Preface ..................................................... xiii
Biography ...................................................... xv
Acknowledgements ............................................. xvii
1 A Practical Approach to Quantitative Metal Analysis of
Organic Matrices Using ICP-OES ............................... 1
1.1 Introduction and Basic Overview ......................... 1
1.2 Schematic Representation of the Energies Generated by
Atomic Spectroscopic Methods ............................ 4
1.3 Excitation Energy (Quantum Theory and Atomic Spectra) ... 5
1.4 Ionisation Energy and Number of Excited Atoms ........... 7
1.5 Width of Atomic Lines ................................... 9
1.5.1 Natural Broadening ............................... 9
1.5.2 Doppler Broadening ............................... 9
1.5.3 Lorentzian Broadening or Pressure Broadening ..... 9
1.5.4 Holtsmark Broadening or Resonance Broadening .... 11
1.5.5 Field Broadening or Stark Broadening ............ 11
1.5.6 Self-Absorption and Self-Reversal Broadening .... 11
1.6 Brief Summary of Atomic Spectroscopic Techniques Used
for Elemental Analysis ................................. 12
1.6.1 The Atomic Absorption Spectrophotometer ......... 12
1.6.2 Atomic Fluorescence Spectroscopy ................ 13
1.6.3 Direct Current Plasma Optical Emission
Spectrometry (DCP-OES) .......................... 13
1.6.4 Microwave Induced Plasma (MIP) .................. 14
1.6.5 Glow Discharge Optical Emission Spectrometry
(GD-OES) ........................................ 15
1.6.6 Inductively Coupled Plasma Optical Emission
Spectrometry (ICP-OES) .......................... 15
1.7 Summary: Applications of Atomic Spectroscopy ........... 16
References .................................................. 18
2 Instrumentations Associated with Atomic Spectroscopy ........ 21
2.1 Instrumentation ........................................ 21
2.2 Types of Plasma Sources ................................ 24
2.2.1 Direct Current Plasma Atomic Emission
Spectrograph .................................... 25
2.2.2 Microwave Induced Plasma ........................ 25
2.2.3 Optical Emission Spectroscopy ................... 26
2.3 Sample Introduction Systems ............................ 30
2.3.1 Mechanical Transfer of Sample/Standards Using
Peristaltic Pump, Pressure Valves, Motorised
Syringes, etc. .................................. 31
2.3.2 Nebulisers ...................................... 31
2.3.3 Brief Outline of Atomic Spectroscopy
Hyphenated Systems .............................. 39
2.4 Spray Chambers ......................................... 43
2.5 ICP-OES Torches ........................................ 45
2.6 Optics ................................................. 49
2.6.1 Grating Orders .................................. 51
2.7 Signal Detectors ....................................... 53
2.7.1 Photomultiplier Tubes ........................... 53
2.7.2 Charge Coupled Devices .......................... 55
References .................................................. 58
3 Methodologies of Metal Analysis of Organic Matrices Using
ICP-OES ..................................................... 59
3.1 Sample Preparation Techniques and Methods of
Analysis ............................................... 59
3.2 Defining Goals ......................................... 60
3.3 Steps in Chemical Analytical Protocol .................. 61
3.4 Sampling and its Importance ............................ 62
3.5 Sample Preparation Methods ............................. 63
3.5.1 Direct Analysis of Organic Solutions ............ 64
3.5.2 Sample Dissolution .............................. 65
3.5.3 Chemical Extraction of Metals from Organic
Matrices ........................................ 65
3.5.4 Dry Ashing without Retaining Aids ............... 66
3.5.5 Dry Ashing with Retaining Aids .................. 69
3.5.6 Acid Digestion Using Microwave Oven ............. 69
3.5.7 Oxygen Bomb Flask Combustion (Low Pressure) ..... 71
3.5.8 High Pressure Oxygen Combustion ................. 72
3.5.9 Sample Preparation Using Fusion Methods ......... 73
3.5.10 Analysis Using Slurry Solution Method ........... 74
