MIYAMOTO, Junshi

SATO, Yoshishige

SUZUKI, Shin-ichi

Kyoto University Research Information Repository

TitleDetermination of Insecticide Residue in Animal and PlantTissues. V : A Device of Preparing the Specific Detector ofGas Chromatograph Highly Sensitive to OrganophosphorusInsecticidesAuthor(s)SATO, Yoshishige; MIYAMOTO, Junshi; SUZUKI, Shin-ichiCitation防虫科学 (1968), 33(1): 8-12Issue Date1968-02-29URL http://hdl.handle.net/2433/158530RightType Departmental Bulletin PaperTextversionpublisherKyoto University防 虫 科 学 第 33 巻-iDeterminationofInsecticideResidueinAnimalandPlantTi88ueB.V.･ADeviceofPreparingtheSpecificDetectorofGasChromatographHighlySensitivetoOrganophosphorusInsecticides.YoshishigeSATO,'JunshiMIYAMOTOandShin･ichiSuzuKI(AgriculturalChemicalsResearchDepartment,OsakaWorks,SumitomoChemicalCo.,Ltd.Osaka)ReceivedJanuary8,1968.BoEyu･Kagakw,33,8,1968.2. 動植物組抵中における残留殺虫剤の定量5･ 有機りん化合物に特異的に高感度を示す熱イオンJjg水諺淵 イオン化検出器の試作 佐藤番免 官本紙2,飴木信一 (住友化学工業株式会祉 大収艶iME2兆研究部)43.1.8受理1964年 Giuffridaらによって Na2S04を用いた熱イオン型水素焔イオン化検出器がはじめて軸/Aされて以来,ガスクロマトグラフによる有機りん良薬の残留成分分析の分野に各種の熱イオン型水菜娼イオン化検出器が用いられて来た.それらの多くはいずれも使用寿命が短かくノイズ.レベルが高く長時間の連続分析に耐え得ないという欠点を有している.著者らは.上述の瓜を改良する目的で熱イオン源にKBrの申約品の盤形品を用いた熱イオン型水 ,素焼イオン化検山淵を試作した.こ･の枚山賀馴ま既存のものに比較して長時間の連続分析が可能であり.(迎統依用時間は100時間以上であり.盤形しなおすことによりさらに100時間以上桃川が可能であった) 雑音レベルが梅めて低い. この検出器を用いて教程の有機りん殺虫剤の分析を行なったところ 1×10~11グラムの最高感度を得,また1×10~Jグラムの実用分析感度を柑た.玄米,gjE,出 ミルク等のサンプルについて残留分析を行ない 0.002ppm まで容易に分析することができた.TntroductionThetheoryandmodeofoperationofthesodiumthermionicdetector(namedSTD)gaschroma･tographywasfirstreportedbyGiuffrida(1964a,b).Recently in theresidualanalysisoforga･nophosphoruscompoundsmanyworkershaveusedthegaschromatographequippedwithSTDandotherspecificdetectorsbelongingtothesamecategory,becausetheSTDwasfoundenormouslysensitivetoorganophosphoruscompoundsandmuchlesssensitivetoothercarboncompounds(Rahman1965.Giuffrida1966).Inthecaseofcoildwire･Coatedwithsodiumorotheralkalimetalsalts.somedifficultywasreportedtohappen.e.g.theaveragelifetimeofthewire･shapeddetectorwasonlyafewdaysatbest.Oaks(1966)devisedsuchatypeofdetectorwithaconsiderably longdurabilitybyuslngpressedsalt(cesiumbromide)tipforsaltreservoir.Thepresentauthorsutilizedapotassiumbromidesinglecrystalassaltsource.Thisdetectorwasnamedpotassium thermionicdetector,PTD,inthispaper,whichfacilitateddailyresidueanalysis,ascomparedwith apreviouswirecoildone(Miyamoto1967),thistypeofPTDensuredlong･8termoperationwithhighreliability.Experimentala) Modificationoftheusualflameionizationdetectortopotassiumthermionicdetector.Thegaschromatograph of type GC-3AF.ShimadzuSeisakushoCo.Ltd.,wasutilizedforthepurpose.PotassiumbromideusedforthemeasurementofIR