Wilson & Wilson's

COMPREHENSIVE ANALYTICAL CHEMISTRY

VOLUME XXX

SPECTROCHEMICAL TRACE ANALYSIS FOR

METALS AND METALLOIDS by

R. LOBINSKI and Z. MARCZENKO

1996 ELSEVIER

AMSTERDAM - LAUSANNE - OXFORD - NEW YORK - SHANNON - TOKYO

Contents

Editor's Preface xxi Authors' Preface xxiii List of Abbreviations xxvii

Part I. General Chapter 1. Sampling 3

References 4

Chapter 2. Decomposition Idissolution techniques 5 2.1. Acid attack 5

2.1.1. Acids 5 2.1.2. Dissolution techniques 8

2.2. Fusion 10 2.2.1. Alkaline fusion 10 2.2.2. Acidic fusion 11 2.2.3. Reductive fusion (fire assay) 11

2.3. Decomposition in gas streams 13 2.3.1. Oxidation (dry ashing) 13 2.3.2. Decomposition with halogens 14

References 14

Chapter 3. Separation and preconcentration 17 3.1. Solvent extraction 18

3.1.1. Extractants and extraction solvents 18 3.1.2. Separation oftraces 20 3.1.3. Separation ofthe matrix 22 3.1.4. Practical aspects 22

3.2. Precipitation and coprecipitation 24 3.2.1. Coprecipitation oftraces 24 3.2.2. Precipitation of macrocomponents 26

3.3. Volatilization 27 3.3.1. Volatilization of trace elements 27

ix

3.3.2. Volatilization of macrocomponents 29 3.4. Sorption 30

3.4.1. Sorption via physical interactions 30 3.4.2. Simple ion-exchange 31 3.4.3. Chelating sorbents 32 3.4.4. Practical aspects 33

3.5. Chromatographie techniques 33 3.5.1. Gas chromatography 34 3.5.2. Liquid chromatography 35 3.5.3. Supercritical fluid chromatography 38

3.6. Electrochemical methods 38 References 39

Chapter 4. Spectrometric determination techniques 45 4.1. Basic coneepts 45 4.2. Sample and sample introduetion 47

4.2.1. Gaseous samples 47 4.2.2. Liquids and Solutions 48 4.2.3. Slurries 50 4.2.4. Solid samples 51

4.3. Spectrophotometry 53 4.3.1. Sample and colour Systems 53 4.3.2. Instrumentation 54 4.3.3. Measurement and calibration 55 4.3.4. Analytical characteristics 56

4.4. Atomic absorption spectrometry (AAS) 57 4.4.1. General 57 4.4.2. Flame AAS 59 4.4.3. Graphite furnace AAS 62 4.4.4. Quartz furnace AAS 66

4.5. Atomic emission spectrometry 66 4.5.1. Sample and sample introduetion 67 4.5.2. Flame AES 67 4.5.3. Inductively coupled plasma AES 68 4.5.4. Other atomic emission techniques 73

4.6. Fluorescence spectrometry 73 4.6.1. Molecular fluorescence spectrometry (spectrofluorimetry) 74 4.6.2. Atomic fluorescence spectrometry (AFS) 75 4.6.3. X-ray fluorescence spectrometry (XRF) 77

4.7. Activation spectrometry 82 4.7.1. Irradiation and measurement 82 4.7.2. Analytical characteristics 83

4.8. Mass spectrometry 85 4.8.1. Inductively coupled plasma mass spectrometry 85 4.8.2. Other MS techniques 91

References

x

Chapter 5. Quantification techniques 105 5.1. Calibration graph 105 5.2. The method of Standard additions 105 5.3. Internal standardization 106 5.4. Isotope dilution analysis 107 References 108

Chapter 6. Speciation analysis 109 6.1. Instrumental approaches 110

6.1.1. Gas chromatography-atomic absorption spectrometry . . 110 6.1.2. Gas chromatography-atomic emission spectrometry . . . 111 6.1.3. Gas chromatography-mass spectrometry 111 6.1.4. Liquid chromatography-mass spectrometry 112 6.1.5. Supercritical fluid chromatography-mass spectrometry . 112

