ICP-MS不确定度评定

ICP-MS不确定度评定,,,,,,,,

,,,,,,,,,

,,,,,,,,,

,,,,,,,,,

,,,,,,,,,

,,,,,,,,,

,,,,,,,,,

,,,,,,,,,

1Objective目的,,,,,,,,

用于评定ICP-MS的不确定度（参考GB/T5750.6-2006）。,,,,,,,,

,,,,,,,,,

2

Scope范围,,,,,,,,

,2.1

参考方法,,,,,,,

,生活饮用水标准检验方法金属指标GB/T5750.6-2006,,,,,,,

,2.2

Instrumentandreagent主要仪器及试剂规格,,,,,,,

,2.2.1硝酸,,,,,,,

,2.2.95％硝酸,,,,,,,

,2.2.1Be、Ti、V、Cr、Co、Ni、Cu、Zn、As、Sr、Cd、Sn、Sb、Ba、Tl、Pb标液(1000mg/L),,,,,,,

,,,,,,,,,

3

Flowchart流程图,,,,,,,,

,Samplingaccordingtostandard.Minmum10mgsampleisrequired按方法要求制样。样品少于10mg不进行检测。,,,,,,,

,,↓,,,,,,

,"weighing0.2gsampleintoflask,accurateto0.1mg准确称取0.2g样品到三角锥形瓶中，精确至0.1mg",,,,,,,

,,↓,,,,,,

,"Addhydrochloricacidaccordingtodifferentmaterial,volumeis50timesofsampleweight.Ifsampleisnotenough0.1g,add5mlhydrochloricacid.按各种材质的不同对其加入盐酸，加入盐酸体积为质量的50倍，不够0.1g的加入5ml。",,,,,,,

,,↓,,,,,,

,"Shakefor1min,checkpHvalue.IfpHisgreaterthan1.5addanhydrochloricsolutionaproximately2mol/luntilpHisbetween1.0and1.5摇动1min，检查pH，如果pH大于1.5，加入2mol/L盐酸直至pH达到1.0-1.5。",,,,,,,

,,↓,,,,,,

,"Putsampleintowaterbath,at（37±2）℃shakingfor1h,shakingfrequency（60±2）times/min,andstandfor1h.将样品放进恒温水浴锅，在（37±2）℃下振荡1h,振荡频率（60±2）次/min,静止1h.",,,,Preparationofstandardsolution制备标准溶液,,,

,,↓,,,↓,,,

,,"Fliter,testbyICP.过滤，ICP读数",,——,ICPtestICP读数,,,

,,,,↓,,,,

,,,,Results结果,,,,

,,,,,,,,,

41.IdentificationofSourcesofUncertainty不确定度来源分析,,,,,,,,

,4.1Mathmodel不确定度模型,,,,,,,

,,,,,,,,,

,,,,,,,,,

,,,,,,,,,

,"Cisthecontentofcertainelementsbeforeadjustment,mg/kg调整前元素含量，mg/kg

Creadistheconcentrationofheavymetalinsamplesolution,mg/l样品溶液中重金属元素的浓度，mg/l

VisthevolumeofHCladdedintotestspecimen,ml加入到测试样品中的HCl的体积，ml

Disdilutionfactor稀释因子

misthemassoftestspecimen,g测试样品的质量，g

",,,,,,,

,4.2SourcesofUncertainty确定不确定度的来源,,,,,,,

,4.2.1UncertaintyofPrecision精密度,,,,,,,

,4.2.2UncertaintyofTrueness准确度,,,,,,,

,4.2.3UncertaintyofCalibrationCurve校准曲线,,,,,,,

,4.2.4Uncertaintyofreferencestandard标准品,,,,,,,

,"Theuncertaintyduetoreferencestandardorpurityforstandard.Ifthereferencestandardissolid,theuncertaintyduetopreparationofstandardsolutionshouldbeconsidered.

标准品的不确定度或纯度。如标准品为固体标物，还需考虑标准品称量引入的不确定度",,,,,,,

,4.2.5Uncertaintyofmassofsamplebybalance天平称量样品质量,,,,,,,

,"Massofsampleisfromaccountwithgrossmassandtaremass.Theuncertaintysourceisfromthreeparts.Oneisrepeatability(itcanaccountinrepeatability4.2.1),thesecondismaximalallowableerror(Thecalibrationitselfhastwopossibleuncertaintysources:thesensitivityandthelinearityofthecalibrationfunction.Becausetheweighingisdoneonthesamescaleandoverasmallrangeofweightthenthesensitivitycontributioncanbeneglected.),andthethirdisthereadingofthescale.

质量m由已扣除皮重的称量得出。制造商的说明书确认扣除皮重称量的三个不确定度来源:重复性（归并为方法重复性中）,天平最大允差(包括天平的灵敏度及其线性,其中灵敏度可忽略,因为减量称量是用同一架天平在很窄范围内进行的)，以及天平的分辨力。",,,,,,,

,4.2.6Uncertaintyofvolumeforsample试样体积,,,,,,,

,"Theuncertaintyofvolumeforsamplesolutionisfromflask,whichisincludingmaximalallowableerrorofflaskandthesolutiontemperaturedifferingfromthecalibrationtemperatureofthepipette.