spectrawascutbyhand,asshowninFig.1,withaholeofca.0.2mmindiameteratthecenter.ThiscrystaltipwasmountedontheceramicnozzleofF‥Dandfixed.Fig.2ShowsschematicalythePTDmodifiedfromconventionalFID.b) Operationalcondition.Asiswelknown,inworkingwithsuchaspecifictypeofdetector,itisofutmostimportancetocontrolthehydrogenflowrate,becausethemagnitudeofthebaselinecurrentwascloselyrelatedtotheflowrateofhydrogen,asshownin Fig.3,and thatresponseto phosphoruscompoundswasdependentonthemagnitudeofthespecificbaselinecurrent,asreproducedinFig.4. Thatis,approximately5.0×10~Bamp.maximumand1.0×10~9amp.minimumofbaselinecurrentwerefoundtobegeneratedrespectivelyatthehydrgenflow rateof化.45mJ/min.防 虫 科 学 卯 33 巻-IlOle0.lmm- pOtaSSlumt)romidesinKtCerySt.llhytrlH･Cnn;tTlC･potnssium hrom i(lぐsindccrystalCeramicnozzle!:‡･5n-tmJFig･1･ Anassemblyofeel.amicnozzleandpotassiumbromidesing一ecrystal.酷ioncr州eclnrFtD I)'rl)ceramicnozZ]e一一 columnerluentplushydrogenhnぐ0日(･L.torr)otasiumsinri･1ccryst.llecr.lmicnoz7.1C- eoTumnctlucntl)IuslytIrogenFig.2. Aschematicdrawingoftheconversionofaflameionizationdetectortoapotassiumthermionicdetector.?? ? ? ?? ? ? ? ?? ????? ? ? ??????10 20 30 40Hydrogenflowrate(mJ/min)Fig.3. EffectofhydrogenflowrateonPTDbaselinecurrent.ノ /l1019 10-& ･lollBaselinecurrent(amp)Fig.4. Effectofbaselinecurrentondetectorsensitivity.防 虫 科 学 第 33 巻-Imaximum andca.20mL/min.minimum.Theflameburningabovethetopofthesalttipgeneratedabaselinecurrentsome200timeshigherthantheconventionalflamedetector.Undertheactualoperationalconditions,hydrogenflowratewassocontroledastoobtainsensitivitygiving100percentrecorderscaleresponseat1.6×10~lAFS,byinjectionof10nanogramsofethylparathion.Thesensitivitywas2,000timesgreateratthemaximum thanthatattainedbytheconventionalflamedetector.Underthesamecondition,otherhydrocarboncompoundssuch???? ? ?????????? ???? ??? ?? ? ?? ??n 5 10Time(min)Fig.5. AnalysisofmixtureofBIiC,dibutylphthalateandSumithionbyFID(upper)andPTD (lower).FID,BHC,dibutylpltbalate,SumithioneachlOJg.PTD.BHC,dibutylphthalate,eachlOFLg.Sumithion,5ng.? ??? ? ? ?? ? ?? ? ? ? ? ? ? ? ? ?0 5 1()Time(min)Fig.6. Analysisofamixtureof5nanogramseachofmethylparathionSumitbionandethylparathionbyPTD.(Curves,leftto right;methylparathion,Sumithionandethylparathion.)10asBHCanddibuthylpbthalateintheorderofmicrogram werehardlydetected,asevidentinFig.5.Fig.6showstheresponseofPTDto5nanogramsofmethylparathion,Sumithion常andethylparathionattheelectrometersettingof1.6×10~8AFS.under2.5×10~8amp.baselinecurrent. Operationalparametersinthiscasewereasfolows;Thepyrexglasscolumn(oncolumninjectionsystem)1.5Mx4mmid.,waspackedwith1:1mixtureof8% DC-200and16%QF-1on60-80meshchromosorbW aw.Thecarriergas,helium,wasadjustedtotheinletpressureof2.0kg/cm2.ca.40ml/min.Conditioningofthiscolumnwascarriedoutatca.250.Cfor24hourswith50mJ/min.helium