Pawe³ Koœcielniak, PhD, is Full Professor employed in the Department of Analytical Chemistry at Jagiellonian University, Krakow, Poland. He is a member of the Committee of Analytical Chemistry of the Polish Academy of Sciences, and is the author, co-author, and editor of more than 300 scientific articles, books, and book chapters. Professor Koscielniak’s main scientific interests include flow analysis, forensic chemistry, and environmental analysis with a special focus on analytical calibration, examination and elimination of interference effects, and optimization and validation of analytical procedures.

• Preface ix1 Calibration Fundamentals 11.1 Analytical Context 11.2 Principles of Analytical Calibration 21.3 Calibration Standards and Models 51.4 Calibration Procedures and Methods 71.5 Calibration in the Context of Measurement Errors 81.5.1 Uncontrolled Analytical Effects 91.5.2 Elimination and Compensation of Uncontrolled Effects 111.6 Calibration in Qualitative Analysis 141.7 Calibration in Quantitative Analysis 181.8 General Rules for Correct Calibration 22References 242 “Calibration-Free” Analysis 252.1 Novel Approach 252.2 Empirical Calibration 262.3 Theoretical Calibration 302.3.1 Fixed Models 302.3.2 Flexible Models 36References 453 Calibration Methods in Qualitative Analysis 473.1 Classification 473.2 External Calibration Methods 493.2.1 External Standard Method 493.2.2 Reference Sample Method 593.3 Internal Calibration Methods 713.3.1 Internal Standard Method 713.3.2 Indirect Method 753.4 Standard Addition Method 80References 834 Introduction to Empirical Calibration in Quantitative Analysis 854.1 Classification 854.2 Formulation of Model Functions 864.3 Examination of Interference Effect 934.4 Mathematical Modeling of Real Function 98References 1005 Comparative Calibration Methods 1035.1 External Calibration Methods 1035.1.1 External Standard Method 1035.1.1.1 Modified Procedures 1105.1.2 Dilution Method 1155.2 Internal Calibration Methods 1255.2.1 Internal Standard Method 1255.2.2 Indirect Method 133References 1416 Additive Calibration Methods 1436.1 Basic Aspects 1436.2 Standard Addition Method 1446.2.1 Extrapolative Variant 1446.2.1.1 Modified Procedures 1556.2.2 Interpolative Variants 1626.2.3 Indicative Variant 1676.3 Titration 1726.4 Isotope Dilution Method 1806.4.1 Radiometric Isotope Dilution 1826.4.2 Isotope Dilution Mass Spectrometry 1896.4.2.1 Modified Procedures 197References 1997 Calibration in Nonequilibrium Conditions 2037.1 Flow Injection Analysis 2037.1.1 Manipulation Techniques 2057.1.2 Gradient Technique 2127.2 Kinetic Analysis 220References 2318 Complex Calibration Approaches 2338.1 Extrapolative Methods 2338.1.1 Extrapolative Indirect Method 2348.1.2 Extrapolative Internal Standard Method 2398.1.3 Extrapolative Dilution Method 2448.2 Mixed Methods 2528.3 Combined Methods 2568.3.1 Integrated Calibration Methods 2568.3.1.1 Simple Integrated Method 2568.3.1.2 Complementary Dilution Method 2618.3.2 Generalized Calibration Strategy 2708.3.2.1 Versatile Flow Injection Calibration Module 2768.3.3 Standard Dilution Analysis 280References 2869 Calibration Approaches for Detection and Examination of Interference Effects 2899.1 Introduction 2899.2 Simple Procedures for Detection and Examination of Interference Effects 2909.3 Detection and Compensation of Additive Interference Effect 2959.3.1 Interpolative Procedure 2979.3.2 Extrapolative Procedure 3019.3.3 Integrated Procedure 308References 31110 Calibration-Based Procedures for Correction of Preparative Effects 31310.1 Introduction 31310.2 Specific Procedures 31410.3 Surrogate Recovery Method 31610.3.1 Reliability of the Method 31810.3.2 Interpretations of the Method 32110.3.3 Recovery vs. Interference Effect 32410.3.4 Recovery vs. Speciation Effect 329References 33311 Calibration-Related Applications of Experimental Plans 33511.1 Introduction 33511.2 Examination of Interference Effects 33711.3 Modeling of Real Functions 34211.4 Multicomponent Analysis 347References 35612 Final Remarks 359References 365Index 367

Pawe³ Koœcielniak, PhD, is Full Professor employed in the Department of Analytical Chemistry at Jagiellonian University, Krakow, Poland. He is a member of the Committee of Analytical Chemistry of the Polish Academy of Sciences, and is the author, co-author, and editor of more than 300 scientific articles, books, and book chapters. Professor Koscielniak’s main scientific interests include flow analysis, forensic chemistry, and environmental analysis with a special focus on analytical calibration, examination and elimination of interference effects, and optimization and validation of analytical procedures.