体积的不确定度主要由容量瓶的不确定度引起,容量瓶的体积主要有两个不确定度来源：a.体积最大允差引起的不确定度；b.由实验室温度变化引起的体积不确定度。",,,,,,,

,4.3sumup列表综述,,,,,,,

"SourcesofUncertainty

不确定度来源",,"Type

类型

（AorB）","Unit

单位",不确定度/半宽度,"factor

概率分布","standarduncertainty

标准不确定度(ui)",,

,,,,,,,,,

"Method

分析方法",精密度Precision,A,mg/L,"标准偏差

",normal正态,,,

,"Trueness

准确度",A,％,,normal正态,,,

"C

样品浓度

","标准曲线

Calibrationcurve",A,mg/L,,normal正态,,,

,,,,,,,,,

,"标准品

Referencestandard",B,mg/Lormg/kg,证书提供的不确定度或纯度,k=2,，k＝2,,

,,,,,,,,,

"Volume

体积","maximalallowableerror

最大允差",B,mL,该级别容量瓶的最大允差,"triangle

三角",,,

,calibrationtemperature容量瓶温度膨胀,B,ml,,rectangle矩形,,,

"Mass

质量","maximalallowableerror

天平最大允差",B,mg,"证书提供的最大允差

",rectangle矩形,,,

,,,,,,,,,

,"distinguishability

天平分辨率",B,mg,,rectangle矩形,,,

5QuantificationofUncertainty各部分不确定度的计算,,,,,,,,

5.1Uncertaintyforprecision方法精密度引入,,,,,,,,

,"Samples(spikeorCRM)ofseverallevelsoverextendedperioldoftimewereusedtodeterminetheprecision.Theresultisasblow.

