Handbook of

X-Ray Spectrometry
Methods and Techniques
edited by
Rene E. Van Grieken
Department of Chemistry
University ofAntwerp
Antwerp, Belgium

Andrzej A. Markowicz
Institute of Physics and Nuclear Techniques
Academy of Mining and Metallurgy
Cracow, Poland

Marcel Dekker, Inc.

New York Basel Hong Kong

Contents

Preface
Contributors
1

X-ray Physics
Andrzej A. Markowicz

I.
II.
III.
IV.
V.
VI.
VII.
VIII.

Introduction
History
General Features
Emission of Continuous Radiation
Emission of Characteristic X-rays
Interaction of Photons with Matter
Intensity of Characteristic X-rays
IUPAC Notation for X-ray Spectroscopy

Appendixes
I. Critical Absorption Wavelengths and Critical Absorption Energies
II. Characteristic X-ray Wavelengths (A) and Energies (keV)
III. Radiative Transition Probabilities
IV. Wavelengths of K Satellite Lines ()
V. Fluorescence Yields and Coster-Kronig Transition Probabilities
VI. Coefficients for Calculating the Photoelectric Absorption
Cross Sections T (Barns/Atom) Via LN-LN Representation

iii
xiii

1
1
1
2
3
8
17
30
33

35
37
49
52
54
59
vii

Contents

VIII

VII.

Coefficients for Calculating the Incoherent Collision

Cross SectionsCTC(Barns/Atom) Via the LN-LN Representation
VIII. Coefficients for Calculating the Coherent Scattering
Cross Sections u R (Barns/Atom) Via the LN-LN Representation
IX. Total Mass Attenuation Coefficients for Low-Energy
Lines
X. Correspondence Between Old Siegbahn and New IUPAC
Notation X-ray Diagram Lines
References
2

Wavelength-Dispersive X-ray Fluorescence

J. A. Heisen and Andrzej Kuczumow

Energy Dispersive X-ray Fluorescence Analysis Using X-ray

Tube Excitation
Joseph M. Jaklevic and Robert D. Giauque

I. Introduction
II. Semiconductor Detectors for X-ray Spectrometry
III. Typical X-ray Tube Excitation Systems for EDXRF
IV. Applications of Tube-Excited EDXRF
V. Summary
References
4

Spectrum Evaluation
Pierre J. M. Van Espen and Koen H. A.

75
78
82
117
134
138
145

151
151
152
168
175
179
179
181

Quantification by XRF Analysis of Infinitely Thick Samples

/ . L. de Vries and Bruno A. R. Vrebos
I.
II.

71
71

Janssens

I. Introduction
IL Fundamental Aspects
III. Spectrum Processing Methods
IV. Background Estimation Methods
V. Simple Net Peak Area Determination
VI. Least-Squares Fitting Using Reference Spectra
VII. Least-Squares Fitting Using Analytical Functions
VIII. Methods Based on the Monte Carlo Technique
IX. Least-Squares Fitting Method
X. Computer Implementation of Various Algorithms
References
5

67
69

75

I. Introduction
II. Fundamentals of Wavelength Dispersion
III. Layout of a Spectrometer
IV. Qualitative and Quantitative Analysis
V. Chemical Shift and Speciation
VI. Instrumentation
References
3

65

Correlation Between Intensities and Concentration

Factors Influencing the Accuracy of the Intensity Measurement

181
182
187
205
213
217
222
254
258
268
291
295
295
300

ix

Contents
III. Remarks on Sample Preparation
IV. Converting Intensities to Concentration
V. Conclusion
References
Suggestions for Further Reading
6

Quantification in XRF Analysis of Intermediate-Thickness Samples

Andrzej A. Markowicz and Rene E. Van Grieken

I. Introduction
II. Emission-Transmission Method
III. Absorption Correction Methods via Scattered Primary Radiation
IV. Quantitation for Intermediate-Thickness Granulr Specimens
References
7

Radioisotope X-ray Analysis

John S. Watt

Synchrotron Radiation-Induced X-ray Emission

Keith W. Jones

I. Introduction
II. Properties of Synchrotron Radiation
III. Description of Synchrotron Facilities
IV. Apparatus for X-ray Microscopy
V. Continuum and Monochromatic Excitation
VI. Quantitation
VII. Sensitivities and Minimum Detection Limits
VIII. Beam-Induced Damage
IX. Applications of SRIXE
X. Tomography
XI. EXAFS and XANES
XII. Future Directions
References
9 Total Reflection XRF
Heinrich Schwenke and Joachim
I.
II.
III.
IV.

339
339
340
344
350
357
359

I. Introduction
II. Basic Equations
III. Radioisotope X-ray Sources and Detectors
IV. X-ray and -y-ray Techniques
V. Choice of X-ray Technique for a Specific Application
VI. Applications
VII. Conclusions
References
8

308
309
336
337
338

359
360
367
377
390
391
407
407
411
411
413
416
418
427
428
432
434
437
443
444
448
449
453

Knoth

Introduction
Physics of Total Reflection of X-rays
Design of Instruments
Analysis of Small Quantities on Reflecting Carriers

453
454
458
463

Contents

V. Surface Analysis
VI. R o l e o f T X R F
References

474
488
488

10

491

Polarized Beam X-ray Fluorescence

Richard W. Ryon and John D. Zahrt

I. Introduction
II. Barkla Systems
III. Bragg Systems
IV. Synchrotron Radiation
V. Results and Examples
VI. Conclusion
Appendix: Crystals That Diffract Selected Characteristic Wavelengths
a t 2 9 = n/2 = 90
References

491
497
506
510
510
511

11 Particle-Induced X-ray Emission Analysis

Willy Maenhaut and Klas G. Malmqvist

517

I.
II.

Introduction
Interactions of Charged Particles with Matter, Characteristic
X-ray Production, and Continuous Photon Background Production
III. Instrumentation
IV. Quantitation, Detection Limits, Accuracy, and Precision
V. Sample Collection and Sample and Specimen Preparation
for PIXE Analysis
VI. Applications
VII. Complementary Ion Beam Analysis Techniques
VIII. Conclusions
References

512
515

517
519
526
538
548
550
565
571
574

12 Electron-Induced X-ray Emission

John A. Small

583

I. Introduction
II. Quantitative Analysis
III. Quantitative Analysis of Thin Specimens
IV. Quantitative Analysis of Particles and Rough Surfaces
V. Spatially Resolved X-ray Analysis
References

583
587
616
621
635
652

13

657

Sample Preparation for XRF

Jasna Injuk and Rene E. Van Grieken

I.
II.
III.
IV.

Introduction
Solid Samples
Fused Specimens
Liquid Samples

657
658
665
669

Contents

xi

V. Biological Samples
VI. Atmospheric Particles
VII. Sample Support Materials
References

676
682
685
687

Index

693