• Preface ix1 Calibration Fundamentals 11.1 Analytical Context 11.2 Principles of Analytical Calibration 21.3 Calibration Standards and Models 51.4 Calibration Procedures and Methods 71.5 Calibration in the Context of Measurement Errors 81.5.1 Uncontrolled Analytical Effects 91.5.2 Elimination and Compensation of Uncontrolled Effects 111.6 Calibration in Qualitative Analysis 141.7 Calibration in Quantitative Analysis 181.8 General Rules for Correct Calibration 22References 242 “Calibration-Free” Analysis 252.1 Novel Approach 252.2 Empirical Calibration 262.3 Theoretical Calibration 302.3.1 Fixed Models 302.3.2 Flexible Models 36References 453 Calibration Methods in Qualitative Analysis 473.1 Classification 473.2 External Calibration Methods 493.2.1 External Standard Method 493.2.2 Reference Sample Method 593.3 Internal Calibration Methods 713.3.1 Internal Standard Method 713.3.2 Indirect Method 753.4 Standard Addition Method 80References 834 Introduction to Empirical Calibration in Quantitative Analysis 854.1 Classification 854.2 Formulation of Model Functions 864.3 Examination of Interference Effect 934.4 Mathematical Modeling of Real Function 98References 1005 Comparative Calibration Methods 1035.1 External Calibration Methods 1035.1.1 External Standard Method 1035.1.1.1 Modified Procedures 1105.1.2 Dilution Method 1155.2 Internal Calibration Methods 1255.2.1 Internal Standard Method 1255.2.2 Indirect Method 133References 1416 Additive Calibration Methods 1436.1 Basic Aspects 1436.2 Standard Addition Method 1446.2.1 Extrapolative Variant 1446.2.1.1 Modified Procedures 1556.2.2 Interpolative Variants 1626.2.3 Indicative Variant 1676.3 Titration 1726.4 Isotope Dilution Method 1806.4.1 Radiometric Isotope Dilution 1826.4.2 Isotope Dilution Mass Spectrometry 1896.4.2.1 Modified Procedures 197References 1997 Calibration in Nonequilibrium Conditions 2037.1 Flow Injection Analysis 2037.1.1 Manipulation Techniques 2057.1.2 Gradient Technique 2127.2 Kinetic Analysis 220References 2318 Complex Calibration Approaches 2338.1 Extrapolative Methods 2338.1.1 Extrapolative Indirect Method 2348.1.2 Extrapolative Internal Standard Method 2398.1.3 Extrapolative Dilution Method 2448.2 Mixed Methods 2528.3 Combined Methods 2568.3.1 Integrated Calibration Methods 2568.3.1.1 Simple Integrated Method 2568.3.1.2 Complementary Dilution Method 2618.3.2 Generalized Calibration Strategy 2708.3.2.1 Versatile Flow Injection Calibration Module 2768.3.3 Standard Dilution Analysis 280References 2869 Calibration Approaches for Detection and Examination of Interference Effects 2899.1 Introduction 2899.2 Simple Procedures for Detection and Examination of Interference Effects 2909.3 Detection and Compensation of Additive Interference Effect 2959.3.1 Interpolative Procedure 2979.3.2 Extrapolative Procedure 3019.3.3 Integrated Procedure 308References 31110 Calibration-Based Procedures for Correction of Preparative Effects 31310.1 Introduction 31310.2 Specific Procedures 31410.3 Surrogate Recovery Method 31610.3.1 Reliability of the Method 31810.3.2 Interpretations of the Method 32110.3.3 Recovery vs. Interference Effect 32410.3.4 Recovery vs. Speciation Effect 329References 33311 Calibration-Related Applications of Experimental Plans 33511.1 Introduction 33511.2 Examination of Interference Effects 33711.3 Modeling of Real Functions 34211.4 Multicomponent Analysis 347References 35612 Final Remarks 359References 365Index 367

Pawe³ Koœcielniak, PhD, is Full Professor employed in the Department of Analytical Chemistry at Jagiellonian University, Krakow, Poland. He is a member of the Committee of Analytical Chemistry of the Polish Academy of Sciences, and is the author, co-author, and editor of more than 300 scientific articles, books, and book chapters. Professor Koscielniak’s main scientific interests include flow analysis, forensic chemistry, and environmental analysis with a special focus on analytical calibration, examination and elimination of interference effects, and optimization and validation of analytical procedures.