制备多个浓度加标样品/标准品进行重复性测试。",,,,,,,

,,,,,,,,,

"Combinedstandarddeviation

合成标准偏差为：",,,,,,,,

,,,,,,,,,

"Combinedrelativestandarddeviation

合成相对标准偏差为：",,,,,,,,

,,,,（n:repeattimes评定时重复测试的次数）,,,,

,,,,,,,,,

"Relativestandarduncertainty

相对标准不确定度为：",,,,,,,,

,mmeansactualtestmethodrepeattimes(实际测试重复次数)：1,,,,,,,

Testresultslistbelow,,,,,,,,

,,,,,,,,,

,测试物质,As,,,,,,

,"matrix

基体名称",本底,加标1,加标2,加标3,,,

,标准值/加标值,20.00,40.00,50.00,80.00,,,

,No,Trial1,Trial2,Trial3,Trial4,,,

,1.00,20.14,37.24,47.65,72.48,,,

,2.00,19.76,37.51,46.71,72.85,,,

,3.00,20.01,37.38,46.38,72.72,,,

,4.00,19.74,37.82,46.35,73.60,,,

,5.00,19.53,37.53,46.03,74.06,,,

,6.00,19.09,36.99,45.06,73.30,,,

,n-1,5.00,5.00,5.00,5.00,,,

,SD,0.37,0.28,0.85,0.59,,,

,RSD,0.02,0.01,0.02,0.01,,,

,合成标准偏差s(p),0.57,,,,,,

,合成相对标准偏差RSD(p）,0.01,,,,,,

,标准不确定度u(p),0.57,,,,,,

,相对标准不确定度u(relp),0.01,,,,,,

,,,,,,,,

,测试物质,Ba,,,,,,

,"matrix

基体名称",本底,加标1,加标2,加标3,,,

,标准值/加标值,20.00,40.00,50.00,80.00,,,

,No,Trial1,Trial2,Trial3,Trial4,,,

,1.00,20.19,35.97,46.68,71.75,,,

,2.00,19.84,35.95,45.98,71.55,,,

,3.00,19.88,36.55,45.56,71.44,,,

,4.00,19.44,36.64,45.45,72.14,,,

,5.00,19.04,36.36,45.21,72.43,,,

,6.00,18.90,35.93,45.24,72.04,,,

,n-1,5.00,5.00,5.00,5.00,,,

,SD,0.51,0.32,0.56,0.38,,,

,RSD,0.03,0.01,0.01,0.00,,,

,合成标准偏差s(p),0.45,,,,,,

,合成相对标准偏差RSD(p）,0.01,,,,,,

,标准不确定度u(p),0.45,,,,,,

,相对标准不确定度u(relp),0.01,,,,,,

,,,,,,,,

,测试物质,Cd,,,,,,

,"matrix

基体名称",本底,加标1,加标2,加标3,,,

,标准值/加标值,20.00,40.00,50.00,80.00,,,

,No,Trial1,Trial2,Trial3,Trial4,,,

,1.00,20.13,37.08,47.60,73.69,,,

,2.00,19.91,37.13,46.84,73.08,,,

,3.00,19.93,37.20,46.43,73.53,,,

,4.00,19.65,37.63,46.73,73.98,,,

,5.00,19.59,37.58,46.12,73.88,,,

,6.00,19.44,37.40,46.35,73.96,,,

,n-1,5.00,5.00,5.00,5.00,,,

,SD,0.26,0.24,0.52,0.34,,,

,RSD,0.01,0.01,0.01,0.00,,,

,合成标准偏差s(p),0.36,,,,,,

,合成相对标准偏差RSD(p）,0.01,,,,,,

,标准不确定度u(p),0.36,,,,,,

,相对标准不确定度u(relp),0.01,,,,,,

,,,,,,,,,

,测试物质,Cr,,,,,,

,"matrix

基体名称",本底,加标1,加标2,加标3,,,

,标准值/加标值,20.00,40.00,50.00,80.00,,,

,No,Trial1,Trial2,Trial3,Trial4,,,

,1.00,19.47,36.20,46.68,75.94,,,

,2.00,19.34,36.78,45.93,75.35,,,

,3.00,19.29,36.90,45.50,74.60,,,

,4.00,18.96,36.93,45.03,75.61,,,

,5.00,18.96,36.57,45.13,76.44,,,

,6.00,18.58,36.54,45.15,74.62,,,

,n-1,5.00,5.00,5.00,5.00,,,

,SD,0.33,0.27,0.63,0.73,,,

,RSD,0.02,0.01,0.01,0.01,,,

,合成标准偏差s(p),0.53,,,,,,

,合成相对标准偏差RSD(p）,0.01,,,,,,

,标准不确定度u(p),0.53,,,,,,

,相对标准不确定度u(relp),0.01,,,,,,

,,,,,,,,

,测试物质,Ni,,,,,,

,"matrix

基体名称",本底,加标1,加标2,加标3,,,

,标准值/加标值,20.00,40.00,50.00,80.00,,,

,No,Trial1,Trial2,Trial3,Trial4,,,

,1.00,20.32,37.75,48.14,74.33,——,——,

,2.00,20.07,38.26,47.67,74.37,——,——,

,3.00,20.01,38.25,47.39,74.11,——,——,

,4.00,19.85,38.24,46.75,74.62,——,——,

,5.00,19.68,37.99,46.55,74.61,——,——,

,6.00,19.72,37.79,46.77,74.31,——,——,

,n-1,5.00,5.00,5.00,5.00,——,——,

,SD,0.24,0.24,0.63,0.19,——,——,

,RSD,0.01,0.01,0.01,0.00,——,——,

,合成标准偏差s(p),0.37,,,,,,

,合成相对标准偏差RSD(p）,0.01,,,,,,

,标准不确定度u(p),0.37,,,,,,

,相对标准不确定度u(relp),0.01,,,,,,

,,,,,,,,,

,测试物质,Pb,,,,,,

,"matrix

基体名称",本底,加标1,加标2,加标3,,,

,标准值/加标值,20.00,40.00,50.00,80.00,,,

,No,Trial1,Trial2,Trial3,Trial4,,,

