COMPENDIUM OF INTERNATIONAL ANALYSIS OF METHODS - OIV Guide for the validation – quality control Practical guide for the validation, quality control, and uncertainty assessment of an alternative oenological analysis method (Resolution 10/2005) Contents 1. PURPOSE ..................................................................................................................... 5 2. PREAMBLE AND SCOPE ......................................................................................... 5 3. GENERAL VOCABULARY ....................................................................................... 6 4. GENERAL PRINCIPLES ......................................................................................... 12 4.1 METHODOLOGY .................................................................................................. 12 4.2 DEFINITION OF MEASUREMENT ERROR ........................................................... 13 5. VALIDATING A METHOD ..................................................................................... 14 5.1 METHODOLOGY .................................................................................................. 14 5.2 SECTION ONE: SCOPE OF METHOD ................................................................... 15 5.2.1 Definition of analyzable matrices ................................................................. 15 5.2.2 Detection and quantification limit ................................................................ 15 5.2.2.1 Normative definition ............................................................................................. 16 5.2.2.2 Reference documents ............................................................................................ 16 5.2.2.3 Application ........................................................................................................... 16 5.2.2.4 Procedure .............................................................................................................. 16 5.2.2.4.1 Determination on blank .................................................................................. 16 5.2.2.4.1.1 Scope ...................................................................................................... 16 5.2.2.4.1.2 Basic protocol and calculations .............................................................. 17 5.2.2.4.2 Approach by linearity study ........................................................................... 18 5.2.2.4.2.1 Scope ...................................................................................................... 18 5.2.2.4.2.2 Basic protocol and calculations .............................................................. 19 5.2.2.4.3 Graphic approach based on the background noise of the recording ............... 21 5.2.2.4.3.1 Scope ...................................................................................................... 21 5.2.2.4.3.2 Basic protocol and calculation................................................................ 21 5.2.2.4.4 Checking a predetermined quantification limit .............................................. 21 5.2.2.4.4.1 Scope ...................................................................................................... 21 5.2.2.4.4.2 Basic protocol and calculation................................................................ 22 5.2.3 Robustness .................................................................................................... 24 5.2.3.1 Definition .............................................................................................................. 24 5.2.3.2 Determination ....................................................................................................... 24 5.3 SECTION TWO: SYSTEMATIC ERROR STUDY .................................................... 24 5.3.1 Linearity study .............................................................................................. 24 5.3.1.1 Normative definition ............................................................................................. 24 5.3.1.2 Reference documents ............................................................................................ 24 5.3.1.3 Application ........................................................................................................... 24 OIV-MA-AS1-12 : R2005 1 COMPENDIUM OF INTERNATIONAL ANALYSIS OF METHODS - OIV Guide for the validation – quality control 5.3.1.4 ISO 11095-type approach ..................................................................................... 25 5.3.1.4.1 Basic protocol ................................................................................................ 25 5.3.1.4.2 Calculations and results .................................................................................. 26 5.3.1.4.2.1 Defining the regression model ................................................................ 26 5.3.1.4.2.2 Estimating parameters ............................................................................ 27 5.3.1.4.2.3 Charts ..................................................................................................... 27 5.3.1.4.2.4 Test of the linearity assumption .............................................................. 29 5.3.1.4.2.4.1 Definitions of errors linked to calibration ....................................... 29 5.3.1.4.2.4.2 Fischer-Snedecor test ...................................................................... 31 5.3.1.5 ISO 8466-type approach ....................................................................................... 32 5.3.1.5.1 Basic protocol ................................................................................................ 32 5.3.1.5.2 Calculations and results .................................................................................. 33 5.3.1.5.2.1 Defining the linear regression model ...................................................... 33 5.3.1.5.2.2 Defining the polynomial regression model ............................................. 33 5.3.1.5.2.3 Comparing residual standard deviations ................................................. 34 5.3.2 Specificity ..................................................................................................... 36 5.3.2.1 Normative definition ............................................................................................. 36 5.3.2.2 Application ........................................................................................................... 36 5.3.2.3 Procedures ............................................................................................................ 36 5.3.2.3.1 Standard addition test ..................................................................................... 36 5.3.2.3.1.1 Scope ...................................................................................................... 36 5.3.2.3.1.2 Basic protocol ......................................................................................... 36 5.3.2.3.1.3 Calculations and results .......................................................................... 37 5.3.2.3.1.3.1 Study of the regression line r = a + b.v ........................................... 37 5.3.2.3.1.3.2 Analysis of the results ..................................................................... 38 5.3.2.3.1.3.3 Overlap line graphics ...................................................................... 40 5.3.2.3.2 Study of the influence of other compounds on the measurement result ......... 40 5.3.2.3.2.1 Scope ...................................................................................................... 40 5.3.2.3.2.2 Basic protocol and calculations .............................................................. 40 5.3.2.3.2.3 Interpretation .......................................................................................... 41 5.3.3 Study of method accuracy ............................................................................ 43 5.3.3.1 Presentation of the step ......................................................................................... 43 5.3.3.1.1 Definition ....................................................................................................... 43 5.3.3.1.2 General principles .......................................................................................... 43 5.3.3.1.3 Reference documents ..................................................................................... 43 5.3.3.2 Comparison of the alternative method with the OIV reference method ................ 44 5.3.3.2.1 Scope .............................................................................................................. 44 5.3.3.2.2 Accuracy of the alternative method compared with the reference method ..... 44 5.3.3.2.2.1 Definition ............................................................................................... 44 5.3.3.2.2.2 Scope ...................................................................................................... 44 5.3.3.2.2.3 Basic protocol and calculations .............................................................. 44 5.3.3.2.2.4 Interpretation .......................................................................................... 46 5.3.3.3 Comparison by interlaboratory tests ..................................................................... 47 5.3.3.3.1 Scope .............................................................................................................. 47