Cover
Title Page
Copyright
Contents
List of Figures
List of Resources
Preface
Glossary of Symbols
Acknowledgments
Chapter 1 Quantification
1.1 Define the Measurand (Analyte)
1.1.1 Quantification and Calibration
1.1.2 Authentic versus Surrogate
1.1.3 Signal Pretreatment and Normalization
1.2 Calibration Modes
1.3 External Calibration (EC)
1.3.1 Authentic Analyte in Authentic Matrix: MMEC
1.3.2 Authentic Analyte in Surrogate Matrix
1.3.3 Surrogate Calibrant in Authentic Matrix
1.3.4 Surrogate Calibrant in Surrogate Matrix
1.4 In‐sample Calibration (ISC)
1.4.1 Authentic Analyte: Standard Addition Method
1.5 Some New Quantification Techniques
1.5.1 Isotopic Pattern Deconvolution (IPD)
1.5.2 Direct Internal Calibration with Labeled Calibrant (IC‐SIL)
References
Chapter 2 Calibration
2.1 Direct and Inverse Calibration
2.2 Least‐squares Regression Method
2.2.1 Straight‐line Computation
2.2.2 Assumptions and Complements
2.3 Software Implementation
2.3.1 Ordinary Least‐squares (OLS) Regression
2.3.2 Weighted Least‐squares (WLS) Regression
2.4 Calibration: Special Topics
2.4.1 Nonlinear Calibration Curve
2.4.2 Misuses of Regression for Calibration
2.4.2.1 Coefficients of Correlation and Determination
2.4.2.2 Definitions of Linearity
2.4.3 Statistical Aspects of Standard Addition Method (SAM)
2.5 Metrological Approach to Calibration
2.5.1 Errors in Inverse‐predicted Values
2.5.2 Calibration as a Source of Uncertainty
References
Chapter 3 Precision
3.1 Outputs of Interlaboratory Studies
3.1.1 Diverse Precision Parameters
3.1.2 Role of Series for Data Collection
3.2 Analysis of Variance (ANOVA)
3.2.1 Computation of Precision Parameters
3.2.2 Additional Parameters
3.2.2.1 Relative Standard Deviation of Parameters
3.2.2.2 Variance of the Grand Mean
3.3 Balanced and Unbalanced Experimental Design
3.4 Software Implementation
3.4.1 ANOVA Classic Algorithm
3.4.2 Detect Outliers and Stragglers
3.4.2.1 Other Algorithms
References
Chapter 4 Trueness
4.1 Trueness and True Value
4.1.1 Bias and Recovery Yield
4.1.2 Evolution of the Concept of True Value
4.1.3 Specificity and Sources of Bias
4.2 Assessment of Trueness
4.2.1 Primary Operating Procedures
4.2.2 Reference Materials
4.2.2.1 Certified Reference Materials (CRM)
4.2.2.2 External Reference Materials (ERM)
4.2.2.3 Internal Reference Materials (IRM)
4.2.2.4 Verification Standard Solutions
4.2.2.5 Standard Addition Method (SAM) and Surrogate Samples
4.3 Proficiency Testing
4.3.1 Interlaboratory Comparison or Proficiency Testing Scheme (PTS)
4.3.2 Organization of Proficiency Testing Schemes
4.3.3 Reference Value of the Test Material
4.3.4 Performance Scores
4.3.5 Algorithm A
4.3.6 Check Material Homogeneity or Stability
4.4 Control Charts
4.4.1 First Phase Assessment of the Reference Value
4.4.2 Second Phase Routine Use
References
Chapter 5 Method Validation
5.1 Review of Validation Procedures
5.1.1 Inconsistencies of Validation Vocabulary
5.1.2 Validation Plans
5.2 Method Accuracy Profile (MAP)
5.2.1 Principles
5.2.2 Method Accuracy Profile by Example
5.3 Statistical Dispersion Intervals
5.3.1 β‐Expectation Tolerance Interval (β‐ETI)
5.3.2 β‐γ Content Tolerance Interval (β‐γ‐CTI)
5.4 Accuracy Profile: Special Topics
5.4.1 Choose the Best Calibration Model
5.4.2 Apply Consistent Experimental Design
5.4.3 Check the Number of Efficient Measurements
5.4.4 Select Probability Values
5.4.5 Select the Type of Tolerance Interval
5.4.6 Proportion of Nonacceptable Measures
References
Chapter 6 Measurement Uncertainty (MU)
6.1 Principle of Measurement Uncertainty
6.2 General Procedure to Estimating MU