,1.00,20.13,37.67,48.75,75.10,,,

,2.00,20.16,37.64,48.38,75.21,,,

,3.00,20.18,37.89,48.00,74.89,,,

,4.00,20.05,37.87,47.55,74.75,,,

,5.00,19.88,37.75,47.48,75.67,,,

,6.00,19.66,37.70,47.82,75.30,,,

,n-1,5.00,5.00,5.00,5.00,,,

,SD,0.21,0.10,0.49,0.32,,,

,RSD,0.01,0.00,0.01,0.00,,,

,合成标准偏差s(p),0.32,,,,,,

,合成相对标准偏差RSD(p）,0.01,,,,,,

,标准不确定度u(p),0.32,,,,,,

,相对标准不确定度u(relp),0.01,,,,,,

,,,,,,,,,

,测试物质,Sb,,,,,,

,"matrix

基体名称",本底,加标1,加标2,加标3,,,

,标准值/加标值,20.00,40.00,50.00,80.00,,,

,No,Trial1,Trial2,Trial3,Trial4,,,

,1.00,19.73,36.02,46.62,71.42,,,

,2.00,19.58,36.35,45.89,71.30,,,

,3.00,19.64,36.44,45.61,70.78,,,

,4.00,19.30,36.69,45.35,71.51,,,

,5.00,19.10,36.35,44.99,71.63,,,

,6.00,18.89,36.07,45.15,71.75,,,

,n-1,5.00,5.00,5.00,5.00,,,

,SD,0.33,0.25,0.60,0.34,,,

,RSD,0.02,0.01,0.01,0.00,,,

,合成标准偏差s(p),0.40,,,,,,

,合成相对标准偏差RSD(p）,0.01,,,,,,

,标准不确定度u(p),0.40,,,,,,

,相对标准不确定度u(relp),0.01,,,,,,

,,,,,,,,,

,测试物质,Cu,,,,,,

,"matrix

基体名称",本底,加标1,加标2,加标3,,,

,标准值/加标值,20.00,40.00,50.00,80.00,,,

,No,Trial1,Trial2,Trial3,Trial4,,,

,1.00,20.15,37.32,47.11,76.11,,,

,2.00,20.01,37.53,46.82,75.44,,,

,3.00,19.89,37.65,46.45,75.41,,,

,4.00,19.67,37.60,46.19,76.32,,,

,5.00,19.54,37.39,46.21,76.15,,,

,6.00,19.34,37.40,46.05,75.78,,,

,n-1,5.00,5.00,5.00,5.00,,,

,SD,0.30,0.13,0.41,0.39,,,

,RSD,0.02,0.00,0.01,0.00,,,

,合成标准偏差s(p),0.33,,,,,,

,合成相对标准偏差RSD(p）,0.01,,,,,,

,标准不确定度u(p),0.33,,,,,,

,相对标准不确定度u(relp),0.01,,,,,,

,,,,,,,,,

5.2UncertaintyofTrueness方法准确度(回收率）引入,,,,,,,,

,Calculatetherecoverybythedata5.1根据5.1计算回收率,,,,,,,

,"Recoveryshouldincludetwopartsasbelow:

回收率可分为以下两部分考虑：

Rm：RecoveryofspikeorCRMsamples

添加或有证基体标准物质平均回收率

Rs：TherevisedvaluefromothermatrixwhichisdifferentwiththematrixofRm.ButwehavecalculaterecoveryofdiferentmatrixinRm,soithasbeenrevisedinRmandwecanignorethispart.

其他不同于Rm基体回收率检测基体的修正值，由于我们只考虑此几种基体的情况，在Rm中已经进行修正，故此处不予考虑。",,,,,,,

,"isgivenby:

则回收率总的不确定度计算公式为：",,,,,,,

,,,,,,,,,

,,,,,,,,,

,,issufficientlysmalltobeneglected.Andtheformulaischangedto:,,,,,,

,很小，可忽略不计，则公式变为：,,,,,,,

,WecangettherecoveryofTrail1to6bytheformulaabove.,,,,,,,

,根据上述公式，计算Trail1～6每组回收率计算结果如下列表,,,,,,,

,,,,,,,,,

,"Rmisstatisticallytestedbyt-testwhereitissignificantlydifferentfromthevalueof1inordertocheckthevalidityofthecontributionofinoveralluncertaintycalculation.

其中，我们需对Rm进行t检验，确认在统计学上此组回收率和1是否明显分别，以确定不确定度的全面性。",,,,,,,

,"Ift>tcrit，theconclusionwillshow""Yes"".Itmeanstherecoveryisstatisticallysignificantlydifferentform1.Theuncertaintymustbeincreasedtotakeaccountofthefactthattherecoveryhasnotbeencorrectedfor.Weshouldusetheincreaseduncertaintyinsteadof.

其中，我们需对Rm进行t检验，如果t>tcrit时，结论处显示""Yes""，表示在统计学上此组回收率和1有明显分别，则需对不确定度进行修正，以修正后的结果代替式一中的进行计算。",,,,,,,

,"Ift<tcrit，theconclusionwillshow""No"".Itmeanstherecoveryisstatisticallysignificantlydifferentform1,noexpansionofuncertaintyisneeded.如t<tcrit时，结论处显示""No""，表示和1无明显分别，可直接采用上述代入式一进行计算",,,,,,,

,ttestisgivedby检验公式为：,,,,,,,

,,,,,,,,,

,"Whenitshouldusetheincreaseduncertainty,isgivedby

需进行修正时，采用以下公式对进行修正。",,,,,,,

,,,,,,,,,

,,,,,,,,,

,"Resultislistasbelow,canbefoundoutbyn-1and95%confidenceintdistributinglist.",,,,,,,

