Funk W. Quality assurance in analytical chemistry (Weinheim, 2007). - ОГЛАВЛЕНИЕ / CONTENTS


Recent acquisitions archives | Russian acquisitions | Foreign acquisitions | Sigla(Rus)
CoverFunk W. Quality assurance in analytical chemistry: applications in environmental, food, and materials analysis, biotechnology, and medical engineering / W.Funk, V.Dammann, G.Donnevert. - 2nd ed. - Weinheim: Wiley-VCH, 2007. - xxiii, 277 p.: ill. + 1 CD-ROM. - Incl. bibl. ref. and index. - ISBN 978-3-527-31114-9
 

Оглавление / Contents
 
   Preface ................................................... XIII
   List of Symbols ........................................... XVII
    
0. Introduction ................................................. 1
   0.1.  General Differentiation of Analytical Processes ........ 3
   0.2.  Quality of Analytical Processes and Results ............ 4
   0.3.  The System of Analytical Quality Assurance ............. 4
   0.4.  The Four-Phase Model of Analytical Quality Assurance ... 6

1. Phase I: Establishing a New Analytical Procedure ............. 9
   1.1.  Introduction ........................................... 9
         1.1.1.  Objectives of Phase I .......................... 9
         1.1.2.  When Are Characteristic Data Obtained? ......... 9
         1.1.3.  The Progression of Phase I .................... 10
         1.1.4.  Results of Phase I; Statistical Data .......... 14
   1.2.  Calibration of the Fundamental Analytical Procedure ... 15
         1.2.1.  Establishment of an Analytical Range .......... 16
         1.2.2.  Preparation of Standard Samples ............... 16
         1.2.3.  Determination of the Calibration Function
                 and Process Data .............................. 17
                 1.2.3.1. Process Data for the Linear
                          Calibration Function ................. 18
                 1.2.3.2. Process Data for the Second-Order
                          Calibration Function ................. 19
                 1.2.3.3. Calculating Analytical Results
                          with the Aid of the Calibration
                          Function ............................. 21
         1.2.4.  Verification of the Fundamental Calibration ... 23
                 1.2.4.1. Verification of Linearity ............ 23
                 1.2.4.2. Verification of Precision ............ 25
   1.3.  Analyses at Very Low Concentrations ................... 29
         1.3.1.  Decision Limit ................................ 32
         1.3.2.  Determining the Minimum Detectable Value ...... 34
                 1.3.2.1. Minimum Detectable Value,
                          Determined Using the Distribution
                          of Blank Values ...................... 34
                 1.3.2.2. Minimum Detectable Value, Obtained
                          Using the Calibration Function ....... 35
         1.3.3.  Limit of Quantification ....................... 35
         1.3.4.  Quick Estimation .............................. 36
         1.3.5.  Estimation of the Decision Limit and Limit
                 of Quantification Using the S/N Ratio ......... 37
   1.4.  Validation of Individual Process Steps and
         Examination of Matrix Influences ...................... 37
         1.4.1.  Systematic Errors ............................. 37
                 1.4.1.1. Constant Systematic Errors,
                          Additive Deviations .................. 37
                 1.4.1.2. Proportional Systematic Errors,
                          Multiplicative Deviations ............ 38
         1.4.2.  Establishment and Assessment of the Recovery
                 Function ...................................... 38
                 1.4.2.1. Prerequisites for the
                          Interpretation of the
                          Recovery Function .................... 39
                 1.4.2.2. Testing for Systematic Errors ........ 40
         1.4.3.  Application of the Recovery Function .......... 41
                 1.4.3.1. Checking Individual Process Steps .... 41
                 1.4.3.2. Determination of the Recovery
                          Function to Prove the Influence
                          of a Matrix .......................... 45
   1.5.  Additional Statistical Methods ........................ 46
   1.6.  Use of Internal Standards ............................. 46
         1.6.1.  Definition, Purpose ........................... 46
         1.6.2.  Conditions and Limitations of the Use of
                 Internal Standards ............................ 47
         1.6.3.  Procedure ..................................... 47
   1.7.  Preparing for Routine Analysis ........................ 49
         1.7.1.  Examination of the Time Dependency of
                 Measured Values ............................... 49
                 1.7.1.1. Comparison of the "Within Batch"
                          Standard Deviation (sw) with the
                          "Between Batches" Standard
                          Deviation (sb) ....................... 49
                 1.7.1.2. Determining the Need for Daily
                          Adjustment of Analytical Equipment ... 51
                 1.7.1.3. The Trend Test ....................... 51
   1.8.  Summary of the Results of Phase I
         (Process Development): Documentation .................. 54