6.3 Traceability at the International System of Units
6.4 Stage 1. Specify the Measurand
6.5 Stage 2. Identify Uncertainty Components
6.6 Stage 3. Quantify Uncertainty Sources
6.6.1 Type A Approach
6.6.1.1 Accuracy Profile
6.6.1.2 Interlaboratory Study
6.6.1.3 Control Chart
6.6.1.4 Proficiency Testing
6.6.2 Type B Approach
6.7 Stage 4. Calculate Combined Uncertainty
6.7.1 Law of Propagation of Uncertainty
6.7.1.1 The Model Only Contains Additions and Subtractions
6.7.1.2 The Model Only Contains Products and Quotients
6.7.1.3 The Model is a Complex Combination of Input Quantities
6.7.2 Kragten Iterative Algorithm
6.8 Calculate Expanded Uncertainty
6.9 Round the Result
6.10 Accuracy, Total Error, and Uncertainty
6.11 Insights on Probability
References
Chapter 7 Measurement Uncertainty in Analytical Sciences
7.1 Published Procedures: An Evaluation
7.2 Use Method Accuracy Profile Data
7.2.1 Stage 1. Generic Measurement Model
7.2.2 Stage 2. Generic Cause‐to‐Effect Diagram
7.2.3 Main Sources of Uncertainty in the Laboratory
7.2.3.1 Manpower
7.2.3.2 Material and Handling of Items
7.2.3.3 Method
7.2.3.4 Machine/Equipment
7.2.3.5 Environment
7.2.3.6 Measurement and Other Sources
7.2.4 Stages 3 and 4. Calculation of Combined Uncertainty
7.3 Use Control Charts Data
7.3.1 Principles of the Shewhart Control Chart
7.3.2 Statistical Dispersion Intervals and Control Charts
7.3.3 Estimation of the Reference Value Uncertainty
7.4 Use Interlaboratory Comparison Data
7.4.1 Proficiency Testing Scheme (PTS)
7.4.2 Interlaboratory Studies
7.5 Uncertainty Functions
7.5.1 Horwitz's Model
7.5.2 Fitting the Uncertainty Function
7.5.2.1 How to Interpret a Power Function?
7.6 Concept of Coverage Interval
7.6.1 Origin of Coverage Interval
7.6.2 Coverage Interval of Given Concentration
7.6.3 Coverage Interval of Given Relative Uncertainty
7.6.4 Obtain the Limits of the Coverage Interval
References
Chapter 8 Measurement Uncertainty and Decision
8.1 Framework for Decision‐Making
8.1.1 Decision versus Uncertainty
8.1.2 Specification Limits and Reference Values
8.1.3 Role of the Analytical Report
8.2 Sample Conformity Assessment
8.2.1 Define the Decision Rule
8.2.2 Guard Band Concept
8.3 Sampling Uncertainty
8.3.1 Sampling and Heterogeneity
8.3.2 Procedure of Homogeneity Check
8.3.3 Example of Copper in Wheat Flour
8.4 Measurement Uncertainty: Special Issues
8.4.1 Influence of the Calibration Model
8.4.2 Uncertainty of Corrected Results
8.4.3 Increase the Number of Replicates
8.4.4 Replication under Repeatability Condition
8.4.5 Replication under Intermediate Precision Condition
References
Chapter 9 MU and Quantification Limits
9.1 Definitions and Assessment of LOQ
9.1.1 Multiple Blank Standard Deviations
9.1.2 Visual Examination
9.1.3 Signal‐to‐Noise Ratio
9.1.4 Empirical Experimental Approach
9.2 LOQ as an Expected Relative Uncertainty
9.3 Decision Limit and Detection Capability
9.3.1 Concepts and Definitions
9.3.2 Initial Procedure (2002)
9.3.3 Modified Procedure (2021)
9.3.4 Example of Calculation
References
Chapter 10 Examples of MU Application
10.1 Standard Addition Method and Drug Quality
10.1.1 SAM Without Replication
10.1.2 SAM with Replication
10.1.3 Estimation from Method Accuracy Profile
10.2 Method Comparison Using Uncertainty
10.2.1 Analyte Defined by the Operating Procedure
10.2.2 Kjeldahl and Dumas Method Comparison
References
Chapter 11 Conclusions
11.1 Role of the Number of Replicates
11.2 Traceability to International Units
11.3 Education about Uncertainty
11.4 Risk Analysis
11.5 Harmonization of MU Estimation Procedures
References
Annexes
Index
EULA