,是根据测试次数n-1及95％的置信概率查t分布表得出。,,,,,,,

,"Combinedeachisgivedby

根据合并公式计算总的",,,,,,,

,,,,,,,,,

,As,,,,,,,

,No,Recovery回收率,,,,,,

,1.000,1.007,0.931,0.953,0.906,,,

,2.000,0.988,0.938,0.934,0.911,,,

,3.000,1.000,0.934,0.928,0.909,,,

,4.000,0.987,0.945,0.927,0.920,,,

,5.000,0.976,0.938,0.921,0.926,,,

,6.000,0.954,0.925,0.901,0.916,,,

,Average,0.986,0.935,0.927,0.915,,,

,SD,0.019,0.007,0.017,0.007,,,

,RSD,0.019,0.008,0.018,0.008,,,

,n,6.000,6.000,6.000,6.000,,,

,,0.008,0.003,0.007,0.003,,,

,t,1.897,22.463,10.526,28.128,,,

,查表,2.570,2.570,2.570,2.570,,,

,结论,No,Yes,Yes,Yes,,,

,,不需修正,0.033,0.037,0.043,,,

,修正后,0.008,0.033,0.037,0.043,,,

,,0.033,,,,,,

,,,,,,,,

,Ba,,,,,,,

,No,Recovery回收率,,,,,,

,1.000,1.009,0.899,0.934,0.897,,,

,2.000,0.992,0.899,0.920,0.894,,,

,3.000,0.994,0.914,0.911,0.893,,,

,4.000,0.972,0.916,0.909,0.902,,,

,5.000,0.952,0.909,0.904,0.905,,,

,6.000,0.945,0.898,0.905,0.900,,,

,Average,0.977,0.906,0.914,0.899,,,

,SD,0.025,0.008,0.011,0.005,,,

,RSD,0.026,0.009,0.012,0.005,,,

,n,6.000,6.000,6.000,6.000,,,

,,0.010,0.003,0.005,0.002,,,

,t,2.178,28.494,18.773,52.548,,,

,查表,2.570,2.570,2.570,2.570,,,

,结论,No,Yes,Yes,Yes,,,

,,不需修正,0.047,0.043,0.051,,,

,修正后,0.010,0.047,0.043,0.051,,,

,,0.041,,,,,,

,,,,,,,,,

,Cd,,,,,,,

,No,Recovery回收率,,,,,,

,1.000,1.006,0.927,0.952,0.921,,,

,2.000,0.995,0.928,0.937,0.913,,,

,3.000,0.997,0.930,0.929,0.919,,,

,4.000,0.982,0.941,0.935,0.925,,,

,5.000,0.980,0.940,0.922,0.924,,,

,6.000,0.972,0.935,0.927,0.925,,,

,Average,0.989,0.933,0.934,0.921,,,

,SD,0.013,0.006,0.010,0.004,,,

,RSD,0.013,0.006,0.011,0.005,,,

,n,6.000,6.000,6.000,6.000,,,

,,0.005,0.002,0.004,0.002,,,

,t,2.149,,15.574,44.971,,,

,查表,2.570,2.570,2.570,2.570,,,

,结论,No,No,Yes,Yes,,,

,,不需修正,不需修正,0.033,0.039,,,

,修正后,0.005,0.002,0.033,0.039,,,

,,0.026,,,,,,

,,,,,,,,,

,Cr,,,,,,,

,No,Recovery回收率,,,,,,

,1.000,0.973,0.905,0.934,0.949,,,

,2.000,0.967,0.920,0.919,0.942,,,

,3.000,0.964,0.923,0.910,0.932,,,

,4.000,0.948,0.923,0.901,0.945,,,

,5.000,0.948,0.914,0.903,0.955,,,

,6.000,0.929,0.914,0.903,0.933,,,

,Average,0.955,0.916,0.911,0.943,,,

,SD,0.016,0.007,0.013,0.009,,,

,RSD,0.017,0.007,0.014,0.010,,,

,n,6.000,6.000,6.000,6.000,,,

,,0.007,0.003,0.005,0.004,,,

,t,6.726,,17.119,,,,

,查表,2.570,2.570,2.570,2.570,,,

,结论,Yes,No,Yes,No,,,

,,0.024,不需修正,0.045,不需修正,,,

,修正后,0.024,0.003,0.045,0.004,,,

,,0.025,,,,,,

,,,,,,,,,

,Hg,,,,,,,

,No,Recovery回收率,,,,,,

,1.000,1.016,0.944,0.963,0.929,,,

,2.000,1.003,0.956,0.953,0.930,,,

,3.000,1.000,0.956,0.948,0.926,,,

,4.000,0.993,0.956,0.935,0.933,,,

,5.000,0.984,0.950,0.931,0.933,,,

,6.000,0.986,0.945,0.935,0.929,,,

,Average,0.997,0.951,0.944,0.930,,,

,SD,0.012,0.006,0.013,0.002,,,

,RSD,0.012,0.006,0.013,0.003,,,

,n,6.000,6.000,6.000,6.000,,,

,,0.005,0.002,0.005,0.001,,,

,t,0.610,,10.929,70.469,,,

,查表,2.570,2.570,2.570,2.570,,,