2. Phase II: An Analytical Process Becomes Routine;
   Preparative Quality Assurance ............................... 57
   2.1.  Introduction .......................................... 57
         2.1.1.  Objectives of Phase II ........................ 57
         2.1.2.  Execution of Phase II ......................... 57
         2.1.3.  Progression of Phase II ....................... 57
         2.1.4.  Results of Phase II ........................... 58
   2.2.  Selection of the Analytical Procedure ................. 59
         2.2.1.  Specificity of the Procedure .................. 60
         2.2.2.  Selectivity of the Analytical Procedure ....... 60
         2.2.3.  Working Range ................................. 60
         2.2.4.  Calibration Function, Sensitivity, and
                 Precision of the Procedure .................... 60
         2.2.5.  Minimum Detectable Value and Limit of
                 Quantification ................................ 61
         2.2.6.  Risk of Systematic Error ...................... 61
         2.2.7.  Effort, Costs ................................. 61
   2.3.  The "Training" Phase of the Process ................... 62
   2.4.  Establishment of Quality Objectives to be Adhered to
         in Routine Usage ...................................... 64
         2.4.1.  External Quality Requirements ................. 65
         2.4.2.  Internal Quality Requirements ................. 66
   2.5.  Control Samples for Internal Quality Assurance ........ 66
         2.5.1.  Requirements of Control Samples ............... 66
         2.5.2.  Types of Control Samples ...................... 67
                 2.5.2.1. Standard Solutions ................... 67
                 2.5.2.2. Blank Samples ........................ 67
                 2.5.2.3. Natural Samples ...................... 67
                 2.5.2.4. Spiked Natural Samples ............... 68
                 2.5.2.5. Synthetic Samples .................... 68
                 2.5.2.6. Certified Reference Materials
                          (CRMs) ............................... 68
         2.5.3.  Requirements for Producers of Control
                 Materials ..................................... 69
         2.5.4.  Applicability of Control Sample Types ......... 69
   2.6.  The Control Chart System .............................. 70
         2.6.1.  Introduction: History of the Control Chart .... 70
         2.6.2.  Principle of a Control Chart .................. 72
         2.6.3.  Average Run Length (ARL) and Evaluation of
                 Control Charts ................................ 73
         2.6.4.  Derivation of the Average Run Length (ARL) .... 74
                 2.6.4.1. Examples of Theoretical
                          Calculations ......................... 75
                 2.6.4.2. Analytical Example ................... 76
         2.6.5.  Concept for the Preparation of Routine
                 Quality Control ............................... 78
         2.6.6.  Evaluation of the Preliminary Period .......... 80
                 2.6.6.1. Variance Analysis .................... 80
                 2.6.6.2. Adherence to Required Quality
                 Objectives .................................... 80
         2.6.7.  Types of Control Charts and Their
                 Applications .................................. 80
                 2.6.7.1. Shewhart Charts ...................... 81
                 2.6.7.2. R-Chart (Range Control Chart) ........ 89
                 2.6.7.3. Difference Chart ..................... 96
                 2.6.7.4. Standard Deviation Chart (s-Chart) ... 98
                 2.6.7.5. Target Value Charts .................. 99
                 2.6.7.6. Cusum Chart ......................... 100
         2.6.8.  Summary of the Characterization of Control
                 Charts ....................................... 112