6.2. Sample preparation for speciation analysis 113 References 114

Chapter 7. Flow-injection analysis 115 7.1. General purpose FI manifold 115 7.2. Liquid-liquid extraction 117 7.3. Liquid-gas extraction 117 7.4. Sorption 118 7.5. Precipitation 119 7.6. Microwave digestion 119 7.7. Speciation analysis 120 7.8. Calibration 121 References 121

Chapter 8. Quality assurance in trace analysis 123 8.1. Standard Solutions 123

8.1.1. Aqueous Standards 123 8.1.2. Non-aqueous Standards 124

8.2. Contamination 124 8.3. Losses 126 8.4. Accuracy verification 127 References 128

PART II. Multielement Trace Analysis of Real Samples

Chapter 9. Environmental and geological materials 133 9.1. Air 133

9.1.1. Sampling and sample handling 134 9.1.2. Determination techniques 135

9.2. Water 136 9.2.1. Sampling and storage 138 9.2.2. Preconcentration 140 9.2.3. Determination techniques 143

xi

9.3. Rocks, soils and Sediments 151 9.3.1. Sampling and physical sample preparation 152 9.3.2. Sample decomposition 152 9.3.3. Determination techniques 156

9.4. Ashes, slags and solid wastes 165 9.5. Speciation 166

9.5.1. Water 166 9.5.2. Sediments and soils 169

9.6. Quality control and assurance 171 9.6.1. Contamination 171 9.6.2. Losses 172 9.6.3. Reference materials 172

References 174

Chapter 10. Biological and clinical materials 187 10.1. General considerations 187

10.1.1. Sampling and storage 187 10.1.2. Direct analysis 188 10.1.3. Digestion 188 10.1.4. Separation and/or preconcentration 188 10.1.5. Determination 188 10.1.6. Microanalysis 189

10.2. Biomedical materials 189 10.2.1. Body fluids 190 10.2.2. Tissues 194

10.3. Ecological materials 196 10.3.1. Plant materials 196 10.3.2. Animal tissues 200

10.4. Foodstuffs 204 10.5. Speciation 207 10.6. Quality assurance 208 References 212

Chapter 11. Inorganic industrial materials 223 11.1. Metals and alloys 223

11.1.1. Ferrous metals and alloys 224 11.1.2. Non-ferrous metals and alloys 227 11.1.3. Refractory metals and alloys 232 11.1.4. Precious metals 235

11.2. Semiconducting materials and related products 237 11.2.1. Semiconducting materials 237 11.2.2. Electronic grade gases and chemicals 242

11.3. Analysis of ceramics and their basic products 242 11.3.1. General analytical approaches 242 11.3.2. Industrial ceramics 246 11.3.3. Catalysts 248

XU

11.4. Nuclear materials 243 11.5. Quality control and assurance 252 References 253

Chapter 12. Organic industrial materials 261 12.1. Petroleum and petroleum products 261

12.1.1. Sample handling prior to measurement 261 12.1.2. Determination techniques 263

12.2. Energy-related solid materials 266 12.2.1. Sample handling prior to measurement 266 12.2.2. Determination techniques 267

12.3. Polymers 268 12.4. Speciation analysisof fossil fuels 269 12.5. Quality assurance 269 References 272

Part III. Determinat ion of Individual Elements

Chapter 13. Aluminium 277 13.1. Separation and preconcentration 277 13.2. Determination techniques 278 13.3. Analysis of real samples 279

13.3.1. General considerations 281 13.3.2. Water, dialysis fluids and pharmaceutical samples . . . 281 13.3.3. Biological samples 283

13.4. Speciation 285 References 288

Chapter 14. Antimony 293 14.1. Separation and preconcentration 293 14.2. Determination techniques 295 14.3. Analysis of real samples 297 References 299

Chapter 15. Arsenic 303 15.1. Separation and Preconcentration 303 15.2. Determination techniques 306 15.3. Analysis of real samples 308

15.3.1. Environmental and geological materials 308 15.3.2. Biological samples 309 15.3.3. Industrial materials 315

15.4. Speciation 315 References 321

Chapter 16. Barium 329 16.1. Analytical techniques 329

xiii

16.2. Analysis of real samples 331 References 332

Chapterl7. Beryllium 333 17.1. Analytical techniques 333 17.2. Analysis of real samples 335 References 337

