PROGRESS IN ANALYTICAL ATOMIC SPECTROSCOPY
CONTENTS CHAPTER AN OVERVIEW OF ICP MASS SPECTROMETRY PRINCIPLES OF OPERATION CHAPTER PRINCIPLES OF ION FORMATION ION FORMATION NATURAL ISOTOPES SAMPLE INTRODUCTION AEROSOL GENERATION DROPLET SELECTION NEBULIZERS CONCENTRIC DESIGN CROSS-FLOW DESIGN MICROFOW DESIGN SPRAY CHAMBERS DOUBLE-PASS SPRAY CHAMBER CYCLONIC SPRAY CHAMBER AEROSOL DILUTION FINAL THOUGHTS PLASMA SOURCE THE PLASMA TORCH FORMATION OF AN ICP DISCHARGE THE FUNCTION OF THE RF GENERATOR IONIZATION OF THE SAMPLE INTERFACE REGION CAPACITIVE COUPLING ION KINETIC ENERGY BENEFTS OF A WELL-DESIGNED INTERFACE ION-FOCUSING SYSTEM ROLE OF THE ION OPTICS DYNAMICS OF ION FLOW COMMERCIAL ION OPTIC DESIGNS MASS ANALYZERS: QUADRUPOLE TECHNOLOGY BASIC PRINCIPLES OF OPERATION QUADRUPOLE PERFORMANCE CRITERIA RESOLUTION ABUNDANCE SENSITIVITY BENEFT OF GOOD ABUNDANCE SENSITIVITY MASS ANALYZERS: DOUBLE-FOCUSING MAGNETIC SECTOR TECHNOLOGY MAGNETIC-SECTOR MASS SPECTROSCOPY: A HISTORICAL PERSPECTIVE USE OF MAGNETIC-SECTOR TECHNOLOGY FOR ICP-MS PRINCIPLES OF OPERATION OF MAGNETIC-SECTOR TECHNOLOGY RESOLVING POWER OTHER BENEFTS OF MAGNETIC-SECTOR INSTRUMENTATION SIMULTANEOUS-MEASUREMENT APPROACH USING ONE DETECTOR MASS ANALYZERS: TIME-OF-FLIGHT TECHNOLOGY BASIC PRINCIPLES OF TOF TECHNOLOGY COMMERCIAL DESIGNS DIFFERENCES BETWEEN ORTHOGONAL AND ON-AXIS TOF BENEFTS OF TOF TECHNOLOGY FOR ICP-MS RAPID TRANSIENT PEAK ANALYSIS IMPROVED PRECISION RAPID DATA ACQUISITION HIGH-SPEED MULTI-ELEMENTAL IMAGING USING LASER ABLATION COUPLED WITH TOF-ICP-MS LASER ABLATION LASER IONIZATION TIME-OF-FLIGHT MASS SPECTROMETRY CHAPTER 10 MASS ANALYZERS: COLLISION/REACTION CELL AND INTERFACE TECHNOLOGY BASIC PRINCIPLES OF COLLISION/REACTION CELLS 10 2 DIFFERENT COLLISION/REACTION CELL APPROACHES 10 3 COLLISIONAL MECHANISMS USING NONREACTIVE GASES AND KINETIC ENERGY DISCRIMINATION 10 4 REACTION MECHANISMS WITH HIGHLY REACTIVE GASES AND DISCRIMINATION BY SELECTIVE BANDPASS MASS FILTERING 10 5 DYNAMIC REACTION CELL 10 6 LOW-MASS CUTOFF COLLISION/REACTION CELL USING REACTION MECHANISMS IN A COLLISION CELL 10 8 THE UNIVERSAL CELL 10 9 THE COLLISION/REACTION INTERFACE 10 10 DETECTION LIMIT COMPARISON OF SINGLE-QUADRUPOLE CRC SYSTEMS 10 11 TRIPLE-QUADRUPOLE SYSTEMS 10 12 M/S MODE 10 13 MS/MS