3.5.11 Sample Preparation Using Leaching Method ........ 75
3.5.12 Sample Preparation Using a UV Digester .......... 75
3.6 Non-Spectral Corrections Using ICP-OES ................. 76
3.6.1 Effect of Solvents on ICP-OES ................... 76
3.6.2 Effect of Viscosity on Signal Response .......... 77
3.6.3 Comparison of Nebulisation Efficiency of
Solvents Using ICP-OES .......................... 78
3.6.4 Choice of Carrier Liquid ........................ 80
3.7 Methodology of Measurement ............................. 81
3.7.1 Choice of Standard Materials .................... 82
3.7.2 Quantitative Analysis Using Calibration Graph
Method .......................................... 82
3.7.3 Quantitative Analysis Using Standard Addition
Method .......................................... 85
3.7.4 Quantitative Analysis Using Internal Standard
Method .......................................... 87
3.7.5 Quantitative Analysis Using Matrix Matching
Method .......................................... 88
3.7.6 Quantitative Analysis Using Flow Injection
Technique ....................................... 89
3.8 Validation of an Analytical Method ..................... 90
3.8.1 Method Validation of Analysis of Organic
Matrices ........................................ 91
3.9 Control and Range Charts ............................... 99
3.10 Brief Outline of Measurement Uncertainty .............. 101
References ................................................. 105
4 Analysis of Plastics, Fibres and Textiles for Metals
Content Using ICP-OES ...................................... 107
4.1 A Brief History of Natural and Synthetic Plastic
Materials ............................................. 107
4.2 A Brief History of Chemistry of Plastics .............. 109
4.3 Chemical Structure of Plastics ........................ 110
4.4 Polymerization Process of Plastics .................... 111
4.4.1 Polymerisation by Addition Reactions ........... 112
4.4.2 Polymerisation by Condensation Reactions ....... 112
4.5 Additives in Plastics ................................. 113
4.6 Methods of Sample Preparation for Metal Content of
Plastics, Fibres and Textiles ......................... 115
4.6.1 Sample Preparation Using Dissolution Method .... 115
4.6.2 Sample Preparation Using Dry Ashing Methods .... 117
4.6.3 Sample Preparation Using Microwave Acid
Digestion Method ............................... 119
4.6.4 Sample Preparation Using Oxygen Bomb
Combustion Method .............................. 121
4.7 Comparative Study of Methods of Analysis of Plastic
Samples for Metals Content ............................ 121
4.8 Study of Leaching of Metals from Plastics ............. 123
4.8.1 Study of Leaching of Metals from Children's
Toys ........................................... 124
4.9 Analysis for Toxic Metals in Plastics and
Non-Electrical Additives Used in Electrical and
Electronic Components as Required by RoHS ............. 125
4.9.1 Method for Metal Analysis of Plastics and
Non-Electrical Additives Used in Electrical
and Electronic Products ........................ 127
4.10 Conclusion ............................................ 131
References ................................................. 132
5 Metal Analysis of Virgin and Crude Petroleum Products ...... 133
5.1 Introduction .......................................... 133
5.2 Brief Introduction to Refining Process in the
Petroleum Industry .................................... 133
5.3 Metals in Crude Oils and Petroleum Products ........... 134
5.4 Requirements for the Determination of Metal Content
in Virgin and Crude Oils .............................. 135
5.5 Wear Metals and Metal Contaminants in Lubricating
Oils .................................................. 138
5.6 Brief Outline of the Determination of Metals in
Organic Materials Using Atomic Spectroscopy Methods ... 139
5.7 Application of Atomic Spectroscopic Techniques in
the Analysis of Virgin and Wear Oils for Metals
Content ............................................... 140
5.7.1 Choice of Solvents Suitable for Metal
Analysis of Crude and Lubricating Oils Using
ICP-OES ........................................ 141
5.7.2 Selection of Representative Samples in the
