SOCIO–ECONOMIC PROJECTION OF ANALYTICAL CHEMISTRY FOUNDATIONS OF ANALYTICAL CHEMISTRY BLOCK III SOCIO–ECONOMIC PROJECTION OF ANALYTICAL CHEMISTRY Chapter 7. Chapter 8. Chapter 9. Analytical problem-solving Analytical Chemistry and Quality Social responsibility of Analytical Chemistry BLOCK I. INTRODUCTION TO ANALYTICAL CHEMISTRY BLOCK II. THE ANALYTICAL PROCESS ANNEX 1. GLOSSARY OF TERMS ANNEX 2. ANSWERS TO THE QUESTIONS 8-1

Chapter 8: Analytical Chemistry and quality BLOCK III SOCIO–ECONOMIC PROJECTION OF ANALYTICAL CHEMISTRY Chapter 8: Analytical Chemistry and quality Contents 8.1.1. Introduction 8.1.2. A general approach to quality 8.1.3. Quality in Analytical Chemistry 8.1.4. Quality Systems in analytical laboratories 8.1.5. Controlling analytical quality 8.1.6. Assessing analytical quality 8.1.7. Supports of Analytical Quality Assurance 8.1.8. Concluding remarks Teaching objectives To define “quality”. To relate quality to the general and specific objectives of Analytical Chemistry. To introduce students to the planning and development of Quality Systems in analytical laboratories. To describe the methodological tools needed to implement control and assessment activities in analytical laboratories. 8-2

8.1.1. Introduction (I) Chapter 8: Analytical Chemistry and quality BASIC APPLIED Relating analytical chemical concepts to quality Implementing Quality Systems ANALYTICAL PROPERTIES ANALYTICAL PROBLEM 8-3

Chapter 8: Analytical Chemistry and quality 8.1.1. Introduction (II) EXAMPLE OF THE NEED FOR LABORATORIES TO USE QUALITY SYSTEMS: several laboratories obtained rather different results in the determination of various elements in a sample of lichen. ELEMENT Lowest value (µg/g) Highest value Ratio Calcium 200 (FRX) 3155 (FRX) 15 Copper 0.80 (FAAS) 38.8 (ICP-AES) 48 Mercury 0.008 (CVAAS) 0.551 (CVAAS) 110 Molybdenum 0.056 (ICR-MS) 2.072 (ICP-AES) 37 Zinc 9.7 (FAAS) 282.5 (ICP-AES) 29 8-4

QUALITY 8.1.2. A general approach to quality (I) Chapter 8: Analytical Chemistry and quality 8.1.2. A general approach to quality (I) 8.1.2.1. INTEGRAL DEFINITION OF “QUALITY” Characteristics Attributes Properties Usefulness, ability Fulfilling requirements Basic side Applied side QUALITY Satisfying needs Following directions Comparison Assessment Indicators Qualitative Quantitative Integral 8-5

8.1.2. A general approach to quality (II) Chapter 8: Analytical Chemistry and quality 8.1.2. A general approach to quality (II) 8.1.2.2. TYPES OF QUALITY EXTERNAL QUALITY 2 EXPECTED PERCEIVED 5 3 4 ACHIEVED INTERNAL QUALITY 1 PLANNED 8-6

8.1.2. A general approach to quality (III) Chapter 8: Analytical Chemistry and quality 8.1.2. A general approach to quality (III) 8.1.2.3. QUALITY TRADE-OFFS Intrinsic properties of the entity Cost-effectiveness Expeditiousness Personnel- related factors 8-7

8.1.2. A general approach to quality (IV) Chapter 8: Analytical Chemistry and quality 8.1.2. A general approach to quality (IV) 8.1.2.4. STRUCTURE OF QUALITY QUALITY POLICY QUALITY MANAGEMENT QUALITY SYSTEM QUALITY ASSURANCE Quality control Quality assessment Internal corrections Examination Action External corrections Products, Systems, Services 8-8 Entity