,结论,No,No,Yes,Yes,,,

,,不需修正,不需修正,0.028,0.035,,,

,修正后,0.005,0.002,0.028,0.035,,,

,,0.023,,,,,,

,,,,,,,,

,Pb,,,,,,,

,No,Recovery回收率,,,,,,

,1.000,1.007,0.942,0.975,0.939,,,

,2.000,1.008,0.941,0.968,0.940,,,

,3.000,1.009,0.947,0.960,0.936,,,

,4.000,1.003,0.947,0.951,0.934,,,

,5.000,0.994,0.944,0.950,0.946,,,

,6.000,0.983,0.943,0.956,0.941,,,

,Average,1.001,0.944,0.960,0.939,,,

,SD,0.010,0.003,0.010,0.004,,,

,RSD,0.010,0.003,0.010,0.004,,,

,n,6.000,6.000,6.000,6.000,,,

,,0.004,0.001,0.004,0.002,,,

,t,0.123,52.718,9.932,36.716,,,

,查表,2.570,2.570,2.570,2.570,,,

,结论,No,Yes,Yes,Yes,,,

,,不需修正,0.028,0.020,0.030,,,

,修正后,0.004,0.028,0.020,0.030,,,

,,0.023,,,,,,

,,,,,,,,,

,Sb,,,,,,,

,No,Recovery回收率,,,,,,

,1.000,0.987,0.901,0.932,0.893,,,

,2.000,0.979,0.909,0.918,0.891,,,

,3.000,0.982,0.911,0.912,0.885,,,

,4.000,0.965,0.917,0.907,0.894,,,

,5.000,0.955,0.909,0.900,0.895,,,

,6.000,0.945,0.902,0.903,0.897,,,

,Average,0.969,0.908,0.912,0.892,,,

,SD,0.017,0.006,0.012,0.004,,,

,RSD,0.017,0.007,0.013,0.005,,,

,n,6.000,6.000,6.000,6.000,,,

,,0.007,0.003,0.005,0.002,,,

,t,4.614,36.256,18.100,62.173,,,

,查表,2.570,2.570,2.570,2.570,,,

,结论,Yes,Yes,Yes,Yes,,,

,,0.017,0.046,0.044,0.054,,,

,修正后,0.017,0.046,0.044,0.054,,,

,,0.043,,,,,,

,,,,,,,,

,Se,,,,,,,

,No,Recovery回收率,,,,,,

,1.000,1.008,0.933,0.942,0.951,,,

,2.000,1.001,0.938,0.936,0.943,,,

,3.000,0.994,0.941,0.929,0.943,,,

,4.000,0.983,0.940,0.924,0.954,,,

,5.000,0.977,0.935,0.924,0.952,,,

,6.000,0.967,0.935,0.921,0.947,,,

,Average,0.988,0.937,0.929,0.948,,,

,SD,0.015,0.003,0.008,0.005,,,

,RSD,0.015,0.003,0.009,0.005,,,

,n,6.000,6.000,6.000,6.000,,,

,,0.006,0.001,0.003,0.002,,,

,t,1.881,47.297,20.855,26.240,,,

,查表,2.570,2.570,2.570,2.570,,,

,结论,No,Yes,Yes,Yes,,,

,,不需修正,0.031,0.035,0.026,,,

,修正后,0.006,0.031,0.035,0.026,,,

,,0.027,,,,,,

,,,,,,,,

,,,,,,,,,

5.3UncertaintyofCalibrationCurve标准曲线的不确定度,,,,,,,,

,,,,,,,,,

,,,,,,,,,

,,,,n=,18,P=,3,

,Cx:,,20.00,mg/L,,,,

,P———numberofmeasurement测试C的次数;,,,,,,,

,n———numberofmeasurementsforthecalibration测试校准溶液的次数;,,,,,,,

,Cx———determinedtargetconcentration试样溶液的浓度;,,,,,,,

,"———meanvalueofthedifferentcalibrationofstandards(nnumberof

measurements)不同校准标准溶液浓度的平均值(n次);",,,,,,,

,"i———indexforthenumberofcalibrationstandards下标,指第几个校准溶液;",,,,,,,

,"j———indexforthenumberofmeasurementstoobtainedthecalibrationcurve

下标,指获得校准曲线的测量次数。",,,,,,,

,,,,,,,,,

,,,,,,,,,

,,,,,,,,,

,,,,,,,,,

,,,,,,,,,

,,,,,,,,,

,As,,,,,,,

,浓度/吸光度,1,2,3,,,,

,0.000,286.68,180.01,60,,,,

,10.000,15745.63,12505.72,22400.99,,,,

,20.000,32166.17,25526.17,44434.71,,,,

,50.000,80973.5,63293.83,109150.85,,,,

,100.000,160959.04,125517.3,214377.1,,,,

,,,,,,,,

,B1(斜率）,1610.53,1254.47,2139.99,,,,

,B0（截距）,47.20,243.53,1045.25,,,,

,标准不确定度U,9.99,,,,,,

,"相对不确定度

Urel",0.50,,,Cx＝2.0,,,

,,,,,,,,,

,Ba,,,,,,,

,浓度/吸光度,1,2,3,,,,

,0.000,4267.47,3020.43,2033.56,,,,