MODE 10 14 ON-MASS MS/MS MODE 10 15 MASS-SHIFT MS/MS MODE 10 16 MULTI-QUAD SYSTEMS 10 17 DIFFERENCE BETWEEN A TRIPLE AND MULTI QUAD SYSTEM 10 18 FINAL THOUGHTS CHAPTER 11 ION DETECTORS CHANNEL ELECTRON MULTIPLIER FARADAY CUP DISCRETE-DYNODE ELECTRON MULTIPLIER EXTENDING THE DYNAMIC RANGE FILTERING THE ION BEAM USING TWO DETECTORS USING TWO SCANS WITH ONE DETECTOR USING ONE SCAN WITH ONE DETECTOR EXTENDING THE DYNAMIC RANGE USING PULSE-ONLY MODE 11 10 SIMULTANEOUS ARRAY DETECTORS CHAPTER 12 PEAK MEASUREMENT PROTOCOL 12 1 MEASUREMENT VARIABLES 12 2 MEASUREMENT PROTOCOL 12 3 OPTIMIZATION OF MEASUREMENT PROTOCOL 12 4 MULTIELEMENT DATA QUALITY OBJECTIVES 12 5 DATA QUALITY OBJECTIVES FOR SINGLE-PARTICLE ICP-MS STUDIES 12 6 FINAL THOUGHTS CHAPTER 13 METHODS OF QUANTITATION QUANTITATIVE ANALYSIS 13 2 EXTERNAL STANDARDIZATION 13 3 STANDARD ADDITIONS 13 4 ADDITION CALIBRATION 13 5 SEMIQUANTITATIVE ANALYSIS 13 6 ISOTOPE DILUTION ISOTOPE RATIOS 13 8 INTERNAL STANDARDIZATION CHAPTER 14 REVIEW OF ICP-MS INTERFERENCES SPECTRAL INTERFERENCES 14 2 OXIDES, HYDROXIDES, HYDRIDES AND DOUBLY CHARGED SPECIES 14 3 ISOBARIC INTERFERENCES 14 4 WAYS TO COMPENSATE FOR SPECTRAL INTERFERENCES 14 5 MATHEMATICAL CORRECTION EQUATIONS COOL/COLD PLASMA TECHNOLOGY COLLISION/REACTION CELLS 14 8 HIGH-RESOLUTION MASS ANALYZERS MATRIX INTERFERENCES 14 10 COMPENSATION USING INTERNAL STANDARDIZATION 14 11 SPACE CHARGE-INDUCED MATRIX INTERFERENCES CHAPTER 15 ROUTINE MAINTENANCE SAMPLE-INTRODUCTION SYSTEM 15 2 PERISTALTIC PUMP TUBING 15 3 NEBULIZERS 15 4 SPRAY CHAMBER 15 5 PLASMA TORCH 15 6 INTERFACE REGION ION OPTICS 15 8 ROUGHING PUMPS 15 9 AIR FILTERS 15 10 OTHER COMPONENTS TO BE PERIODICALLY CHECKED 15 11 THE DETECTOR 15 12 TURBOMOLECULAR PUMPS 15 13 MASS ANALYZER AND COLLISION/REACTION CELL 15 14 FINAL THOUGHTS CHAPTER 16 SAMPLING AND SAMPLE-PREPARATION TECHNIQUES COLLECTING THE SAMPLE 16 2 PREPARING THE SAMPLE 16 3 CRYOGENIC GRINDING 16 4 SAMPLE DISSOLUTION 16 5 REASONS FOR DISSOLVING SAMPLES 16 6 DIGESTED SAMPLE WEIGHTS MICROWAVE DIGESTION CONSIDERATIONS 16 8 WHY USE MICROWAVE DIGESTION? 