Chapter 18. Bismuth 339 18.1. Separation and preconcentration 339 18.2. Determination techniques 340 18.3. Analysis of real samples 341 References 342

Chapter 19. Boron . . . . ; 347

19.1. Separation and preconcentration 348 19.2. Determination techniques 349 19.3. Analysis of real samples 352 References 357

Chapter 20. Cadmium 361 20.1. Separation and preconcentration 361 20.2. Determination techniques 362 20.3. Analysis of real samples 363 20.4. Speciation 374 References 374

Chapter 21. Caesium 377 21.1. Separation and preconcentration 377 21.2. Determination techniques 378 21.3. Analysis of real samples 379 References 380

Chapter 22. Calcium and magnesium 383 22.1. Determination 383 References 385

Chapter 23. Chromium 387 23.1. Separation and preconcentration 387 23.2. Determination techniques 389 23.3. Speciation 391 23.4. Analysis of real samples . . . 393 References 398

Chapter 24. Cobalt 405 24.1. Separation and preconcentration 405

xiv

24.2. Determination techniques 406 24.3. Analysis of real samples 408 References 411

Chapter 25. Copper 413 25.1. Separation and preconcentration 413 25.2. Determination techniques 414 25.3. Analysis of real samples 416 25.4 Speciation 419 References 422

Chapter 26. Gallium 427 26.1. Analytical techniques 427 26.2. Analysis of real samples 429 References 430

Chapter 27. Germanium 433 27.1. Separation and preconcentration 433 27.2. Determination techniques 434 27.3. Analysis of real samples 436 References 436

Chapter 28. Gold 439 28.1. Separation and preconcentration 440 28.2. Determination techniques 441 28.3. Analysis of real samples 443

28.3.1. Geological materials 443 28.3.2. Other materials 447 28.3.3. Accuracy considerations 450

References 451

Chapter 29. Hafnium 455 29.1. Determination 455 References 457

Chapter 30. Indium 459 30.1. Separation and preconcentration 459 30.2. Determination techniques 460 30.3. Analysis of real samples 461 References 461

Chapter 31. Iridium 465 31.1. Separation and preconcentration 465 31.2. Determination techniques 466 31.3. Analysis of real samples 467 References 470

xv

Chapter 32. Iron 473 32.1. Analytical techniques 473 32:2. Analysis of real samples 476 32.3. Speciation 476 References 476

Chapter 33. Lead 481 33.1. Separation and preconcentration 481 33.2. Determination techniques 483 33.3. Analysis of real samples 485

33.3.1. Environmental and geological materials 485 33.3.2. Biological materials 487 33.3.3. Industrial materials 488

33.4. Speciation oforganolead Compounds 489 33.4.1. Instrumental approaches 489 33.4.2. Analysis of real samples 490

References 493

Chapter 34. Lithium 501 34.1. Separation and preconcentration 501 34.2. Determination techniques 502 34.3. Analysis of real samples 504 References 505

Chapter 35. Manganese 509 35.1. Separation and preconcentration 509 35.2. Determination techniques 510 35.3. Analysis of real samples 511 References 514

Chapter 36. Mercury 517 36.1. Separation and preconcentration 517

36.1.1. Volatilization 518 36.1.2. Other methods 519

36.2. Determination techniques 519 36.3. Analysis of real samples for total mercury content 522

36.3.1. Environmental and geological materials . . : 522 36.3.2. Biological materials 525 36.3.3. Industrial materials 526

36.4. Speciation 529 36.4.1. Analytical techniques 529 36.4.2. Speciation analysis of real samples 535

References 536

Chapter 37. Molybdenum 543 37.1. Separation and preconcentration 543

xvi

37.2. Determination techniques 544 37.3. Analysis of real samples 547 References 551

Chapter 38. Nickel 555 38.1. Separation and preconcentration 555 38.2. Determination techniques 556 38.3. Analysis of real samples 558 References 563

Chapter 39. Niobium 567 39.1. Separation and preconcentration 567 39.2. Determination techniques 568 39.3. Analysis of real samples 569 References 569

Chapter 40. Osmium 571 40.1. Separation 571 40.2. Determination techniques 572 40.3. Analysis of real samples 573 References 576