flow rate.Thus,undertheaboveconditions,thisPTDgavenoise･less.Welbalancedbaselinecurrentandwashighlysensitivetoorganophosphoruscompounds.Moreover,itcouldbeusedsatisfactorilyformorethan100hours,givingreliable,reproduciblepeaks.C) Ilustrativeexamples.Onehundredequivalentoftomato,cucumberorapplehomogenatesfortifiedwith10microgramseachofmethylparathion.Sumithionぜandethylparathion wasprocessedasin thepreviouspaper(Miyamoto1967),excepttbatタ卜hexane･acetonitrile clean･up stepwasomitted. Onehundredgramsoffinelypowderedricegrainweresoaked together with10microgramsoftheorganophosphoruscompoundsin200mJofbenzeneovernight. BenZenelayer wasseparatedbyfiltrationandthefiltercakewaswashedtwicewithlOOmJeachofbenzene.Afterevaporationofthebenzenesolutionl'nvacuo.theresiduewaspartitionedbetweenJ卜hexaneandacetonitrile.Acetonitrilelayerwasseparatedandconcentrated.Afterdissolvedtheresidueinaknownvolumeofacetone,analiquotwasgaschromatographed.TypicalchromatogramsofcontrolandfortifiedsamplesareshowninFig.7.AsevidentfromFig.7,peaksattheretentiontimeoforgan･ophosphoruscompoundswerelessthan0.002ppmequivalent.Organophosphoruscompoundsaddedtothehomogenatewererecoveredsubstantialycompletly. Under tle presentexperimentalconditions.therefore,phosphoruscontainingln･Secticidespresentinsamplesattheconcentration防 虫 科 学 節 33 巻-ID.? ???? ? ??? ??? ? ? ? ? ??????? ? ??? ?? ? ?? ?? ? ??? ????? ??? ?? ? ? ? ?? ??I Cnntrollll l lI lI Recoveredl t l l f l0 :～ Jl rl A l0 12 11IminControll l l l l t lI ReCOVCrCdI0 17 4 6 8 10 12 14mincontrolll l l l l lt Ⅰ Reeovered0 l LI 6 8 10 12 1`lmin? ? ? ? ?????????????? ???? ? ??? ??? ? ? ? ? ? ??0 2 4 6 8 10 12 11minControlll l l l lt t ll Re亡OYeredo :2 1 6 8 10 12 14minFig.7. Chromatogramsforrecoveryof0.lppmorderofmethylparathion,Sumithiomandethylparathionfrom plantandanimaltissues.A.RecoveryofSumithionfrom freshmilka.RecoveryofmethylandethylparathionfromcucumberC.Recoveryofmethylandethylparathionfrom tomatoD.RecoveryofmethylandethylparathionfromappleE.Recoveryofmethylparathion,Sumithionandethylparathionfrom ricegrainI.Methylparathion II.SumitbionIII.Ethylparathionll防 虫 科 学 第 33 巻-Iofabove0.002ppmcanbedetermined.Di且Cu8aion8ComparedwithPTDreportedhere.thepreviouscoiledwireSTD(Miyamoto1967)wasoffarshorterdurabilityandgaveless reproduciblepeaks.Moreover.thisSTD requiredfarlongerpre･conditioningperiodbeforeuse.TheseunfavorableipropertiesoftheSTD areseeminglyduelforexample.tothefactthattiledistancebetweenspiralandburningflameisvaried,andthatalkalimetalsaltlayerisnotalwaysuniformlycoated.whichmakesiontemperatureunstable.The㌣TDisfreefrom suchunfavorablefactorsandiontemperatureispresumablysolelyde･pendentontilehydrogenflow