8.1.2. A general approach to quality (V) Chapter 8: Analytical Chemistry and quality 8.1.2. A general approach to quality (V) 8.1.2.5. BENEFITS OF QUALITY BENEFITS DIRECT INDIRECT Planning and documenting accepted IMPROVED FEATURES (product, system, service) CLIENT SATISFACTION INCREASED CREDIBILITY AND PRESTIGE Rational performance of activities Minimal improvisation Optimal use of resources Commitment to improvement and innovation Motivated personnel New jobs 8-9

8.1.3. Quality in Analytical Chemistry (I) Chapter 8: Analytical Chemistry and quality 8.1.3. Quality in Analytical Chemistry (I) 8.1.3. GENERALITIES WHY? HOW? ANALYTICAL CHEMISTRY QUALITY WHEN? WHERE? 8-10

8.1.3. Quality in Analytical Chemistry (II) Chapter 8: Analytical Chemistry and quality 8.1.3. Quality in Analytical Chemistry (II) 8.1.3.1. TYPES OF QUALITY IN ANALYTICAL CHEMISTRY EXTERNAL QUALITY (quality of client’s entities) Client’s information needs ANALYTICAL QUALITY - Capital Quality of results Analytical properties Analytical problem - Basic - Productivity- related Quality of analytical processes Quality of work and its organization Quality of analytical tools 8-11

8.1.3. Quality in Analytical Chemistry (III) Chapter 8: Analytical Chemistry and quality 8.1.3. Quality in Analytical Chemistry (III) 8.1.3.2. QUALITY AND ANALYTICAL PROPERTIES Accuracy Capital Types Analytical properties Analytical Quality Represen- tativeness Robustness Precision Sensitivity Selectivity Expeditiousness Cost-effectiveness Personnel-related factors Proper sampling Quality of results Quality of analytical process Basic Productivity- related COMPLEMENTARY AND CONTRADICTORY RELATIONSHIPS 8-12

8.1.3. Quality in Analytical Chemistry (IV) Chapter 8: Analytical Chemistry and quality 8.1.3. Quality in Analytical Chemistry (IV) 8.1.3.3. QUALITY AND THE ANALYTICAL PROBLEM QUALITY Body of properties Comparison Client satisfaction Comparison with TANGIBLE STANDARDS WRITTEN STANDARDS CLIENT’S REQUIREMENTS Analytical properties Analytical problem-solving ANALYTICAL QUALITY 8-13

8.1.4. Quality systems in analytical laboratories (I) Chapter 8: Analytical Chemistry and quality 8.1.4. Quality systems in analytical laboratories (I) 8.1.4.1. ELEMENTS OF QUALITY ASSURANCE (1) QUALITY ASSURANCE Analytical problem QUALITY ASSESSMENT Results QUALITY CONTROL Analytical laboratory Internal corrective actions Corrective actions 8-14

8.1.4. Quality systems in analytical laboratories (II) Chapter 8: Analytical Chemistry and quality 8.1.4. Quality systems in analytical laboratories (II) 8.1.4.1. ELEMENTS OF QUALITY ASSURANCE (2) QUALITY CONTROL Before the analytical process During the analytical process QUALITY ASSURANCE ACTIVITIES ASSESSMENT QUALITY CORRECTIVE ACTIONS After the analytical process 8-15

8.1.4. Quality systems in analytical laboratories (III) Chapter 8: Analytical Chemistry and quality 8.1.4. Quality systems in analytical laboratories (III) 8.1.4.1. ELEMENTS OF QUALITY ASSURANCE (3) SOPs Quality Manual Quality Assurance Unit Good Laboratory Practices (GLPs) ISO 17025 General standard ISO 9000 QUALITY SYSTEMS IN ANALYTICAL LABORATORIES Others Critical point systems Total Quality Management (TQM) Combinations of standards 8-16