16 9 CHOICE OF ACIDS 16 10 COMMERCIAL MICROWAVE TECHNOLOGY 16 11 DIGESTION STRATEGIES 16 12 FUNDAMENTAL PRINCIPLES OF MICROWAVE DIGESTION TECHNOLOGY 16 13 SEQUENTIAL SYSTEMS 16 14 ROTOR-BASED TECHNOLOGY 16 15 SINGLE REACTION CHAMBER TECHNOLOGY 16 16 SINGLE CAVITY MODE 16 17 PRINCIPLES OF SINGLE CAVITY MODE 16 18 AUTOMATION WITH SINGLE CAVITY MODE 16 19 SAMPLING PROCEDURES FOR MERCURY 16 20 REAGENT BLANKS 16 21 FINAL THOUGHTS CHAPTER 17 A PRACTICAL GUIDE TO REDUCING ERRORS AND CONTAMINATION USING PLASMA SPECTROCHEMISTRY UNDERSTANDING DATA ACCURACY AND PRECISION ESTIMATING ERROR TYPES OF ERRORS STANDARDS AND REFERENCE MATERIALS USING STANDARDS AND REFERENCE MATERIALS CALIBRATION CURVES DYNAMIC RANGE, CONCENTRATION AND ERROR LABORATORY SOURCES OF ERROR AND CONTAMINATION SOURCES OF LABORATORY CONTAMINATION AND ERROR 17 10 WATER QUALITY 17 11 REAGENTS 17 12 LABORATORY ENVIRONMENT AND PERSONNEL 17 13 GENERAL PRINCIPLES AND PRACTICES CHAPTER 18 PERFORMANCE- AND PRODUCTIVITY-ENHANCEMENT TECHNIQUES PERFORMANCE-ENHANCING TECHNIQUES LASER ABLATION 18 2 COMMERCIAL LASER ABLATION SYSTEMS FOR ICP-MS 18 3 EXCIMER LASERS 18 4 BENEFTS OF LASER ABLATION FOR ICP-MS 18 5 OPTIMUM LASER DESIGN BASED ON THE APPLICATION REQUIREMENTS 18 6 193-NM LASER TECHNOLOGY FLOW INJECTION ANALYSIS 18 8 ELECTROTHERMAL VAPORIZATION (ETV) 18 9 CHILLED SPRAY CHAMBERS AND DESOLVATION DEVICES 18 10 WATER-COOLED AND PELTIER-COOLED SPRAY CHAMBERS 18 11 ULTRASONIC NEBULIZERS 18 12 SPECIALIZED MICROFOW NEBULIZERS WITH DESOLVATION TECHNIQUES 18 13 DIRECT INJECTION NEBULIZERS 18 14 PRODUCTIVITY-ENHANCING TECHNIQUES 18 15 FASTER ANALYSIS TIMES 18 16 AUTOMATED IN-LINE AUTO-DILUTION AND AUTO-CALIBRATION 18 17 AUTOMATED SAMPLE IDENTIFCATION AND TRACKING CHAPTER 19 COUPLING ICP-MS WITH CHROMATOGRAPHIC SEPARATION TECHNIQUES FOR SPECIATION STUDIES HPLC COUPLED WITH ICP-MS CHROMATOGRAPHIC SEPARATION REQUIREMENTS ION EXCHANGE CHROMATOGRAPHY (IEC) REVERSED-PHASE ION-PAIR CHROMATOGRAPHY (RP-IPC) 19 5 COLUMN MATERIAL ISOCRATIC OR GRADIENT ELUTION SAMPLE-INTRODUCTION REQUIREMENTS OPTIMIZATION OF ICP-MS PARAMETERS COMPATIBILITY WITH ORGANIC SOLVENTS 19 10 COLLISION/REACTION CELL OR INTERFACE CAPABILITY 19 11 OPTIMIZATION OF PEAK MEASUREMENT PROTOCOL 19 12 FULL SOFTWARE CONTROL AND INTEGRATION 19 13 FINAL THOUGHTS CHAPTER 20 OVERVIEW OF THE ICP-MS APPLICATION LANDSCAPE 20 1 APPLICATION CAPABILITY 20 2 ANALYTICAL CHALLENGES 20 3 MAJOR TRENDS 20 4 WHAT IS DRIVING ICP-MS DEVELOPMENT? 