GB/T15000.3-2008

20081029GB/T15000.3-2008

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GB/T1500019945: GB/T15000.1-1994 GB/T15000.2-1994 GB/T15000.3-1994 GB/T15000.4-1994 GB/T15000.5-1994 19966 GB/T15000.6-1996 20017 GB/T15000.7-2001 20038GB/T15000.4 GB/T15000.8-2003 GB/T15000.4-2003 2008GB/T15000.3,GB/T15000.3-1994GB/T15000.5-1994 GB/T15000.3-2008

GB/T15000.1-1994 GB/T15000.2-1994 GB/T15000.3-2008 GB/T15000.4-2003 GB/T15000.6-1996 GB/T15000.7-2001 GB/T15000.8-2003

ISOISO GuideGB/T15000.1-1994ISO Guide 6:1978GB/T15000.2-1994ISO Guide 30:1991GB/T15000.3-2008ISO Guide 35:2006GB/T15000.4-2003ISO Guide 31:2000GB/T15000.7-2001ISOGuide34:2000GB/T15000.8-2003ISO Guide33:2000

ISOISO Guide 30:1992 Terms and definitions used in connection with reference materialsISO Guide 31:2000 Reference materials-Contents of certificates and labelsISO Guide 32:1997 Calibration in analytical chemistry and use of certified reference materialsISO Guide 33:2000 Uses of certified reference materialsISO Guide 34:2000 General requirements for the competence of reference material producersISO Guide 35:2006 Reference materials-General and statistical principles for certification

GB/T15000.3/51994GB/T15000.3-1994ISO Guide 35:198951 2 3 4 5 GB/T15000.5-1994 5 5 10

GB/T15000.32008200837200881ISO Guide 35:2006112GB/T15000.3-1994GB/T15000.5-1994

ISO Guide 351981ISO Committee on Reference Materials (REMCO)

19851

19892

20063

ISO Guide 3519891 Scope2 Definitions3 The role of reference materials in measurement science4 Measurement uncertainty5 Homogeneity of materials6 General principles of certification7 Certification by a definitive method8 Certification by interlaboratory testing9 Certification based on a metrological approach

20061 Scope 2 Normative references 3 Terms, definitions and symbols 4 Symbols 5 Design of a certification project 6 Evaluating measurement uncertainty 7 Homogeneity study 8 Stability study 9 Determination of the property values 10 Data and uncertainty evaluation 11 Certification Annex A (informative) Statistical approaches Annex B (informative) Examples

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ISO Guide 30:199231Terms related to materials (8)Reference material (RM)Certified reference material (CRM)Primary standardSecondary standardCharacterizationHomogeneityStabilitySampleTerms related to measurement and testing (10)Certified valueUncertified valueConsensus value (of a given quantity)Uncertainty of a certified valuePrecisionAccuracyAccepted reference valueTraceabilityInterlaboratory testReference methodTerms related to certification and issuance of reference materials (5)Certification of a reference materialReference material certificateCertification reportCertifying bodyCertified reference material producerAdditional terms (8)(production) batchValue (of a quantity)True value (of a quantity)Systematic errorRandom errorLevel of confidenceRepeatability (of results of measurements)Reproducibility (of results of measurements)

GB/T15000.2-1994257 5 1

3 9

GB/T15000.3-20081RM reference material2CRMcertified reference material3 property value (of a reference material)4 characterization ( of a reference material)5 between-bottle homogeneity6 within-bottle homogeneity7 blending8 matrix material9 spiking10 short-term stability11 long-term stability12 life time (of a reference material)13RM/CRM shelf life (of an RM/CRM)

ISO Guide 301992 reference material(RM): Material or substance one or more of whose property values are sufficiently homogeneous and well established to be used for the calibration of an apparatus, the assessment of a measurement method, or for assigning values to materials. NOTE A reference material may be in the form of a pure or mixed gas, liquid or solid. Examples are water for the calibration of viscometer, sapphire as a heat-capacity calibrant in calorimetry, and solutions used for calibration in chemical analysis. GB/T15000.2-1994 /JJF 1005-2005

RM reference material material, sufficiently homogeneous and stable with respect to one or more specified properties, which has been established to be fit for its intended use in a measurement process.)1234RM

ISO Guide 301992 certified reference material (CRM):Reference Material, accompanied by a certificate, one or more of whose property values are certified by a procedure which establishes its tracebility to accurate realization of the unit in which the property values are expressed, and for which each certified value is accompanied by an uncertainty at a stated level of confidence.