rate,givingrisetothestablesensitivitytophosphoruscontainingcompounds. Furthermore,potassium bromidesinglecrystalcontainsminimumamountofim･purities.whichfavorsalsotogainstablebaselinecurrent;powderedpotassium bromideofguaranteedreagentgradecompressedtoatabletcouldnotbeusedpracticalybecauseofnoisesoftengenerated.Asshownaboye.PTD requiredmuchlowerhydrogenflowrateforagivenbaselinecurrentthancoiledSTD(Oaks1966.Itaya1966).Althoughithasnotyetbeencertainthatthisenhancedbaselinecurrentinitselfresultsdirectlyinthehighersensitivtytobhosphorus,forthesensitivtyratherdependsonthetemperatureofpotassiumionemitted(Itaya1966),theincreasedbaselinecurrentgreatlyaffectsthesensitivity.Therefore,Fitwasfoundnecessarytocontrolflowrateofhydrogen very strictly,which was attainedsometimesonlywithdifficultywithsuchatypeofapparatus.Whenapotassium bromidetipwasmountedononeofthedualdetectornozzlesandgas･chromatographwasrun.rnuChmoreamountofbaselinecurrentwasgeneratedon㌣TDside,12anditwasdifficulttoadjusttherecorder.Thus,theoperationcouldnotbedoneatthehydrogenflowrateofmorethan30mJ/min.(above2.8×1018amp.ofbaselinecurrent). Thisdifficultywasovercomebyintroducingaselectorswitchbetweenmercurialbatteries(bydoublingthecapacityofbattery,ifnesessary,)inthefeed･backcircuitofelectrometer,tocounter･balancetheenhancedbaselinecurrent,andastheresultsthesensitivitywasincreasedfurtherbymorethantentimes.TluS,thepotassium thermionicdetectorde･velopedherecanbeeffectivelyused,asshowninFig.7,forthemicrodeterminationoforganopbos･phoruscompoundsinanimalandplanttissues.Indeed,Combinedwithsuitableextractionandclean-upprocedures.theresidulessthan0.Olppmcouldbeveryeasilymeasuredgaschroma･tograpbicalywiththemodifieddetector.Acknwledgement: The authors are verygratefultoDr.M.ItayaofShimadzuSeisakusho,CoリLtd.forlisinvaluablesuggestionandadvice･TheywishtoexpresstheirthankstoSumitomoChemicalCo.Ltd.forpermissiontopublishthiswork.I.iteratureBLCitedGiuffrida,L.:Jour.ofA.0.AC･,47.293(1964a)･Giuffrida,L.andF.Ives:l'bid.47,1112(1964b).Giuffrida.L.,F.IvesandD.Bostwick:1'bid.49.8(1966).Itaya,M.:SpeechatThe15th JointAnnualMeetingoftheJapanSocietyforAnalyticalChemistry(Fukuoka)(1966).Miyamoto,J.,Y.Sato and S.Suzuki:Botyu-Kagaku,32.95(1967).Oaks,D.M.,K.P.Dimick and H.Hartmann:VarianAerographreprintNo.122(1966).Rahman.A.andA.E.Refai:Jour.ofA.0.A.C.,48,374(1965).

2.動植物組織中における残留殺虫剤の定量 5 : 有機りん化合物に特異的に高感度を示す熱イオン型水素焰イオン化検出器の試作

http://repository.kulib.kyoto-u.ac.jp/dspace/bitstream/2433/158530/1/btk03301_008.pdf

2.動植物組織中における残留殺虫剤の定量 5 : 有機りん化合物に特異的に高感度を示す熱イオン型水素焰イオン化検出器の試作

Abstract

Similar works

Full text

Available Versions

Kyoto University Research Information Repository