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1 AOAC Int. GMO

2 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 Methods of Analysis of AOAC Int. 17 ed. volume II, Gaithersburg, MD,USA. )ISO (6): 1994 or Accuracy (trueness and precision) of measurement methods and results - Part : Basic method for the determination of repeatability and reproducibility of a standard measurement method. JIS Z ISO 575 3)Horwitz, W. (1995). Protocol for the Design, Conduct and Interpretation of Method-Performance Studies. Pure & Appl. Chem., 67(), AOAC International, ISO, International Union of Pure and Applied Chemistry (IUPAC, )Harmonized protocol AOAC International AOAC InternationalHarmonized protocol

3 SR = SL + Sr m S L S r m S r S R Horwitz Horwitz, W., Kamps, L.R. and Boyer, K.W. (1980). Quality control. Quality assurance in the analysis of foods for trace constituents. J. AOAC, (6),

4 5 /9 5 Youden5% 5 material valid data S R Harmonized protocol S R Harmonized protocol Split level YoudenYouden

5 6 Harmonized protocol Harmonized protocolaoac Int. Thompson, M.. and Wood, R. (1993). International Harmonized Protocol for Proficiency Testing of (Chemical) Analytical Laboratories. J. AOAC Int., (4), Thompson, M.. and Wood, R. (1993). The International Harmonized Protocol for the Proficiency Testing of (Chemical) Analytical Laboratories. Pure & Appl. Chem., (9), AOAC Int. (00). OMA Program Manual Appendix E. A Statistical Model to Evaluate Analyte Homogeneity for a Material.

6 S L x 11 x1 x L1 S r x 1 x x L S r S R T 1 T d 1 d Youden T L d L 7 S L S r S R S L S r Harmonized protocolt i d i S R S r Youden d i S r

7 Youden Y X 8 Harmonized protocol Youden Youden

8 Cochran Grubbs Single- and paired- repeatability standard deviations r reproducibility standard deviations R S R S r S r S R S r S R r S R r Cochran, W.G. (1941). The distribution of the largest of a set of estimated variances as a fraction of their total. Annals of Eugenics,, Grubbs, F.E. (1950). Sample criteria for testing outlying observations. Ann. Math. Statist. Assn.,, 7-58.

9 HORRAT(Horwitz Ratio) HORRAT = RSDR,% PRSD,% R Horwitz =100 (%) YoudenXY Pitman 10 HORRAT RSD R Reproducibility Relative Standard DeviationHorwitz PRSD R Predicted Reproducibility Relative Standard DeviationAOAC Int.HORRAT PRSD R RSD R HORRAT HORRAT 1) ph )empirical methods 3) Qualty measurement drained weight Pitman, E.J.G. (1939). A note on normal correlation. Biometrika,, 9-1.

10 Horwitz J. AOAC, 63, (1980) 50 RSD R,% 1 0.5log 10 = C C C a(%) =a10 - C a(ppm) =a10-6 Horwitz RSD,% R = σ = 0.0C R 0.15 C RSDR,% = σ C 100 R 11 Horwitz Horwitz, W., Kamps, L.R. and Boyer, K.W. (1980). Quality control. Quality assurance in the analysis foods for trace constituents. J. AOAC,, Horwitz, W., Albert, R., Deutsch, M.J. and Thompson, J.N. (1990). Precision parameters of methods of analysis required for nutrition labeling. part I. J. AOAC,, Horwitz, W. and Albert, R. (1996). Reliability of the determinations of polychlorinated contaminants (biphenyls, dioxins, furans), J. AOAC, Int.,, Thompson, M. (000). Recent trends in inter-laboratory precision at ppb and sub-ppb concentrations in relation to fitness for purpose criteria in proficiency testing. Analyst,, McClure, F.D. and Lee, J-K (003). Computation of HORRAT Values. J. AOAC Int.,, Horwitz, W. and Albert, R. (004). Letters to the editor. J. AOAC Int., (), 34A. McClure, F.D. and Lee, J-K (004). Letters to the editor. J. AOAC Int., (), 35A-40A.

11 trace(less than) 1 S R RSD R

12 1) ) 3) 4) 5) 6) repeatability standard deviation, s r 7)RSD r 8)r=.8s r 10)s R 11)RSD R 1)HORRAT 13)R=.8s R 14)% Rec Fisher lsd.. = t( α; df) V n= t( α; df) s e 9)s r s e =.8 t 13 S r S R S r S R S S S

13 AOAC Int. Manual (00)m=8r=3 Harmonized protocol for proficiency Test (1993) m=10r= m S sam S an r 14 m mr S an r S sam Harmonized protocol AOAC Int. mr Thompson, M.. and Wood, R. (1993). International Harmonized Protocol for Proficiency Testing of (Chemical) Analytical Laboratories. J. AOAC Int., (4), Thompson, M.. and Wood, R. (1993). The International Harmonized Protocol for the Proficiency Testing of (Chemical) Analytical Laboratories. Pure & Appl. Chem., (9), AOAC Int.OMA Program Manual Appendix E (00). A Statistical Model to Evaluate Analyte Homogeneity for a Material.

