航海技术外文翻译渔船上吸入氟利昂22二氟甲烷致死事故Word文档格式.docx

航海技术外文翻译渔船上吸入氟利昂22二氟甲烷致死事故Word文档格式.docx

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ForensicScienceInternational168（2007）208–211

AnaccidentaldeathduetoFreon22（monochlorodifluoromethane）inhalationinafishingvessel

Casereport

AkoKoreeda*,KoseiYonemitsu,SohtarouMimasaka,YukiOhtsu,ShigeyukiTsunenari

DepartmentofForensicMedicine,GraduateSchoolofMedicalSciences,KumamotoUniversity,1-1-1Honjo,Kumamoto860-8556,Japan

Received15June2005;

receivedinrevisedform22December2005;

accepted12January2006

Availableonline21February2006

Abstract

AcaseofaccidentalFreon22（monochlorodifluoromethane）poisoninginafishingvesselisreported.Forensicautopsyrevealedseverepulmonaryedemaandcongestion（leftlung;

576g,rightlung;

740g）.GC–MSanalysisclearlyshowedthatthedeceasedinhaledFreon22gaspriortohisdeath.Freon22concentrationwas1697.0mg/mlintheheartblood.ThedistributionpatternofFreon22intissuesampleswassimilartothatinpreviouslyreportedcases.ThebrainhadthehighestconcentrationofFreon22followedbythespleen,liver,kidneyandlung,respectively.

Histopathologically,OilredOstainingofthelivershowedmanysmall,positiveredareasinthecytosol,whichhavebeenreportedinothercasesofFreon22poisoning.However,SchmorlstainingrevealedthatmostareasofOilredOpositivitywerelipofuscingranules.Lipofuscinintheliver,whichcloselyrelatestoagingandothercellstresses,couldhavearelevancetoFreon22exposure,butfurtherexperimentalstudiesareneededtoconfirmit.

1.Introduction

Monochlorodifluoromethane（Freon22）isachlorofluorocarbon,whichhasbeenwidelyusedasarefrigerantforfreezers,refrigeratorsandairconditioners[1].Itisacolorless,non-flammablegaswithaslightlyetherealodoratroomtemperatureandhasahighvapordensity（3.03;

air=1）[2].AccordingtotheclassificationofsolventandgastoxicitybyUnderwritersLaboratoriesInc.,Freon22belongstogroup5a,andthetoxicityisinthesameclasswithFreon11（1,2dibromotetrafluoroethane）andcarbondioxide[3].AlthoughFreon22isbelievedtohavealowtoxicitycomparedtootherchlorofluorocarbons,fatalitiescausedbyaccidentalinhalationhavebeenreported,especiallyinfishingvessels[4–8].

Wehadaforensicautopsycaseofamanwhodiedaccidentallywhilemaintainingafreezingsysteminafishingvessel.WepresentthedetailsofthecaseandatoxicologicalanalysisofFreon22inthebody.Thecauseandmannerofdeatharediscussedbasedonthetoxicologicalandhistopathologicalfindings.2.Casehistory

Thechiefengineerandadeck-handofadeep-seatrawlerwerefoundunconsciousintheirvesselatabout08:

30am.Theyhadbeenworkinginthevesselfrom07:

30thatmorningtoprepareforthenextvoyage.Theircolleaguesrescuedthem.Thedeckhand,whowaslyingonthemiddledeckofthevessel,survived（Fig.1B）.Thechiefengineerwhowasonthebottomdeckdied（Fig.1A）at10:

22amafterhospitalization.Thecolleaguesdidnotnoticeanystrangeodorinthecabins,buttheynearlyfaintedwithinaminuteofenteringthecabin.

Threemonthsbeforethefatalincident,thefreezingsystemofthevesselhadagas-leakingaccident.Althoughitwasrepaired,afurtherFreongas-leakwasexpectedbecausethesystemwastooold.Thepoliceonlyinvestigatedthescenethenextdayafterventilatingthecabinspacefortheirownsafety,therefore,theoxygenandFreon22concentrationsinthecabinatthetimeoftheaccidentarenotknown.

Fig.1.Sideviewofthedeep-seafishingvessel.（A）Chiefengineer（decedent）;

（B）deckhand（survived）;

（C）compressoroftherefrigerator.

38-year-oldmanweighing64kgand174cmtall.Therewasseverepulmonaryedemaandcongestion（leftlung;

740g）.Mucosalhemorrhageswerenotedinmostpartsofthesmallintestine.Therewerenospecificfindingsinotherorgansexceptforseverecongestion.TissueswereformalinfixedandexaminedbyHEandSchmorlstainingsafteranammonia-ethanoltreatmenttoremoveformaldehyde-derivedartifacts[9].OilredOstainingofthelivertissuewasalsoperformedusingcryostatsections[10].Fortoxicologicalanalysis,bloodandtissuesampleswerecollectedinthickplasticbags（UnipackG-4,SeinichiCo.Ltd.,Japan）,vacuumsealedandimmediatelystoredat308Cuntilanalysis.

4.Toxicologicalanalysis

4.1.Chemicals

StandardFreon22gas（99.9%）waspurchasedfromFukuhoteisanCo.,Fukuoka,Japanandusedforcalibration.Allsolventsandchemicalswereofanalyticalgradeandpurchasedthroughlocalsuppliers.StandardFreon22gaswastransferredintoaglassvialbythewaterdisplacementmethod.Briefly,aglassvialwassubmergedintapwaterandthewaterinthevialwasdisplacedbythestandardFreon22gas.ThevialwasthensealedwithaTeflonrubberunderwater.TheexactvolumeofFreon22wastakenfromthevialbyusinggas-tightcyringesandusedforcalibration.ThevolumeofFreon22wasconvertedintoweightaccordingtotheAvogadro’slaw.