8.1.4. Quality systems in analytical laboratories (IV) Chapter 8: Analytical Chemistry and quality 8.1.4. Quality systems in analytical laboratories (IV) 8.1.4.2. UNE-EN ISO 17025:2000 TITLE GENERAL REQUIREMENTS FOR THE COMPETENCE OF TESTING AND CALIBRATION LABORATORIES Establishing an internal Quality Management System without external recognition Consistent with ISO 9000:1994 (not with ISO 9000:2000) GOALS External recognition of the laboratory’s technical competence (by clients, regulatory authorities or accreditation bodies) ISO 17025 REPLACES ISO 25 (and EN 45001) APPLICABLE TO PHYSICAL AND (BIO)CHEMICAL MEASUREMENTS THE BASIS FOR LABORATORY ACCREDITATION (any type of testing or calibration laboratory) NOT VALID FOR LABORATORY CERTIFICATION CERTIFICATION WITHIN THE FRAMEWORK OF ISO 9000 DOES NOT BY ITSELF IMPLY COMPETENCE OF A LABORATORY TO DELIVER TECHNICALLY VALID RESULTS 8-17

GLPs 8.1.4. Quality systems in analytical laboratories (V) Chapter 8: Analytical Chemistry and quality 8.1.4. Quality systems in analytical laboratories (V) 8.1.4.3. GOOD LABORATORY PRACTICES (GLPs) “The body of rules, operating procedures and practices established by a given organization (e.g., OECD, EU) that are considered to be mandatory with a view to ensuring quality and correctness in the results produced by a laboratory” GLPs STANDARD OPERATING PROCEDURES QUALITY ASSURANCE UNIT Detailed description of all laboratory activities Independent of the laboratory Answerable to the management of the parent body Sample handling Audited internally by the body but not by the laboratory Reagent control Reference material control Implements, monitors and assesses quality with a view to its improvement Equipment and methods Archiving activities… 8-18

8.1.4. Quality systems in analytical laboratories (VI) Chapter 8: Analytical Chemistry and quality 8.1.4. Quality systems in analytical laboratories (VI) 8.1.4.4. QUALITY ASSURANCE SYSTEMS IN ANALYTICAL CHEMISTRY (1) The operations of the CMP should be accurately described, explained and understood so that their uncertainty can be fully described in detail in terms of SI units PRIMARY Well-defined uncertainty in base standards No need for analyte standard METROLOGICAL QUALITY Described and understood REFERENCE Used to confirm the accuracy or uncertainty (traceability) of quantification methods Metrological quality STANDARD Developed, validated and issued by standardization bodies OFFICIAL Legally required to endorse the results of different laboratories QUANTIFICATION METHODS Tested in order to establish their intrinsic features (analytical properties) and extrinsic features (consistency with the analytical problem) VALIDATED TRACEABLE Standard, official or other types of methods sharing a common reference (primary standard, CRM, SI unit) that is a link in the traceability chain 8-19

8.1.4. Quality systems in analytical laboratories (VII) Chapter 8: Analytical Chemistry and quality 8.1.4. Quality systems in analytical laboratories (VII) 8.1.4.4. QUALITY ASSURANCE SYSTEMS IN ANALYTICAL CHEMISTRY (2) Formal demonstration that a system operates and will continue to operate as it should. Applicable to samples, data and parameters. Related to the analytical parameters accuracy, precision, sensitivity, selectivity, range/linearity and ROBUSTNESS, among others. VALIDATION ROBUSTNESS Related to consistency in the results obtained under slightly different experimental conditions. Related to RELIABILITY OF METHOD PRECISION TRANSFERABILITY CALIBRATION (rigorous and appropriate) CHEMOMETRICS ACCURACY OF RESULTS REFERENCE MATERIALS 8-20

8.1.5. Analytical quality control Chapter 8: Analytical Chemistry and quality 8.1.5. Analytical quality control QUALITY CONTROL QUANTITATIVE CONNOTATIONS Comparison of data Numerical references Activities (a) Implementing and using control charts based on RMs RMs CRMs Different methods applied to the same sample (b) Examining and correcting equipment (c) Examining the purity and stability of reagents and solutions (d) Examining laboratory conditions (e) Examining the sample custody system (d) Using RMs and CRMs (blind samples) to examine CMPs (f) Examining the results after a change in tools and/or personnel 8-21

8.1.6. Assessing analytical quality (I) Chapter 8: Analytical Chemistry and quality 8.1.6. Assessing analytical quality (I) 8.1.6.1. TYPES (1) Before the analytical process Qualitative During the analytical process Quantitative When? What? After the analytical process Integral QUALITY ASSESSMENT By whom? External Internal 8-22