GB/T15000.2-1994

JJF 1005-2005

CRMcertified reference material (reference material, characterized by a metrologically valid procedure for one or more specified properties, accompanied by a certificate that provides the value of the specified property, its associated uncertainty, and a statement of metrological traceability.)12GB/T15000.7-2001aSIbcCRMRM3GB/T15000.4-2003

property value (of a reference material) value attributed to a quantity representing a physical, chemical or biological property of a (certified) reference material.

characterization (of a reference material) 1 2 process of determining the property values of a reference material, as part of the certification process. NOTE 1The characterization process provides the values for the properties to be quantified. NOTE2 In batch certifications, the characterization refers to the property values of the batch.

CharacterizationGB/T15000.2-1994characterizationJJF 1005-2005characterizationISO Guide 30:1992Characterization: For a reference material, determination of one or more physical, chemical, biological, or technological property values that are relevant to its intended end use.

Homogeneity Homogeneity Condition of being of uniform structure or composition with respect to one or more specified properties. A reference material is said to be homogeneous with respect to a specified property if the property value, as determined by tests on samples of specified size, is found to lie within the specified uncertainty limits, the samples being taken either from different supply units (bottles, packages, etc.) or from a single supply unit. between-bottle homogeneitybottle-to-bottle variation of a property of a reference material. within-bottle homogeneityvariation within one bottle of a property of a reference material.

stabilitystability Ability of a reference material, when stored under specified conditions,to maintain a stated property value within specified limits for a specified period of time. short-term stabilitystability of a property of a reference material during transport under specified transport conditions long-term stabilityCRMstability of a property of a reference material under specified storage conditions at the CRM-producer

matrix materialblendingspikinglife timeshelf lifeCRM

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1

2

3

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1 23xiAB1 23uck23

1

2

3

ABGUMk

xCRM xchar xbb xlts xsts

Yes

No

NoOKubbustsultsuchar)ucU

BIPM, IEC, IFCC, ISO, IUPAC, IUPAP and OIML Guide to the expression of uncertainty in measurement (GUM),1993. Corrected and reprinted 1995.JJF 1059-1999 Eurachem/Citac GuideQuantifying uncertainty in analytical measurement, 2nd edition, 2001.CNAS-GL06 (www.cnas.org.cn

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103010 GB/T15000.5-1994100015201000 1525100030random sampling(stratified random sampling)(systematic sampling)

i i=1,2,,a)j j=1,2,,n)

xij xij Ai ijAiijAi2A ij 2Aiij

(1)Withingroups

Between groupsBottle No.1nsubsamplesntransformationsnmeasurementsBottle No.2nsubsamplesntransformationsnmeasurementsBottle No.ansubsamplesntransformationsnmeasurements

(2)Withingroups

Between groupsBottle No.1transformationnmeasurementsBottle No.2transformationnmeasurementsBottle No.atransformationnmeasurements

1x11x12x1jx1n12x21x22x2jx2n2ixi1xi2xijxiniaxa1xa2xajxana

1

i

2

F

3

nn0 = n

1 mg/kgBottleData-1Data-2Data-3132330131023403343163320321309431533832153263383256325302304732433131783103103319336321328103103283121131431430212329300299133203293111432231231115332317299163132942931732431433518321342316

2ANOVA Table for Barium in soil

=318mg/kg =11mg/kg (~3.5%)

= 5.2mg/kg (~1.6%)

SSdfMSFP-valueF crit3488.98117205.23421.6896850.0915671.9153214372.66736121.4637861.64853

ubb

2s4/

MS*amongsbb

ubbFederer

from Federer WT (1968) J. Royal Stat Soc C 17:171-174.

mg/L)10.2180.2300.22620.2150.2180.21430.2110.2300.21040.2210.2230.20850.2160.2190.21860.2340.2180.23070.2310.2150.22880.2260.2120.21890.2230.2250.215100.2240.2300.218110.2310.2110.227120.2290.2070.221130.2230.2070.228140.2300.2150.231150.2340.2160.224

SSdfMSFP-valueF crit0.000577144.12E-050.6114440.8342962.037420.002021306.74E-050.00259744sr0.008207043sbb2-8.72381E-06ubb'0.002407705ubb(Federer)0.001859673

Within Groups Among groups

BottleSubsampleNo.1SubsampleNo.2SubsampleNo.aTransformationTransformationTransformationnmeasurementsnmeasurementsnmeasurements

swb

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Storage time(months)0123456789101112T1(e.g.+18)T2(e.g.+4)T3(e.g. -20)Tref(e.g.- 50)AnalysisXStorage at temperature TStorage at reference temperature