20 5 FUTURE DIRECTION CHAPTER 21 FUNDAMENTAL PRINCIPLES AND APPLICATIONS OF ATOMIC ABSORPTION AND ATOMIC FLUORESCENCE FLAME AAS ADVANTAGES OF FLAAS FLAAS INTERFERENCES AND THEIR CONTROL DISADVANTAGES OF FLAAS 21 5 GRAPHITE-FURNACE AAS ADVANTAGES OF GFAAS GFAAS INTERFERENCES AND THEIR CONTROL DISADVANTAGES OF GFAAS 21 10 VAPOR-GENERATION AAS 21 11 ADVANTAGES OF COLD-VAPOR AAS 21 12 DISADVANTAGES OF COLD-VAPOR AAS 21 13 HYDRIDE-GENERATION AAS 21 14 ADVANTAGES OF HYDRIDE-GENERATION AAS 21 15 DISADVANTAGES OF HYDRIDE-GENERATION AAS 21 16 HYPHENATED TECHNIQUES 21 17 ATOMIC FLUORESCENCE 21 18 ADVANTAGES AND DISADVANTAGES OF AFS 21 19 FINAL THOUGHTS CHAPTER 22 FUNDAMENTAL PRINCIPLES, METHOD DEVELOPMENT AND OPERATIONAL REQUIREMENTS OF ICP-OPTICAL EMISSION SPECTROSCOPY 22 1 BASIC DEFNITIONS 22 2 PRINCIPLES OF EMISSION 22 3 ATOMIC AND IONIC EMISSION 22 4 INSTRUMENTATION 22 5 SAMPLE INTRODUCTION 22 6 AEROSOL GENERATION 22 7 NEBULIZERS 22 8 SPRAY CHAMBERS 22 9 TORCHES 22 10 SPECTROMETERS 22 11 FORE-OPTICS 22 12 OPTICAL DESIGNS 22 13 DETECTORS 22 14 HISTORICAL PERSPECTIVE 22 15 PHOTOMULTIPLIER TUBES 22 16 PHOTODIODE ARRAYS 22 17 CHARGE-TRANSFER DEVICES 22 18 CHARGE-COUPLED DEVICES 22 19 CHARGE-INJECTION DEVICES 22 20 ANALYTICAL PERFORMANCE 22 21 DEPENDENCE ON ENVIRONMENTAL OPERATING CONDITIONS 22 22 EXHAUST REQUIREMENTS 22 23 ELECTRICAL REQUIREMENTS 22 24 TEMPERATURE AND PRESSURE REQUIREMENTS 22 25 MAINTENANCE 22 26 DEPENDENCE ON PLASMA OPERATING CONDITIONS 22 27 RF POWER 22 28 PLASMA GASES 22 29 PUMP SETTINGS 22 30 PLASMA VIEWING HEIGHT 22 31 PRECISION AND ACCURACY 22 32 DETECTION LIMITS 22 33 LIMIT OF QUANTITATION 22 34 BACKGROUND EQUIVALENT CONCENTRATION 22 35 SENSITIVITY 22 36 METHOD-DEVELOPMENT CONSIDERATIONS 22 37 ANALYTICAL-WAVELENGTH CONSIDERATIONS 22 38 INTERFERENCES 22 39 PHYSICAL INTERFERENCES 22 40 CHEMICAL INTERFERENCES 22 41 SPECTRAL INTERFERENCES 22 42 DATA ACQUISITION 22 43 METHOD VALIDATION 22 44 FINAL THOUGHTS CHAPTER 23 OTHER COMPLEMENTARY ATOMIC SPECTROSCOPY TECHNIQUES 23 1 X-RAY FLUORESCENCE 23 2 XRF INSTRUMENTAL CONFGURATION 23 3 QUANTITATION BY XRF 23 4 XRF DETECTION LIMITS 23 5 SAMPLE PREPARATION FOR XRF 23 6 X-RAY DIFFRACTION 23 7 LASER INDUCED BREAKDOWN SPECTROSCOPY 23 8 LIBS FUNDAMENTAL PRINCIPLES 23 9 LIBS CAPABILITIES 23 10 LIBS APPLICATION AREAS 23 