14 1 m x11 x1 x m1 x1r xr x mr San x1. x. x m. x..() Ssam S = S + S x an sam S S sam an 15 S an rs sam Horwitz

15 F San + rssam α F = < F ( α, df1, df df ) 1 San df Fp<0.05 Harmonized protocol for Proficiency Test (1993) σ p S sam < 0.3σ S Horwitz R 1ppm ( ) σ 0.0 (1 10 R = ) = = 0.16 ppm p σ p σ R S sam S R 5% Ssam < = 0.048( ppm) 16 r CochranAOAC Int. FAPAS Harmonized protocol AOAC Int.F F Fp S R Horwitz Harmonized protocol S R Horwitz S R S R Harmonized protocol S sam S sam S R S R S R

16 3) Ssam < 0.3σ p σ p FAPAS protocol 6th ed. (00) GMOHorwitz Proficiency test S R S R 17 Harmonized protocol FAPAS S sam S sam S sam S sam S sam S sam S sam Harmonized protocol

17 GMO PCR PCR FAPAS 95% ( 1 ) p= 0.05, n= ± 0.04 p ± 1.96 p p n GMO5%100GMO95% Clopper and Pearson (1934) 18 PCR GMO GMO GMOGMO GMOGMOGMO GMO Clopper and Pearson Clopper and Pearson

18 Valid Cochran N Y /9 (/9 1Grubbs Y /9 Y N Grubbs N N Y /9 19

19 S r S R Youden S r = L L d ( d ) i i d i= 1 i= 1 Sr = L ( L ) 1 Youden S R = S + S d r S = L i= 1 d ( Ti T) ( L ) 1 Excel S d S r 0 Harmonized protocols r S R T i d i Ld i Ld i L S r d i S r S r Youden d i d i S r d i d i LL-1 L-1d i L d i d i L-1

20 Horwitz Thompson, M. (000). Recent trends in inter-laboratory precision at ppb and sub-ppb concentrations in relation to fitness for purpose criteria in proficiency testing. Analyst, 15, σ R ( C< 7) ( C ) 0. C = C ( C> 0.138) C FAPAS protocol 6th ed. (00) AOAC Int. 1 Horwitz 000FAPAS AOAC Int. AOAC Int. ( )HORRAT HORRAT

21 AOAC Official Methods F.D.MClure AOAC Int.OMA Program Manual Appendix E (00) 1)Cochran test 5% )Intra-class correlation analysis Ssam ρ = F San + Ssam 5% 3) S sam 1 < S 3 an 5% S 10 an x = an + sam = an + = an = an S S S S S S 3 9 S x Cochran testm r intra-class correlation F intra-class correlations sam S an intra-class correlationaoac Int.OMA Program Manual Appendix E (00) S sam S an Harmoized protocol S R S an S r S sam S an S x

22 S an, S sam S an = m r ( xij xi.) i= 1 j= 1 ( 1) mr m i= 1 ( x x ) i. i.. m 1 = S + rs an sam Excel Excel S an = S sam = r Excel 3 mtest sample r test portion S sam S an S an rm mr-1 r mrm m-1r r S sam Excel S sam S an

23 FAPASprotocol 6th ed. (00) T.Fearn and M. Thompson (001) 1)Cochran test 5% ) S < σ = 0.3σ χ S S F F S m 1 sam all p m 1,0.95 Fm 1, m, sam σall + an = 1σall + an F σ all σ p Allowable sample SD target SD 1993Proficiency Test Harmonized protocol ( 0.3 ) S + S = S + S R sam R R = 1.09S = 1.04S R 5% R S < σ = 0.3σ sam all p sufficient homogeneity σ p S R Horwitz σ R 4 FAPAS Cochran testm r S sam S sam S sam S sam S sam S sam Harmonized protocol S sam p Harmonized protocol S sam S sam FAPAS FAPASF Harmonized protocol

24 p0 p y = ln 1 p -+ y p y y= sin 1 p p=3070% 5 FAPASGMOGMO GMO

356 Nippon Shokuhin Kagaku Kogaku Kaishi Vol. /., No.1, -/0-0+ (,**1) 44 For Quality Control and Quality Assurance in Food Analysis Akemi Yasui Analyt

356 Nippon Shokuhin Kagaku Kogaku Kaishi Vol. /., No.1, -/0-0 (,**1) 44 For Quality Control and Quality Assurance in Food Analysis Akemi Yasui Analytical Science Division, National Food Research Institute,