4.2.Samplepreparations

Onemilliliterofdefrostedbloodand1geachofslicedfrozentissuewassealedinaglassvialwithasiliconseptum.Forquantitativecalibrations,exactvolumesofpureFreon22gasweretransferredintosealedvialscontaining1mlofblancbloodusinggas-tightsyringes.Eachvialwasheatedat508Cinanelectricaluminumblockheater（EiraCo.Ltd.,Tokyo,Japan）for15minandits100mLoftheheadspacewereintroducedontotheGC–MSbyusingagas-tightsyringe.Eachsampleandcalibrationvialwaspreparedintriplicate.

4.3.GC–MSconditions

GC–MSanalysiswasperformedbyShimadzuQP-5000（ShimadzuCo.,Kyoto,Japan）.TheGCconditionswereasfollows:

splitlessinjectionmode;

column,DB-WAXcapillarycolumn,30m0.25mmi.d.,250nmfilmthickness;

injectionporttemperature,1808C;

carriergas,helium;

flowrate,1.2ml/min;

columntemperature,308C.TheMSconditionswereasfollows:

fullscanmodeforqualification（m/z30–150）,selectedionmonitoring（SIM）modeforquantification（m/z51）;

ionization,EI;

interfacetemperature,2308C.

5.Results

5.1.Histologicalfindings

HEstainingofthelungshowedseverecongestionandedema.Therewerenomarkedfindingsinotherorgansexceptforcongestion.OilredOstainingofthelivershowedmanysmallpositiveredareasinthecytosol（Fig.2A）.SchmorlstainingrevealedthatmostportionsoftheOilredOstainingpositiveareaswerelypofuscingranules（Fig.2B）.

5.2.Toxicologicalanalysis

ThepresenceofFreon22inthebloodandtissueswasconfirmedbytheGC–MSanalysis.Freon22waselutedataretentiontimeof1.4minandtheobtainedmasschromatogramwasthesameasthatobtainedfromauthenticFreon22（Fig.3）.Noothervolatilesubstances,includingfluorocarbons,weredetectedinanyofthesamples.Linearityofthecalibrationcurvewasobservedfrom0to380mg/mlofpureFreon22withacorrelationcoefficientof0.995（Fig.4）.ResultsofFreon22analysisareshowninTable1.TheconcentrationofFreon22inbloodwas1697.0mg/ml.Intissuesamples,thehighestFreon22levelwasobservedin.

6.Discussion

ItiswellrecognizedthathalogenatedhydrocarbonsincludingFreon22depressthecentralnervoussystemand

Fig.4.（A）SIM（m/z51）chromatogramsof

（1）heartblood,

（2）standardFreon22,（3）blancblood.（B）AtypicalstandardcurveofFreon22inblood.

inducebothcardiacarrhythmiasandexcessivesecretioninthetrachea[11–13].Thesedirecttoxiceffectsofthechemicalcouldbeacauseofdeath.Ontheotherhand,duetotheheavyvapordensityofFreon22,itdisplacesairandresultsininsufficientoxygenconcentration,whichcouldalsobeacauseofdeath.

Inthepresentcase,toxicologicalanalysisclearlyshowedthatthedeceasedinhaledFreon22gaspriortohisdeath.Theautopsyfindingsexcludedsuffocationduetoexcessivesecretionsinthetracheafromthecausesofdeath.However,toxicologicalandhistologicalfindingscouldnotfullyelucidatethemannerorthedirectcauseofdeath.Firstofall,asinmost

previouslyreportedcases[4–8],bothFreon22andoxygenconcentrationsatthescenewereunknown,andasphyxiaduetolowoxygenconcentrationscannotbeconfirmedasacauseofdeath.Secondly,autopsyfindingsspecifictoFreon22poisoninghavenotyetbeenreported.GranularfatdropletspositivetoSudanIIIstaininginthehepatocyteswerereportedinsimilarFreon22poisoningcases,butthemechanismsofthefindingsarecontroversial[4–7].Moritaetal.reportedtwoFreon22poisoningcasesandsuspectedthatthefatdropletsintheliverwereproducedbytheeffectofFreon22.OtherreportssuggestedthattheywerenotspecifictothetoxicityofFreon22[5–7].Kazamaetal.showedinanimalexperimentsthatfinefatdropletsappearedtemporarilyinthecourseofinhalingFreon22,butitdisappearedimmediatelyafterstoppingtheinhalationandtheyweredifferentfromhepatictoxicityreportedinchronicexposuretochloroformandotherchlorinatedhydrocarbons[5].

Inthepresentcase,similarpathologicalfindingswereobservedintheliver.However,mostofthemwerepositivetoSchmorlstaining,whichisspecifictolipofuscinpigment.Thishasnotbeenmentionedinsimilarpreviouscasereports[4–8].Lipofuscinislocatedinlysosomesandcontainsproductsoftheperoxidationofunsaturatedfattyacids,whichcloselyrelatetoagingandothercellstresses[14].Itisreportedthattheexistenceoflipofuscinintissuescouldbeamarkerofchronicexposurestolowconcentrationofchemicalsubstances[15].HighFreon22concentrationintheliverma