/

YX0110

b10XYYXH010

94/t1TTn-2t

H0

n-2t

H0H0

/t2 nYXYiXi

Sy

/t(3)T

n-2t t H0H0

/F1XYXYeYX(n-11n-2YXXYYXYXFFF(1n-2)H0YX

98 /F2

/F3F

1

2

r2

F1SSregMS reg

n-2SSresMSresn-1SStotal

tXYXXYYXY1097.76095570212101.23144102481214.76324102.14576104332451.3643697.7212969549.23517.9272398.852016397867184.04n4Lxy4.74Lxx720Lyy15.977875r20.001953013r0.0442b10.006583333b099.594Sy2.82370944sb10.105233438t0.06255933t4.30

F Multiple R0.044192908R Square0.001953013Adjusted R Square-0.497070482.823709444 dfSSMSFF0.9510.0312050.03120.00390.95581215.946677.9733315.977875

A

B

W

A B W 11212112121221212122p

FASSAA=a-1MSA=SSA/AFA=MSA/MSeBSSBB=b-1MSB=SSB/BFB=MSB/MSeABSSAxBAxB=(a-1)(b-1)MSAxB=SSAxB/AxBFAxB=MSAxB/MSe

eSSee=ab(n-1)MSe=SSe/eSS=abn-1

FASSAA=a-1MSA=SSA/AFA=MSA/MSeBSSBB=b-1MSB=SSB/BFB=MSB/MSeeSSee=a-1)(b-1)MSe=SSe/eSS=ab-1

Results of stability tests for total glucosinolate in rapeseed.(BCR190R)t=0 monthst=6 monthst=9 monthst=12 monthsBottle121.8423.2623.2522.2521.7421.6222.3922.2222.4522.5522.5122.22Bottle222.3223.4222.5423.8921.8923.1622.6122.7821.3722.7523.7322.84

SSdfMSFP-valueF 0.95F0.991.0416711.04173.7580.070404.4948.533.2517731.08393.9100.028563.2395.291.0079730.33601.2120.337343.2395.294.4347160.27729.736123

tXYXXYYXY1021.9350481.144202622.79336519.5208136.7583922.83881521.5742205.54241222.7144515.29272.42790.2662612037.529614.7n4Lxy5.4045Lxx78.75Lyy0.541629r20.684792r0.827521b10.068629b022.10326Sy0.292169sb10.032924t2.08447T4.30

FdfSSMSFF0.9510.3709030.3709034.3450.172520.1707260.08536330.541629

sstab0sbb

YY0bX

Y0Xbu(Y0)u(X)u(b)Y

u(Y)bxu(Y0)ucharubbYY01 YXY0bb u(b)YbY0Xxults ults xu(b)

RMP

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VIMSIpHabcd e

1aSIbcCRMRM

2 Part of a measurement chainSampleSubsampleDigestionExtractionDerivatizationSeparationMeasurementCalculation of result (+uncertainty)Reporting of result(+uncertainty)Matrix CRM/QC materialBlank materialSpiked sample/extractBlank extractCalibration by reference materialCorrectionBlank values

GB/T15000.32008 a) b) c) d) GB/T15000.72001 a) b) c) d) primary methodreference methodmethod-specific approach

1 aCCQMSICCQM

2////

No

No Yes

Yes

Yes

No Yes NoPreparation of the materialStability and homogeneity testingMeasurement campaignCalculation of property valueObjectives met?Material can be certifiedHomogeneity confirmed?Continuation of measurement campaignImprovement possible?Material cannot be certified

/23681015 634 1/ 2/

/

yxi

GCISO ISO 6142:2001 Gas analysis-Preparation of calibration gas mixtures-Gravimetric methodISO 6143:2001 Gas analysis-Comparison methods for determining and checking the composition of calibration gas mixtures GB/T 5274???? GB/T 106282008

pH

8

Yes

No Yes No No

Yes

No

Yes

Measurement campaignTechnically invalid resultsStatistically invalid resultsSufficient homogeneity/stability Calculation of property value and its uncertaintyCriteria for certificationReportDiscard or replace dataDiscard or replace dataMaterial cannot be certifiedMaterial cannot be certified

1

Grubbs xp

Dixon nx1x2xn-1xn x1 xn

GrubbsDixon Grubbs Dixon35

2 GrubbsDixonDixonGrubbsCochran

/ a) / b/ c

1/

2

3/ u u u u

9

5GSB - -

1 2 3 4 5 6 7891011 GB/T 15000.4-20034

1 1.11.2 1.3 1.4 2 2.1 2.2 2.3 GB/T15000.4ISO312.4 300/3/33.1 3.2 3.3 3.4 3.5 3.6

1 52 3 4 4.174.2 154.3 4.44.5674.65

1 23456U95SrSR78910

1 2 3 4U95 5 6