食糧　その科学と技術　No.46( )

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1 Horwitz IUPAC/ISO/AOAC International AOAC International AOAC S S R.. RSD R,%./....

2 repeatabilityreproducibility Fisher JIS Z Excel RAND ExcelINTRAND n n

3 Horwitz Horwitz, Horwitz RSD R,% C C./ PRSD R,%.log C Thompson PRSD R,% C.log C. PRSD R,%predicted reproducibility relative standard deviationprsd R,% C R C R

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5 R.C.C.C C C..C PRSD R,% C. PRSD,%. R C. C.. C.C FAPAS HorRat AOAC S R.S r S r S r Horwitz, HorRatpH empirical methods drained weight Qualitymeasurement HorRat Horwitz mg/kgppbg/kg.ppm R PRSD R,% Horwitz C ppb ppm mg/kg g/kg C ppm R..... ppm PRSD R,%.

6 R PRSD R, mg/kg ppb % g/kg. ppm. mg/kg ppb. %. g/kg. ppm.. % % % % %,, AOAC, test sample AOAC, test portion /

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9 S sam Excel S ans an rs sam Excel S an Ssam r S an S sam Cochran F mg/kg , Cochran Cochran

10 S i S i Cochran. D i D i Cochran Cochran CochranS i D i D i r D i x i x i r D i x i x i x i x i x i x i CochranS i D i S i D i Cochran CS max S i m i C D max m D i i S i D i Cochran CS max S i... m i m D i i 1 CDmax... Cochran

11 Cochran Cochran CochranJIS Z JIS Z m r Cochran.Cochran.. S i.. S i Cochran. Di D i Cochran Cochran CS max S i m i= m D i i= CD max... mrcochran. Cochran..

12 Excel S an S an..mg/kg.mg/kg Horwitz R....mg/kg S an.. R. F F cal.f... F F F sam sam F

13 S sam. p p Horwitz R. sam R. R R R R sam R R sam. R R sam S sam S sam mg/kg R. S sam.. R... S sam AOAC

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15 all. p. R F F AOAC ISO JIS Z R r IUPACISOAOAC AOAC S r S r blind duplicatesplit levelsyouden x ij α i ij

16 m S L S r N m m, R 0 0 N0, L N0, r n x ij i j α i ij L N, L ij r N, r L r L r S L S r S ans r S sam S L R S R S S S R r L

17 S R S R L S L r S r R S R Excel S r S r rs L S r S R r S r S R S r SR r AOAC,

18 Cochran N Y Grubbs N Grubbs N Y Y Y N AOAC Cochran Cochran Cochran AOAC Cochran. Lr

19 Cochran..Cochran... Cochran.L r... single Grubbs SD SD H SD L SD H SD L SD SD H /SD SD L /SDsingle Grubbs, Single Grubbs SD H /SD SD L /SD SD H /SD SD L /SD

20 Cochran single Grubbs SDL SD H L SD L L SD H /SD -SD L /SD.. SD H /SD SD L /SD AOAC.. single Grubbs SD L /SD. Grubbs, L One highest or lowest Cochran

21 Cochran single Grubbs SDL SD H L SD L L SD H /SD -SD L /SD paired Grubbs SD 2L L SD 2H L SD HL L SD 2L /SD -SD 2H /SD -SD HL /SD... single Grubbs Cochran...L r. Single GrubbsSD H /SD...L. single Grubbs SD L SD H SD HL paired Grubbs,

22 AOAC SD L /SD SD H /SD SD HL /SD AOAC Paired Grubbs SD L /SD SD H /SD SD HL /SD paired Grubbs AOAC SD L /SD SD H /SD Cochran SD HL /SD paired Grubbs paired Grubbs paired Grubbs AOAC AOAC.. Paired Grubbs SD H /SD...L Two highest or two lowest.

23 % S r %.S r % RSD r % S R %.S R % RSD R % HorRat Paired Grubbs SD HL /SD...L One highest and one lowest. F F Excel.

24 . F F F FFS L S r S R S r S r.s R S R., IUPAC/ISO/AOAC IUPAC ELISAPCR GMO Lateral fl ow AOAC AOAC McClure AOAC

25 Lm Lm ISO blind sample Annex B DNA DNA NISTDNA FBIDNA DNA Forensic Science Communications DNA Developmental ValidationDNA Internal Validation Internal Validation DNA Internal Validation method

26 N pp N pn N pp N pn N np N nn N np N nn N pp N np N pn N nn NN pp N pn N np N nn N pp N pn N np N nn N verification reproducibilitymethod ValidationInternal Validation sensitivity ratespecificity ratefalse positive ratefalse negative rate positive N pp /N pp N pn, negative N nn /N np N nn, N np /N np N nn, N pn /N pp N pn, McClure repeatability

27 reproducibilityaccordance concordancecorconcordance Odds Ratio ISO Appendix L accordance concordance accordance accordance % ++! C!! concordance concordance % ++ {} concordance COR accordance % concordance % COR concordance % accordance % accordanceconcordance CORaccordanceconcordance COR..COR accordancecor accordanceconcordance COR ISO relative accuracyrelative sensitivity

28 relative specifi city ACN pp N nn/ N SEN pp / N pp N np SPN nn / N nn N pn McClure Cochran Cochran Cochran, / repeatabilityaccordance.reproducibilityconcordance. concordance r rnl nl nl AnL n concordance % 2 nl L rln Aaccordanceaccordance /. concordance % 100. %

29 accordance. Concordance Odds Ratio COR COR accordance concordance % % % %... concordance accordance

30 concordance/. McNemar NcNemar admcnemar cal cal bc bc ad b cbc

31 a b c d b cb c cal αα α z calα... αmcnemar α cal bc αyates cal 1... Excel CHIINV., b c bcmcnemar nbc xbor c nbcxb p.bc xx Px & x.

