCRIMINATINGCOMPOUNDS
GCxGC-ISCCRivadelgarda2018
Binarized
Normalized
BAYESIANAPPROACH:RESULTSUSINGDISCRIMINATINGCOMPOUNDS
GCxGC-ISCCRivadelgarda2018
(%AUCcalibraCon/%AUCtest)
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
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
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
ACKNOWLEDGEMENTS
THANKYOUFORYOURATTENTION!Dino
GCxGC-ISCCRivadelgarda2018