,10.000,44230.26,34576.57,55781.64,,,,

,20.000,86220.65,68074.95,108049.74,,,,

,50.000,206427.43,165668.95,263324.35,,,,

,100.000,409565.20,326499.31,525260.84,,,,

,,,,,,,,

,B1(斜率）,4052.00,3239.02,5222.53,,,,

,B0（截距）,4270.36,2963.40,2878.88,,,,

,标准不确定度U,8.96,,,,,,

,"相对不确定度

Urel",4.48,,,Cx＝2.0,,,

,,,,,,,,,

,Cd,,,,,,,

,浓度/吸光度,1,2,3,,,,

,0.000,310.01,233.34,40.00,,,,

,10.000,51603.79,37182.68,69124.46,,,,

,20.000,102633.68,75864.36,136486.88,,,,

,50.000,259683.20,189216.43,337212.49,,,,

,100.000,518025.82,378387.34,668971.47,,,,

,,,,,,,,

,B1(斜率）,5183.16,3784.8,6679.9,,,,

,B0（截距）,-142.55,-75.66,1892.12,,,,

,标准不确定度U,10.55,,,,,,

,"相对不确定度

Urel",35.17,,,Cx＝0.3,,,

,,,,,,,,,

,Cr,,,,,,,

,浓度/吸光度,1,2,3,,,,

,0.000,17981.40,13369.75,183852.56,,,,

,10.000,165754.20,121744.75,380885.33,,,,

,20.000,311514.79,231112.59,580680.80,,,,

,50.000,750661.00,560489.42,1148208.34,,,,

,100.000,1524960.71,1096633.03,2162417.26,,,,

,,,,,,,,

,B1(斜率）,15056.07,10841.55,19732.67,,,,

,B0（截距）,12155.97,14374.20,180832.69,,,,

,标准不确定度U,14.40,,,,,,

,"相对不确定度

Urel",47.99,,,Cx＝0.3,,,

,,,,,,,,

,Hg,,,,,,,

,浓度/吸光度,1,2,3,,,,

,0.000,360.02,286.68,590.03,,,,

,10.000,77562.95,56913.24,105581.55,,,,

,20.000,152397.87,112461.73,209620.49,,,,

,50.000,387223.75,284021.61,512997.30,,,,

,100.000,765603.19,557971.19,1016218.99,,,,

,,,,,,,,

,B1(斜率）,7661.31,5582.36,10137.99,,,,

,B0（截距）,822.22,1365.82,4034.07,,,,

,标准不确定度U,11.11,,,,,,

,"相对不确定度

Urel",37.04,,,Cx＝0.3,,,

,,,,,,,,

,Pb,,,,,,,

,浓度/吸光度,1,2,3,,,,

,0.000,35810.07,27395.53,34705.25,,,,

,10.000,1434983.99,1073622.96,1858086.34,,,,

,20.000,2830364.96,2122823.93,3738243.12,,,,

,50.000,7099253.75,5320878.31,9141773.46,,,,

,100.000,14081345.42,10502733.33,17865860.57,,,,

,,,,,,,,

,B1(斜率）,140599.86,104877.55,178225.21,,,,

,B0（截距）,34756.75,33899.10,111626.12,,,,

,标准不确定度U,9.90,,,,,,

,"相对不确定度

Urel",4.95,,,Cx＝2.0,,,

,,,,,,,,

,Sb,,,,,,,

,浓度/吸光度,1,2,3,,,,

,0.000,120.00,40.00,40.00,,,,

,10.000,113722.62,89270.01,150677.94,,,,

,20.000,226167.24,177292.18,300470.64,,,,

,50.000,573345.19,449084.36,736684.02,,,,

,100.000,1136861.13,889922.44,1486080.55,,,,

,,,,,,,,

,B1(斜率）,11381.31,8908.45,14830.70,,,,

,B0（截距）,315.97,417.66,885.59,,,,

,标准不确定度U,9.55,,,,,,

,"相对不确定度

Urel",4.78,,,Cx＝2.0,,,

,,,,,,,,,

,Se,,,,,,,

,浓度/吸光度,1,2,3,,,,

,0.000,9853.58,7508.85,9309.97,,,,

,10.000,228965.53,168174.21,309771.97,,,,

,20.000,441330.39,328605.56,602573.90,,,,

,50.000,1104688.03,808192.83,1473334.98,,,,

,100.000,2235420.02,1663461.49,2922374.43,,,,

,,,,,,,,

,B1(斜率）,22264.32,16545.35,29084.09,,,,

,B0（截距）,2535.83,-444.10,16445.95,,,,

,标准不确定度U,10.62,,,,,,

,"相对不确定度

Urel",5.31,,,Cx＝2.0,,,

5.4Uncertaintyofreferencestandard标准品的不确定度,,,,,,,,

,5.4.1As标准品不确定度,,,,,,,

,TheuncertaintyforAsstandardsolutionis,,,,1002±5,μg/L,则a＝,1

,As标准溶液的不确定度为,,1002±5,μg/L,,,,

,k＝2，,,0.005,,,,,