Study of Metal Analysis of High Viscosity and
Low Viscosity Oil Blends ....................... 141
5.7.3 Physical Properties of Selected Solvents for
Dissolving High Viscosity and Low Viscosity
Oils for Metal Analysis ........................ 142
5.7.4 Methods of Sample Preparation for Metal
Analysis of High Viscosity and Low Viscosity
Oil Blends ..................................... 142
5.7.5 Long-Term Study of Metal Analysis Using
Kerosene, Teralin and Decalin Solvents Using
ICP-OES ........................................ 143
5.7.6 Comparative Study of Non-Destructive Methods
of Analysis of Metals 'Spiked' in High
Viscosity and Low Viscosity Oil Blends Using
ICP-OES ........................................ 144
5.8 Analysis of Type С and D Fractions for Metal Content
Using Dry Ashing Method ............................... 149
5.9 Analysis of 'Metal Spiked' Oil Blends Using
Microwave Acid Digestion for Metals Content ........... 150
5.10 Analysis of 'Metal Spiked' Oil Blends Using High
Pressure Oxygen Combustion for Metals Content ......... 152
5.11 Comparative Study of Analysis of Trace Levels of
Toxic Metals Using Microwave Acid Digestion and
Oxygen Bomb Combustion ................................ 153
5.11.1 Conclusion to Trace Analysis of Toxic Metals
in Oil Products ................................ 155
5.12 Extraction Method for the Determination of Metals of
High Viscosity and Low Viscosity Oil Blends ........... 155
5.13 Analysis of Old Lubricating Oil for Total Metal
Content Using a Slurry Method with Internal Standard .. 156
5.14 Conclusion ............................................ 158
References ................................................. 160
6 Metal Analysis of Structural Adhesives ..................... 161
6.1 Introduction .......................................... 161
6.2 Setting and Curing of Adhesives ....................... 162
6.3 Introduction to Modern Synthetic Adhesives ............ 162
6.3.1 Cyanoacrylate Adhesives ........................ 162
6.3.2 Anaerobic and Acrylic Adhesives ................ 163
6.3.3 Epoxy Structural Adhesives ..................... 165
6.3.4 Phenolic Adhesives ............................. 167
6.3.5 Polyurethane Adhesives ......................... 167
6.4 Metal Salts and Concomitant Metals in Adhesives ....... 168
6.5 Metals Associated with Cyanoacrylate Adhesives ........ 169
6.6 Non-Destructive Methods of Analysis for Metals
Content in Cyanoacrylate Adhesives .................... 170
6.6.1 General Method ................................. 170
6.6.2 Standard Addition Method ....................... 171
6.6.3 Internal Standard Method ....................... 171
6.7 Destructive Methods of Analysis for Metals Content
in Cyanoacrylate Adhesives ............................ 172
6.7.1 Sample Preparation Using Ashing Method ......... 173
6.7.2 Sample Preparation Using Microwave Acid
Digestion ...................................... 174
6.7.3 Sample Preparation Using Oxygen Bomb
Combustion ..................................... 174
6.8 Conclusion to Analysis of Cyanoacrylate Products ...... 175
6.9 Metals Associated with Anaerobic Adhesives ............ 176
6.10 Destructive Methods of Sample Preparation for Metals
Content in Anaerobic Adhesives ........................ 177
6.10.1 Ashing Method of Type A and Type В Anaerobic
Adhesives ..................................... 177
6.10.2 Sample Preparation of Anaerobic Adhesives
Using Microwave Acid Digestion ................ 178
6.10.3 Sample Preparation of Anaerobic Adhesive
Using Oxygen Bomb Combustion .................. 180
6.10.4 Conclusion to Analysis of Anaerobic
Adhesives ..................................... 180
6.11 Metal Analysis of Chemical Raw Materials Used to
Manufacture Anaerobic Adhesives ....................... 181
6.11.1 Column Extraction of Metal from Liquid
Monomers ....................................... 181
6.12 Analysis of Metal Salt Content Dissolved in Aerosol
Solvent(s) ............................................ 182
6.12.1 Sample Preparation and Analysis of Metals in
Aerosol ........................................ 183
6.13 A Study of the Effects of Anaerobic Adhesives on