3. Phase III: Routine Quality Assurance ....................... 115
   3.1.  Introduction ......................................... 115
         3.1.1.  Setting the Objectives of Phase III .......... 115
         3.1.2.  Execution of Phase III ....................... 115
         3.1.3.  Progression of Phase III ..................... 115
   3.2.  Fundamental Measures of Internal Quality Assurance ... 118
         3.2.1.  The Laboratory and Laboratory Management ..... 118
         3.2.2.  Personnel .................................... 119
         3.2.3.  Outfitting and Equipment ..................... 119
                 3.2.3.1. Performance Monitoring,
                          Calibration and Adjustment
                          of Measuring Equipment .............. 119
                 3.2.3.2. Maintenance of Equipment ............ 120
         3.2.4.  Materials .................................... 121
                 3.2.4.1. Certifying Sample Quality ........... 121
                 3.2.4.2. Analysis-Related Materials .......... 121
                 3.2.4.3. Control Samples for Routine
                          Quality Control ..................... 122
         3.2.5.  Instituted Analytical Processes .............. 122
         3.2.6.  Testing the Equivalency of Analytical
                 Results ...................................... 122
                 3.2.6.1. Testing the Equivalency for a
                          Single Matrix ....................... 123
                 3.2.6.2. Testing the Equivalency in
                          Different Matrices .................. 126
         3.2.7.  Uncertainty of Measurements .................. 130
                 3.2.7.1. New Terms According to the
                          EURACHEM Guide ...................... 131
                 3.2.7.2. Overview of Common Procedures for
                          the Determination of Measurement
                          Uncertainty ........................ 133
                 3.2.7.3. Indication of Measurement
                          Uncertainty in Test Reports ......... 142
                 3.2.7.4. Interpretation of Measurement
                          Uncertainty in the Context of
                          Limit Value Monitoring .............. 143
                 3.2.7.5. Summary ............................. 144
         3.2.8.  Reporting Analytical Results ................. 145
   3.3.  Routine Quality Control .............................. 145
         3.3.1.  Trueness Control ............................. 146
                 3.3.1.1. General ............................. 146
                 3.3.1.2. Blank Value Monitoring .............. 146
                 3.3.1.3. χ-Chart .............................. 148
                 3.3.1.4. Recovery Rate Control Chart ......... 148
         3.3.2.  Precision Control ............................ 148
                 3.3.2.1. General ............................. 148
                 3.3.2.2. Precision Control Using an
                          R-Chart ............................. 149
                 3.3.2.3. Securing Precision Using a
                          Standard Deviation Control Chart .... 149
         3.3.3.  Revision of Quality Control Charts ........... 150
         3.3.4.  Quality Assurance in the Case of Time-
                 Consuming or Infrequent Analyses ............. 150
   3.4.  Special Quality Problems in Routine Analysis ......... 151
         3.4.1.  Matrix Effects ............................... 151
   3.5.  Corrective Measures .................................. 154
         3.5.1.  Sources of Error in Analytical
                 Laboratories ................................. 154
         3.5.2.  Systematic Troubleshooting ................... 155
                 3.5.2.1. Analytical Errors That Can Be
                          Detected Using Statistical Quality
                          Control Methods ..................... 161
                 3.5.2.2. Plausibility Checks ................. 162
   3.6.  Documentation and Archiving .......................... 166