• Preface ix1 Calibration Fundamentals 11.1 Analytical Context 11.2 Principles of Analytical Calibration 21.3 Calibration Standards and Models 51.4 Calibration Procedures and Methods 71.5 Calibration in the Context of Measurement Errors 81.5.1 Uncontrolled Analytical Effects 91.5.2 Elimination and Compensation of Uncontrolled Effects 111.6 Calibration in Qualitative Analysis 141.7 Calibration in Quantitative Analysis 181.8 General Rules for Correct Calibration 22References 242 “Calibration-Free” Analysis 252.1 Novel Approach 252.2 Empirical Calibration 262.3 Theoretical Calibration 302.3.1 Fixed Models 302.3.2 Flexible Models 36References 453 Calibration Methods in Qualitative Analysis 473.1 Classification 473.2 External Calibration Methods 493.2.1 External Standard Method 493.2.2 Reference Sample Method 593.3 Internal Calibration Methods 713.3.1 Internal Standard Method 713.3.2 Indirect Method 753.4 Standard Addition Method 80References 834 Introduction to Empirical Calibration in Quantitative Analysis 854.1 Classification 854.2 Formulation of Model Functions 864.3 Examination of Interference Effect 934.4 Mathematical Modeling of Real Function 98References 1005 Comparative Calibration Methods 1035.1 External Calibration Methods 1035.1.1 External Standard Method 1035.1.1.1 Modified Procedures 1105.1.2 Dilution Method 1155.2 Internal Calibration Methods 1255.2.1 Internal Standard Method 1255.2.2 Indirect Method 133References 1416 Additive Calibration Methods 1436.1 Basic Aspects 1436.2 Standard Addition Method 1446.2.1 Extrapolative Variant 1446.2.1.1 Modified Procedures 1556.2.2 Interpolative Variants 1626.2.3 Indicative Variant 1676.3 Titration 1726.4 Isotope Dilution Method 1806.4.1 Radiometric Isotope Dilution 1826.4.2 Isotope Dilution Mass Spectrometry 1896.4.2.1 Modified Procedures 197References 1997 Calibration in Nonequilibrium Conditions 2037.1 Flow Injection Analysis 2037.1.1 Manipulation Techniques 2057.1.2 Gradient Technique 2127.2 Kinetic Analysis 220References 2318 Complex Calibration Approaches 2338.1 Extrapolative Methods 2338.1.1 Extrapolative Indirect Method 2348.1.2 Extrapolative Internal Standard Method 2398.1.3 Extrapolative Dilution Method 2448.2 Mixed Methods 2528.3 Combined Methods 2568.3.1 Integrated Calibration Methods 2568.3.1.1 Simple Integrated Method 2568.3.1.2 Complementary Dilution Method 2618.3.2 Generalized Calibration Strategy 2708.3.2.1 Versatile Flow Injection Calibration Module 2768.3.3 Standard Dilution Analysis 280References 2869 Calibration Approaches for Detection and Examination of Interference Effects 2899.1 Introduction 2899.2 Simple Procedures for Detection and Examination of Interference Effects 2909.3 Detection and Compensation of Additive Interference Effect 2959.3.1 Interpolative Procedure 2979.3.2 Extrapolative Procedure 3019.3.3 Integrated Procedure 308References 31110 Calibration-Based Procedures for Correction of Preparative Effects 31310.1 Introduction 31310.2 Specific Procedures 31410.3 Surrogate Recovery Method 31610.3.1 Reliability of the Method 31810.3.2 Interpretations of the Method 32110.3.3 Recovery vs. Interference Effect 32410.3.4 Recovery vs. Speciation Effect 329References 33311 Calibration-Related Applications of Experimental Plans 33511.1 Introduction 33511.2 Examination of Interference Effects 33711.3 Modeling of Real Functions 34211.4 Multicomponent Analysis 347References 35612 Final Remarks 359References 365Index 367