Metallic Substrates ................................... 183
6.14 Metals Associated with Epoxy Adhesives ................ 186
6.14.1 Composition of Epoxy Adhesives ................. 187
6.14.2 Preparation of Epoxy Adhesive 'Spiked' with
Ge(AcAc)BF4 .................................... 187
6.14.3 Determination of the Concentration of
Ge(AcAc)BF4 in Epoxy Adhesives Using Non-
Destructive Methods ............................ 188
6.14.4 Determination of the Concentration of
Ge(AcAc)BF4 in Epoxy Adhesives Using
Destructive Methods ............................ 190
6.14.5 Conclusion of Metal Analysis of Epoxy
Adhesives ...................................... 192
6.15 Metals Associated with Phenolic Adhesives ............. 193
6.15.1 Preparation of Typical Phenolic Adhesives
Containing Calcium and Copper Sulphonate
Salts .......................................... 193
6.15.2 Non-Destructive Methods of Analysis of
Phenolic Adhesives ............................. 194
6.16 Metals Associated with Polyurethane Adhesives ......... 194
6.16.1 Preparation and Analysis of Polyurethane
Adhesives Containing Organometallic Catalysts .. 195
6.17 Conclusion to Metal Analysis of Phenolic and
Polyurethane Adhesives ................................ 197
References ................................................. 198
7 Hyphenated and Miscellaneous Techniques Used with
ICP-OES .................................................... 199
7.1 Introduction .......................................... 199
7.2 Coupling of Flow Injection Analysis with ICP-OES ...... 200
7.2.1 Theory of Flow Injection ....................... 201
7.2.2 Configuration of ICP-OES/FIA System ............ 202
7.2.3 Signal Acquisition and Data Management ......... 203
7.2.4 Reproducibility of Measurements Using
ICP-OES/FIA .................................... 204
7.2.5 Dispersion and Diffusion of 'Sample Plug' in
a Carrier Stream ............................... 205
7.2.6 Metal Analysis of Organic Compounds Using
ICP-OES-FIA .................................... 206
7.2.7 Effect of Loop Size on Signal Response ......... 207
7.2.8 Comparative Measurements of Peak Height and
Peak Area ...................................... 208
7.2.9 Effect of Viscosity Using ICP-OES/FIA .......... 209
7.2.10 A Study of Solvent Effects Using ICP-OES/FIA ... 210
7.2.11 Determination of Limit of Detection and
Quantification ................................. 210
7.2.12 Conclusions of Analysis Using ICP-OES-FIA ...... 211
7.3 Use of Internal Standard(s) with ICP-OES .............. 213
7.3.1 Conclusion to Internal Standard(s) Study ....... 217
7.4 Coupling of Ion Chromatography with ICP-OES ........... 218
7.4.1 Preconcentration of Metals Using Ion
Chromatography ................................. 220
7.4.2 Analysis of Lanthanide and Transition Metals
with ICP-OESAC ................................. 221
7.5 Coupling of Gas Chromatography with ICP-OES or
Atomic Emission Detector ............................. 222
7.6 Metal Analysis Using ICP-OES Coupled with Electro-
Thermal Vaporisation .................................. 224
7.7 Surface Analysis Using Laser Ablation with ICP-OES .... 226
7.8 Determination of Thickener Content of Paints,
Pharmaceutical Products and Adhesives Using ICP-OES ... 227
7.9 Metal Analysis of Metallo-Pharmaceutical Products ..... 230
7.9.1 Metallic Type Antibiotic Drugs ................. 233
7.9.2 Platinum and Palladium Drugs for Cancer
Treatments ..................................... 234
7.10 Metal Analysis of Infusion and Dialysis and
Bio-Monitoring Solutions .............................. 235
7.11 Organometallic Compounds .............................. 236
7.12 Metals and Metalloid Analysis in Support of Forensic
Science ............................................... 237
7.13 Non-Prescription Nutritional Dietary Supplements ...... 239
7.14 Trace Metal Analysis of Foods ......................... 244
7.14.1 General Methods of Metal Analysis of Foods ..... 244
7.14.2 Conclusion to Food Analysis .................... 246
References ................................................. 246
Index ......................................................... 249
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