8.1.6. Assessing analytical quality (II) Chapter 8: Analytical Chemistry and quality 8.1.6. Assessing analytical quality (II) 8.1.6.1. TYPES (2) QUALITY ASSESSMENT Personnel conducting the assessment First criterion Second criterion From laboratory INTERNAL INTERNAL From laboratory’s parent body External– internal EXTERNAL External– external (audits) External to laboratory and its parent body EXTERNAL 8-23

8.1.6. Assessing analytical quality (III) Chapter 8: Analytical Chemistry and quality 8.1.6. Assessing analytical quality (III) 8.1.6.2. ANALYTICAL LABORATORY ACCREDITATION (1) Formal recognition in writing that a laboratory is fit and competent for conducting a given analysis or group of analyses What? ANALYTICAL LABORATORY ACCREDITATION By whom? Features An public or private body Voluntary Temporary Partial A given activity rather than the laboratory as a whole At the laboratory’s request For a specified period Based on standards (EU, OECD, ISO) 8-24

8.1.6. Assessing analytical quality (IV) Chapter 8: Analytical Chemistry and quality 8.1.6. Assessing analytical quality (IV) 8.1.6.2. ANALYTICAL LABORATORY ACCREDITATION (2) Access for periodic controls QUALITY MANUAL Maintain QUALITY ASSURANCE SYSTEM Auditors TRADE-OFFS Pay CERTIFICATE OF ACCREDITATION Documental and visual (qualitative) inspection LABORATORY Challenge - + REPORT 8-25 8-24

8.1.6. Assessing analytical quality (V) Chapter 8: Analytical Chemistry and quality 8.1.6. Assessing analytical quality (V) 8.1.6.3. PROFICIENCY TESTING (1) INTERLABORATORY EXERCISES This is an external-external mode of quality assessment. The laboratory concerned takes part in an exercise involving analysing the same analytes in the same sample for comparison of its results with those of the other participating laboratories in order to have its proficiency evaluated. Training Validating a CMP Collaborative (same CMP) INTERLABORATORY EXERCISES GOALS Certifying an RM Proficiency testing Cooperative (different CMPs) 8-26

8.1.6. Assessing analytical quality (V) Chapter 8: Analytical Chemistry and quality 8.1.6. Assessing analytical quality (V) 8.1.6.3. PROFICIENCY TESTING (2) 11 10 7 1 20 5 12 16 18 19 17 22 15 21 13 8 2 4 9 3 6 -6 -4 -2 Laboratory code z score 8-27

8.1.7. Supports of analytical quality assurance Chapter 8: Analytical Chemistry and quality 8.1.7. Supports of analytical quality assurance HUMAN FACTOR SUPPORT BY THE BODY’S MANAGEMENT COMPUTERS QUALIMETRICS SUPPORT BY THE LABORATORY’S MANAGEMENT INTERLABORATORY EXERCISES COOPERATION OF THE LABORATORY STAFF CONSTRUCTIVE ATTITUDE OF AUDITORS DOCUMENTATION AND ARCHIVING 8-28

8.1.8. Concluding remarks (I) Chapter 8: Analytical Chemistry and quality 8.1.8. Concluding remarks (I) 8.1.8.1. DIFFICULTIES AND BENEFITS OF QUALITY ASSURANCE Abrupt implementation Compatibility with routine work Costs Lack of perseverance Human factor Complex literature Lack of leadership DIFFICULTIES QUALITY ASSURANCE BENEFITS Clear goals Rational work Endorsement by a third party Optimal resource usage Laboratory’s credibility Minimal indecision Less improvisation Client’s confidence Well-trained, motivated personnel New jobs 8-29

8.1.8. Concluding remarks (II) Chapter 8: Analytical Chemistry and quality 8.1.8. Concluding remarks (II) 8.1.8.2. CHANGES IN CLIENT–LABORATORY RELATIONSHIPS TRANSPARENCY CREDIBILITY Client Client Mutual recognition User User Auditing (accreditation) Lab Lab Proficiency testing INDEPENDENT BODY Lab Lab Company Company Relations Binary (direct) Ternary (indirect) Endorsement by a third party 8-30