Chapter 41. Palladium 579 41.1. Separation and preconcentration 579 41.2. Determination techniques 580 41.3. Analysis of real samples 581 References 586

Chapter 42. Platinum 589 42.1. Separation and preconcentration 589 42.2. Determination techniques 590 42.3. Analysis of real samples 592 References 598

Chapter 43. Rare earth elements 601 43.1. Separation and preconcentration 602 43.2. Determination techniques 604 43.3. Analysis of real samples 611 References 617

Chapter 44. Rhenium 623 44.1. Analytical techniques 623 44.2. Analysis of real samples 625 References 627

Chapter 45. Rhodium 629 45.1. Separation and preconcentration 629 45.2. Determination techniques 630 45.3. Analysis of real samples 631 References 633

xvii

Chapter 46. Rubidium 635 46.1. Analytical techniques 635 46.2. Analysis of real samples 637 References 637

Chapter 47. Ruthenium 639 47.1. Separation and preconcentration 639 47.2. Determination techniques 640 47.3. Analysis of real samples 642 References 643

Chapter 48. Scandium 645 48.1. Separation and preconcentration 645 48.2. Determination techniques 646 48.3. Analysis of real samples 648 References 646

Chapter 49. Selenium 649 49.1. Separation and preconcentration 649 49.2. Determination techniques 651 49.3. Analysis of real samples 653

49.3.1. Environmental and geological materials 654 49.3.2. Biological materials 654 49.3.3. Industrial samples 661

49.4. Speciation 661 References 663

Chapter 50. Silicon 671 50.1. Analytical techniques 671 50.2. Analysis of real samples 673 References 674

Chapter 51. Silver 677 51.1. Separation and preconcentration 677 51.2. Determination techniques 678 51.3. Analysis of real samples 679 References 685

Chapter 52. Sodium and potassium 687 52.1. Analytical techniques 687 52.2. Analysis of real samples 688 References 689

Chapter 53. Strontium. 691 53.1. Separation and preconcentration 691 53.2. Determination techniques 692

xviii

53.3. Analysis of real samples 693 References 693

Chapter 54. Tantalum 695 54.1. Separation and preconcentration 695 54.2. Determination 696 References 698

Chapter 55. Technetium 699 55.1. Separation and preconcentration 699 55.2. Determination techniques 700 55.3. Analysis of real samples 701 References 704

Chapter 56. Tellurium 707 56.1. Separation and preconcentration 707 56.2. Determination techniques 708 56.3. Analysis of real samples 709 References 711

Chapter 57. Thallium 713 57.1. Separation and preconcentration 713 57.2. Determination techniques 714 57.3. Analysis of real samples 716 References 718

Chapter 58. Thorium 721 58.1. Separation and preconcentration 721 58.2. Determination techniques 722 58.3. Analysis of real samples 724 References 727

Chapter 59. Tin 729 59.1. Separation and preconcentration 729 59.2. Determination techniques 730 59.3. Analysis of real samples 732 59.4. Speciation 736

59.4.1. Sample preparation 736 59.4.2. Instrumental techniques 737 59.4.3. Speciation analysis of real samples 738

References 742

Chapter 60. Titanium 747 60.1. Analytical techniques 747 60.2. Analysis of real samples 748 References 749

xix

Chapter 61. Transuranium elements 751 61.1. Separation and preconcentration 751 61.2. Determination techniques 752 61.3. Analysis of environmental samples 753 References 757

Chapter 62. Tungsten 761 62.1. Analytical techniques 761 62.2. Analysis of real samples 763 References 763

Chapter 63. Uranium 765 63.1. Separation and preconcentration 765 63.2. Determination techniques 766 63.3. Analysis of real samples 768 References 773

Chapter 64. Vanadium 777 64.1. Separation and preconcentration 777 64.2. Determination techniques 778 64.3. Analysis of real samples 780 References 784

Chapter 65. Zinc 787 65.1. Analytical techniques 787 65.2. Analysis of real samples 789 References 791

Chapter 66. Zirconium 797 66.1. Separation and preconcentration 797 66.2. Determination techniques 798 66.3. Analysis of real samples 799 References 799

Index 803

xx