Table Of ContentW.Funk,V.Dammann,G.Donnevert
QualityAssurance
inAnalyticalChemistry
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Werner Funk,Vera Dammann, Gerhild Donnevert
Quality Assurance in Analytical Chemistry
Applications in Environmental, Food,
and Materials Analysis, Biotechnology,
and Medical Engineering
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UniversityofAppliedSciences data,illustrations,proceduraldetailsorotheritems
Gießen-Friedberg mayinadvertentlybeinaccurate.
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ISBN 978-3-527-31114-9
InMemoriam
Professor Werner Funk
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ISBN978-0-471-26918-2
VII
Contents
Preface XIII
ListofSymbols XVII
0 Introduction 1
0.1 GeneralDifferentiationofAnalyticalProcesses 3
0.2 QualityofAnalyticalProcessesandResults 4
0.3 TheSystemofAnalyticalQualityAssurance 4
0.4 TheFour-PhaseModelofAnalyticalQualityAssurance 6
1 PhaseI:EstablishingaNewAnalyticalProcedure 9
1.1 Introduction 9
1.1.1 ObjectivesofPhaseI 9
1.1.2 WhenAreCharacteristicDataObtained? 9
1.1.3 TheProgressionofPhaseI 10
1.1.4 ResultsofPhaseI;StatisticalData 14
1.2 CalibrationoftheFundamentalAnalyticalProcedure 15
1.2.1 EstablishmentofanAnalyticalRange 16
1.2.2 PreparationofStandardSamples 16
1.2.3 DeterminationoftheCalibrationFunctionandProcessData 17
1.2.3.1 ProcessDatafortheLinearCalibrationFunction 18
1.2.3.2 ProcessDatafortheSecond-OrderCalibrationFunction 19
1.2.3.3 CalculatingAnalyticalResultswiththeAidoftheCalibration
Function 21
1.2.4 VerificationoftheFundamentalCalibration 23
1.2.4.1 VerificationofLinearity 23
1.2.4.2 VerificationofPrecision 25
1.3 AnalysesatVeryLowConcentrations 29
1.3.1 DecisionLimit 32
1.3.2 DeterminingtheMinimumDetectableValue 34
1.3.2.1 MinimumDetectableValue,DeterminedUsingtheDistribution
ofBlankValues 34
VIII Contents
1.3.2.2 MinimumDetectableValue,ObtainedUsingtheCalibration
Function 35
1.3.3 LimitofQuantification 35
1.3.4 QuickEstimation 36
1.3.5 EstimationoftheDecisionLimitandLimitofQuantification
UsingtheS/NRatio 37
1.4 ValidationofIndividualProcessStepsandExaminationofMatrix
Influences 37
1.4.1 SystematicErrors 37
1.4.1.1 ConstantSystematicErrors,AdditiveDeviations 37
1.4.1.2 ProportionalSystematicErrors,MultiplicativeDeviations 38
1.4.2 EstablishmentandAssessmentoftheRecoveryFunction 38
1.4.2.1 PrerequisitesfortheInterpretationoftheRecoveryFunction 39
1.4.2.2 TestingforSystematicErrors 40
1.4.3 ApplicationoftheRecoveryFunction 41
1.4.3.1 CheckingIndividualProcessSteps 41
1.4.3.2 DeterminationoftheRecoveryFunctiontoProvetheInfluence
ofaMatrix 45
1.5 AdditionalStatisticalMethods 46
1.6 UseofInternalStandards 46
1.6.1 Definition,Purpose 46
1.6.2 ConditionsandLimitationsoftheUseofInternalStandards 47
1.6.3 Procedure 47
1.7 PreparingforRoutineAnalysis 49
1.7.1 ExaminationoftheTimeDependencyofMeasuredValues 49
1.7.1.1 Comparisonofthe“WithinBatch”StandardDeviation(s )
w
withthe“BetweenBatches”StandardDeviation(s ) 49
b
1.7.1.2 DeterminingtheNeedforDailyAdjustmentofAnalytical
Equipment 51
1.7.1.3 TheTrendTest 51
1.8 SummaryoftheResultsofPhaseI(ProcessDevelopment):
Documentation 54
2 PhaseII:AnAnalyticalProcessBecomesRoutine;PreparativeQuality
Assurance 57
2.1 Introduction 57
2.1.1 ObjectivesofPhaseII 57
2.1.2 ExecutionofPhaseII 57
2.1.3 ProgressionofPhaseII 57
2.1.4 ResultsofPhaseII 58
2.2 SelectionoftheAnalyticalProcedure 59
2.2.1 SpecificityoftheProcedure 60
2.2.2 SelectivityoftheAnalyticalProcedure 60
2.2.3 WorkingRange 60
2.2.4 CalibrationFunction,Sensitivity,andPrecisionoftheProcedure 60
Contents IX
2.2.5 MinimumDetectableValueandLimitofQuantification 61
2.2.6 RiskofSystematicError 61
2.2.7 Effort,Costs 61
2.3 The“Training”PhaseoftheProcess 62
2.4 EstablishmentofQualityObjectivestobeAdheredtoinRoutine
Usage 64
2.4.1 ExternalQualityRequirements 65
2.4.2 InternalQualityRequirements 66
2.5 ControlSamplesforInternalQualityAssurance 66
2.5.1 RequirementsofControlSamples 66
2.5.2 TypesofControlSamples 67
2.5.2.1 StandardSolutions 67
2.5.2.2 BlankSamples 67
2.5.2.3 NaturalSamples 67
2.5.2.4 SpikedNaturalSamples 68
2.5.2.5 SyntheticSamples 68
2.5.2.6 CertifiedReferenceMaterials(CRMs) 68
2.5.3 RequirementsforProducersofControlMaterials 69
2.5.4 ApplicabilityofControlSampleTypes 69
2.6 TheControlChartSystem 70
2.6.1 Introduction:HistoryoftheControlChart 70
2.6.2 PrincipleofaControlChart 72
2.6.3 AverageRunLength(ARL)andEvaluationofControlCharts 73
2.6.4 DerivationoftheAverageRunLength(ARL) 74
2.6.4.1 ExamplesofTheoreticalCalculations 75
2.6.4.2 AnalyticalExample 76
2.6.5 ConceptforthePreparationofRoutineQualityControl 78
2.6.6 EvaluationofthePreliminaryPeriod 80
2.6.6.1 VarianceAnalysis 80
2.6.6.2 AdherencetoRequiredQualityObjectives 80
2.6.7 TypesofControlChartsandTheirApplications 80
2.6.7.1 ShewhartCharts 81
2.6.7.2 R-Chart(RangeControlChart) 89
2.6.7.3 DifferenceChart 96
2.6.7.4 StandardDeviationChart(s-Chart) 98
2.6.7.5 TargetValueCharts 99
2.6.7.6 CusumChart 100
2.6.8 SummaryoftheCharacterizationofControlCharts 112
3 PhaseIII:RoutineQualityAssurance 115
3.1 Introduction 115
3.1.1 SettingtheObjectivesofPhaseIII 115
3.1.2 ExecutionofPhaseIII 115
3.1.3 ProgressionofPhaseIII 115
3.2 FundamentalMeasuresofInternalQualityAssurance 118