11 LIBS DETECTION CAPABILITY 23 12 LIBS ON MARS 23 13 MICROWAVE INDUCED PLASMA OPTICAL EMISSION SPECTROSCOPY 23 14 BASIC PRINCIPLES OF THE MP-AES TECHNOLOGY 23 15 BENEFTS OF MIP-AES 23 16 TYPICAL APPLICATIONS OF MP-AES 23 17 LASER ABLATION LASER IONIZATION TIME-OF-FLIGHT MASS SPECTROMETRY 23 18 MASSBOX 23 19 BASIC PRINCIPLES LALI-TOF-MS 23 20 MATRIX EFFECTS 23 21 DIFFUSION AND TRANSPORT 23 22 INTERFERENCES 23 23 TRANSMISSION EFFCIENCY 23 24 INORGANIC AND ORGANIC ANALYSIS 23 25 OPERATIONAL USE 23 26 USER INTERFACE 23 27 PERFORMANCE CAPABILITIES 23 28 FINAL THOUGHTS CHAPTER 24 PERFORMANCE CHARACTERISTICS OF COMMON ATOMIC SPECTROSCOPY TECHNIQUES 24 1 FLAME ATOMIC ABSORPTION 24 2 ELECTROTHERMAL ATOMIZATION 24 3 HYDRIDE/VAPOR GENERATION AA 24 4 ATOMIC FLUORESCENCE 24 5 RADIAL ICP-OES 24 6 AXIAL ICP-OES ICP-MS 24 8 COMPARISON HIGHLIGHTS CHAPTER 25 RUNNING COSTS OF COMMON AS TECHNIQUES 25 1 GASES 25 1 1 FAA 25 1 2 AIR—C2H2 25 1 2 1 ETA 25 1 2 2 ICP-OES AND ICP-MS 25 2 ELECTRICITY 25 2 1 FAA 25 2 2 ETA 25 2 3 ICP-OES AND ICP-MS 25 3 CONSUMABLES 25 3 1 FAA 25 3 2 ETA 25 3 3 ICP-OES 25 3 4 ICP-MS 25 4 COST PER SAMPLE 25 4 1 FAA 25 4 2 ETA 25 4 3 ICP-OES 25 4 4 ICP-MS 25 5 RUNNING COSTS OF ATOMIC FLUORESCENCE 25 6 FINAL THOUGHTS CHAPTER 26 HOW TO EVALUATE AN ICP MASS SPECTROMETER: SOME IMPORTANT ANALYTICAL CONSIDERATIONS 26 1 EVALUATION OBJECTIVES 26 1 1 ANALYTICAL PERFORMANCE 26 1 1 1 DETECTION CAPABILITY 26 1 1 2 PRECISION 26 1 1 3 ISOTOPE RATIO PRECISION 26 1 1 4 ACCURACY 26 1 1 5 DYNAMIC RANGE 26 1 1 6 INTERFERENCE REDUCTION 26 1 1 6 1 REDUCING SPECTRAL INTERFERENCES 26 1 1 6 2 RESOLUTION IMPROVEMENT 26 1 1 6 3 HIGHER ABUNDANCE SENSITIVITY SPECIFCATIONS 26 1 1 6 4 USE OF COOL PLASMA TECHNOLOGY 26 1 1 6 5 USING COLLISION/REACTION CELL AND INTERFACE TECHNOLOGY 26 1 1 7 REDUCTION OF MATRIX-INDUCED INTERFERENCES 26 1 1 8 SAMPLE THROUGHPUT 26 1 1 9 TRANSIENT SIGNAL CAPABILITY 26 1 1 10 SINGLE-PARTICLE ICP-MS TRANSIENT SIGNALS 26 1 2 USABILITY ASPECTS 26 1 2 1 EASE OF USE 26 1 2 2 ROUTINE MAINTENANCE 26 1 2 3 COMPATIBILITY WITH ALTERNATIVE SAMPLING ACCESSORIES 26 1 2 4 INSTALLATION OF INSTRUMENT 26 1 2 5 TECHNICAL SUPPORT 26 1 2 6 TRAINING 26 1 3 RELIABILITY ISSUES 26 1 3 1 SERVICE SUPPORT 26 2 FINANCIAL CONSIDERATIONS 26 3 THE EVALUATION PROCESS: A SUMMARY