4. Phase IV: External Analytical Quality Assurance ............ 169
   4.1.  Introduction ......................................... 169
   4.2.  Audits ............................................... 169
   4.3.  Interlaboratory (or Round Robin) Tests ............... 170
         4.3.1.  Interlaboratory Tests for Process
                 Standardization .............................. 171
         4.3.2.  Interlaboratory Tests as Proof of
                 Laboratory Performance ....................... 171
         4.3.3.  Other Interlaboratory Tests .................. 172
         4.3.4.  Planning and Execution of Interlaboratory
                 (or Round Robin) Tests ....................... 173
                 4.3.4.1. Quality Management System of the
                          Provider of an Interlaboratory
                          Test ................................ 173
                 4.3.4.2. Planning the Interlaboratory Test ... 174
                 4.3.4.3. Interlaboratory Test Samples ........ 175
         4.3.5.  Procedures for the Execution and Evaluation
                 of Interlaboratory Tests ..................... 176
                 4.3.5.1. Interlaboratory Test Programs
                          According to ISO 5725-2 ............. 177
                 4.3.5.2. The Youden Method of
                          Interlaboratory Tests ............... 179
                 4.3.5.3. Interlaboratory Tests According
                          to ISO Guide 43 ..................... 188
   4.4.  Effects of Internal Quality Assurance on the
         Results of Interlaboratory Tests ..................... 191
   4.5.  Conclusion ........................................... 194

5. Definitions ................................................ 195
   5.1.  Quality and Quality Management ....................... 195
   5.2.  Analytical Terms ..................................... 197
   5.3.  Analytical Results ................................... 201
   5.4.  Deviation, Uncertainty ............................... 202
   5.5.  Materials, Samples ................................... 205
   5.6.  Statistical Tests .................................... 206

6. References

Appendix 1
   A1 Sample Calculations ..................................... 219
      A1.1 Fundamental Calibration ............................ 219
      A1.2 Linearity Tests .................................... 222
           A1.2.1  Visual Linearity Test ...................... 221
           A1.2.2  Second-Order Calibration Function .......... 222
           A1.2.3  Linearity Test: Goodness-of-Fit Test ....... 224
           A1.2.4  Variance Homogeneity Test .................. 226
           A1.2.5  Outlier Tests for Linear Calibration ....... 228
           A1.2.6  Securing the Lower Range Limit ............. 230
           A1.2.7  Decision Limit, Minimum Detectable Value,
                   and Limit of Quantification ................ 231
           A1.2.8  Recovery Function .......................... 236
           A1.2.9  Testing Analytical Results for Temporal
                   Stability .................................. 239
           A1.2.10 Trend Test ................................. 242
           A1.2.11 Practice Phase: Checking the Analysis
                   Quality Achieved Based on the Process
                   Standard Deviation ......................... 243
      A1.3 Phases II and III: Control Charts .................. 244
           A1.3.1  Blank Value Control Chart .................. 245
           A1.3.2  χ-Chart for Standard Solutions ............. 246
           A1.3.3  Recovery Rate (RR) Control Chart ........... 247
           A1.3.4  Verifying Precision by Means of R-Charts
                   and s-Charts ............................... 249
           A1.3.5  Testing for Series-Internal Drift .......... 251
           A1.3.6  RR-Control Chart by Addition of a
                   Standard ................................... 253
           A1.3.7  Cusum Chart ................................ 254
           A1.3.8  Equivalency ................................ 258
           A1.3.9 Standard Addition ........................... 261

Appendix 2
   A2 Statistical Tables ...................................... 263
      A2.1  t-Table ........................................... 263
      A2.2  F-Table(95%) ...................................... 264
      A2.2  F-Table (99%) ..................................... 265
      A2.3  Grubbs Table ...................................... 267
      A2.4  χ2-Table .......................................... 268

Appendix 3
   A3 Contents of the CD ...................................... 269
      A3.1  Checklists ........................................ 269
      A3.2  Instructions for Using the Calculation Examples ... 269
      A3.3  Statistical Table Values .......................... 270

Subject Index ................................................. 271


Recent acquisitions archives | Russian acquisitions | Foreign acquisitions | Sigla(Rus)
 


[ Home | Library | Akademgorodok | News | Exhibitions | Resources | InfoPilot | Biblio | Partners | Search | Russian Pages ]

Send Suggestions | E-mail to: www@prometeus.nsc.ru
Russification of your software | Access Statistics: archives | current
© 1998-2010 Branch of SPSL SB RAS, Novosibirsk, Russia
Rambler's Top100

Updated: Wed Feb 27 14:35:58 2019. Size: 22,018 bytes.
Visit No. 1054 since 28.09.2010