,5.4.2Ba标准品不确定度,,,,,,,

,TheuncertaintyforBastandardsolutionis,,,,999±2,μg/L,则a＝,5

,Ba标准溶液的不确定度为,,999±2,μg/L,,,,

,k＝2，,,0.001,,,,,

,5.4.3Cd标准品不确定度,,,,,,,

,TheuncertaintyforCdstandardsolutionis,,,,999±2,μg/L,则a＝,5

,Cd标准溶液的不确定度为,,999±2,μg/L,,,,

,k＝2，,,0.001,,,,,

,,,,,,,,,

,5.4.4Cr标准品不确定度,,,,,,,

,TheuncertaintyforCrstandardsolutionis,,,,1002±5,μg/L,则a＝,5

,Cr标准溶液的不确定度为,,1002±5,μg/L,,,,

,k＝2，,,0.002,,,,,

,,,,,,,,,

,5.4.5Hg标准品不确定度,,,,,,,

,TheuncertaintyforHgstandardsolutionis,,,,1001±2,μg/L,则a＝,5

,Hg标准溶液的不确定度为,,1001±2,μg/L,,,,

,k＝2，,,0.001,,,,,

,,,,,,,,,

,,,,,,,,,

,5.4.6Pb标准品不确定度,,,,,,,

,TheuncertaintyforPbstandardsolutionis,,,,1001±2,μg/L,则a＝,5

,Pb标准溶液的不确定度为,,1001±2,μg/L,,,,

,k＝2，,,0.001,,,,,

,,,,,,,,,

,,,,,,,,,

,5.4.7Sb标准品不确定度,,,,,,,

,TheuncertaintyforSbstandardsolutionis,,,,1002±2,μg/L,则a＝,5

,Sb标准溶液的不确定度为,,1002±2,μg/L,,,,

,k＝2，,,0.001,,,,,

,,,,,,,,,

,5.4.8Se标准品不确定度,,,,,,,

,TheuncertaintyforSestandardsolutionis,,,,1000±5,μg/L,则a＝,5

,Se标准溶液的不确定度为,,1000±5,μg/L,,,,

,k＝2，,,0.003,,,,,

,,,,,,,,,

,"Theuncertaintyfromdilutionofpreparationforstandardsolutionissufficientlysmalltobeneglected.

根据《标准溶液稀释的不确定度计算》结果可知，将标准溶液逐级稀释为标准工作溶液中间引起的不确定度可以忽略不计。",,,,,,,

,"Ifthisreferencestandardissolid,theuncertaintyfromweighedpreparationshouldbeconsidered.

此标准品是否固体标物，如是，则需考虑称量标物质量的不确定度，反之，则无需考虑",,,,,,,

,"Thisreferencestandardissolution,thepreparationforstandardsolutioncanbeneglected.",,,,,,,

,,,,,,,,,

5.5Uncertaintyofvolumeforsample试样体积,,,,,,,,

,5.5.1Calibration(maximalallowableerrorofflask)校准(容量瓶最大允许误差),,,,,,,

,ThemaxallowableerrorofdegreeAflaskin20±5℃is,,,,(10±0.01),ml，uflask＝,0.01,ml

,经校准的A级容量瓶在（20±5）℃的体积与允差为,,,,(10±0.01),ml，uflask＝,0.01,ml

,"Fortriangulardistribution,ucalisgivenby",,,,,,,

,假设为三角分布,,,0.004,ml,,,

,5.5.2Temperature:温度,,,,,,,

,"Accordingtothemanufacturertheflaskhasbeencalibratedatatemperatureof20°C,whereasthelaboratorytemperaturevariesbetween0℃～30℃.Theuncertaintyfromthiseffectcanbecalculatedfromtheestimateofthetemperaturerangeandthecoefficientofthevolumeexpansion.Thevolumeexpansionoftheliquidisconsiderablylargerthanthatoftheflask,soonlytheformerneedstobeconsidered.Thecoefficientofvolumeexpansionforwateris1×10-3ml/℃.Sothevolumevariesis:

由于实验的温度是在20℃～30℃之间变动，温度波动影响应为单边，则波动值为10℃，该影响引起的不确定度可通过估算该温度范围和体积膨胀系数来进行计算。液体的体积膨胀明显大于容量瓶的体积膨胀，因此只需考虑前者。有机液体的体积膨胀系数A为1×10-3ml/℃，因此体积变化为",,,,,,,

,Vexpand=,A×温度波动×容量瓶体积＝,,,,,,

,＝,1×10-3,×10×,100,0.210,ml,,

,"Forrectangulardistribution,utempisgivenby

假设温度变化为矩形分布，则",,,,,,,

,,,0.577,ml,,,,

,5.3.3CombinedstandarduncertaintyforVolume体积的合成标准不确定度,,,,,,,

,,,0.577,ml,,,,

,,,,,,,,,

5.6Uncertaintyofmassofsamplebybalance质量的不确定度,,,,,,,,

"ThecertificationfromSCMofbalanceindicatedthatthemaxallowableerrorofthisbalanceis±0.5mg(a=0.5)anditisforrectangular.Thiscontributionhastobecountedtwice,onceforthetareandonceforthegrossweight,becauseeachisanindependentobservationandtheeffectsar