32 a b ab c d cd ac bd N x n x x n x P x & x ncxp p ncx p p x x x x x C. C.. x. x x x!!.. x x! x! x x! x! x. Excel BINOMDIST,,., TRUE+ BINOMDIST,,., TRUE p. BINOMDIST,,., TRUE ad cal cal = N adbc N ab cd ac bd cal α α α z McNemar α cal N/ Yates

33 cal.. Fisher abcdacbd Fisher Fisher acbd ab cd ac bd.. Horwitz, W.. Protocol for the Design, Conduct and Interpretation of Method Performance Studies. Pure & Appl. Chem.,,. JIS.. ISO. A. random sampling. Agricultural food products Layout for a standard method of sampling from a lot.. Excel RAND. Horwitz, W., Kamps, L.R. and Boyer, K.W.. Quality assurance in the analysis foods for trace constituents. J. AOAC,,. Thompson, M., Ellison, S.L.R. and Wood, R.. The International Harmonized

34 Protocol for the Profi ciency Testing of Analytical Chemistry Laboratories. Pure & Appl. Chem.,,. AOAC Int.. Appendix D: Guidelines for Collaborative Study Procedures to Validate Characteristics of a Method of Analysis. In Offi cial Methods of Analysis of AOAC Int. ed., Gaithersburg, MD,USA. AOAC Int.. AOAC Guidelines for Single Laboratory Validation of Chemical Methods for Dietary Supplements and Botanicals. website/slv_guidelines.pdf ISO. Statistical methods for use in profi ciency testing by interlaboratory comparisons. Thompson, M.. A natural history of analytical methods. Analyst,,. Horwitz, W. and Albert, R.. The Horwitz Ratio HorRat: A Useful Index of Method Performance with Respect to Precision. J. AOAC Int.,,. Thompson, M.. Limitations of the application of the Horwitz Equation: A rebuttal. Trends in Analytical Chemistry,,. EU. Laying down the methods of sampling and analysis for the offi cial control of the levels of lead, cadmium, mercury, inorganic tin, MCPD and benzo apyrene in foodstuffs. Commission Regulation ECNo /. Codex.. Report of the twentyeighth session of the Codex Committee on Methods of Analysis and Sampling. Thompson, M.. Recent trends in interlaboratory precision at ppb and sub ppb concentrations in relation to fi tness for purpose criteria in profi ciency testing. Analyst,,. FAPAS. Food Analysis Performance Assessment Scheme FAPASprotocol for the organisation and analysis of data th ed., FAPAS central science laboratory, UK. AOAC Int.. Appendix E: Laboratory Quality Assurance. In Offi cial Methods of Analysis of AOAC Int. ed., Gaithersburg, MD,USA. Thompson, M. and Wood, R.. The International Harmonized Protocol for the

35 Proficiency Testing ofchemicalanalytical Laboratories. Pure & Appl. Chem.,,. AOAC Int.. OMA Program Manual Appendix E. A Statistical Model to Evaluate Analyte Homogeneity for a Material. Youden W.J. and Steiner, E.H.. Reduction of data to standard form. Statistical Manual of the AOAC, p.. JIS Z..... Fearn, T. and Thompson, M.. A new test for 'suffi cient homogeneity'. Analyst,,. ISO. Accuracy trueness and precisionof measurement methods and results Part : Basic method for the determination of repeatability and reproducibility of a standard measurement method. IUPAC. Establishment of guidelines for the validation of qualitative and semi quantitative screeningmethods by collaborative trial: a harmonized protocol. McClure, F. D.. Design and analysis of qualitative collaborative studies: minimum collaborative program. J. AOAC,,. Feldsine, P., Abeyta, C. and Andrews, W.H.. AOAC International Methods Committee Guidelines for Validation of Qualitative and Quantitative Food Microbiological Offi cial Methods of Analysis. J. AOAC Int.,,. ISO. Microbiology of food and animal feeding stuffs Protocol for the validation of alternative methods.. DNA. NIST. Validation Information to Aid Forensic DNA Laboratories. FBI DNA Advisory Board. Quality Assurance Standards for Forensic DNA Testing Laboratories, Forensic Science Communications. Scientifi c Working Group on DNA Analysis Methods SWGDAM. Revised

36 Validation Guidelines. Forensic Science Communications. standards.htm Trullols, E., Ruisánchez, I. and Rius, F.X.. Validation of qualitative analytical methods. Trends Anal. Chem.,,. Fleiss, J.L., Levin, B. and Paik, M.C.. Statistical Methods for Rates and Proportions rd Ed., John Wiley & Sons, p.. Langton, S.D., Chevennement, R., Nagelkerke, N. and Lombard, B.. Analysing collaborative trials for qualitative microbiological methods: accordance and concordance. Int. J. Food Microbiol.,,. Zar, J.H.. Paired sample testing of nominal scale data. Biostatistical analysis th ed., Prentice Hall, pp.. Zar, J.H.. The contingency table. Biostatistical analysis th ed., Prentice Hall, pp..

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untitled AOAC Int. GMO Harmonized protocol -- AOAC Int., ISO, IUPAC 1)AOAC Int. (003). Appendix D: Guidelines for Collaborative Study Procedures to Validate Characteristics of a Method of Analysis. In Official

食糧 その科学と技術 No.46( )

食糧　その科学と技術　No.46( )