Starting from fundamentals and moving through a thorough
discussion of equipment, methods, and techniques, the Handbook
of Laser-Induced Breakdown Spectroscopy provides a unique
reference source that will be of value for many years to come for
this important new analysis method. The authors, with a total
of over 60 years of experience in the LIBS method, use a
combination of tutorial discussions ranging from basic principles
up to more advanced descriptions along with extensive figures and
photographs to clearly explain topics addressed in the text. In
this second edition, chapters on the use of statistical analysis
and advances in detection of weapons of mass destruction have been
added. Tables of data related to analysis with LIBS have been
updated.

The Handbook of Laser-Induced Breakdown Spectroscopy, Second
Edition:

* provides a thorough but understandable discussion of the basic
principles of the method based on atomic emission spectroscopy,
including recently available data leading to better
characterization of the LIBS plasma;

* presents a discussion of the many advantages of the method
along with limitations, to provide the reader a balanced overview
of capabilities of the method;

* describes LIBS instrumentation ranging from basic set-ups to
more advanced configurations;

* presents a comprehensive discussion of the different types of
components (laser, spectrometers, detectors) that can be used for
LIBS apparatuses along with suggestions for their use, as well as
an up-to-date treatment of the newest advances and capabilities of
LIBS instruments;

* presents the analytical capabilities of the method in terms of
detection limits, accuracy, and precision of measurements for a
variety of different sample types;

* discusses methods of sampling different media such as gases,
liquids, and solids;

* presents an overview of some real-world applications of the
method, with new emphasis on sampling of biologically and
physically dangerous materials;

* provides an up-to-date list of references to LIBS literature
along with the latest detection limits and a unique list of element
detection limits using a uniform analysis method;

* provides annotated examples of LIBS spectra which can serve as
references for the general reader and will be especially useful for
those starting out in the field.

David A. Cremers, Applied Research Associates Inc, Albuquerque, NM, USA

Leon J. Radziemski , Tucson, AZ, USA

Starting from fundamentals and moving through a thorough discussion of equipment, methods, and techniques, the Handbook of Laser-Induced Breakdown Spectroscopy provides a unique reference source that will be of value for many years to come for this important new analysis method. The authors, with a total of over 60 years of experience in the LIBS method, use a combination of tutorial discussions ranging from basic principles up to more advanced descriptions along with extensive figures and photographs to clearly explain topics addressed in the text. In this second edition, chapters on the use of statistical analysis and advances in detection of weapons of mass destruction have been added. Tables of data related to analysis with LIBS have been updated.

The Handbook of Laser-Induced Breakdown Spectroscopy, Second Edition:

• provides a thorough but understandable discussion of the basic principles of the method based on atomic emission spectroscopy, including recently available data leading to better characterization of the LIBS plasma;
• presents a discussion of the many advantages of the method along with limitations, to provide the reader a balanced overview of capabilities of the method;
• describes LIBS instrumentation ranging from basic set-ups to more advanced configurations;
• presents a comprehensive discussion of the different types of components (laser, spectrometers, detectors) that can be used for LIBS apparatuses along with suggestions for their use, as well as an up-to-date treatment of the newest advances and capabilities of LIBS instruments;
• presents the analytical capabilities of the method in terms of detection limits, accuracy, and precision of measurements for a variety of different sample types;
• discusses methods of sampling different media such as gases, liquids, and solids;
• presents an overview of some real-world applications of the method, with new emphasis on sampling of biologically and physically dangerous materials;
• provides an up-to-date list of references to LIBS literature along with the latest detection limits and a unique list of element detection limits using a uniform analysis method;
• provides annotated examples of LIBS spectra which can serve as references for the general reader and will be especially useful for those starting out in the field.

Preface xi

Acronyms, Constants, and Symbols xv

1 Introduction 1

1.1 Atomic Optical Emission Spectrochemistry (OES) 1

1.1.1 Conventional OES 1

1.1.2 Laser OES 1

1.2 Laser-Induced Breakdown Spectroscopy (LIBS) 2

1.3 LIBS History 1960-1980 7

1.4 LIBS History 1981-1990 9

1.5 LIBS History 1991-2000 11

1.6 LIBS History 2001-2012 14

References 18

2 Basics of the LIBS Plasma 29

2.1 LIBS Plasma Fundamentals 29

2.1.1 Spectral Lines and Line Profiles 32

2.1.2 Determining Electron Densities from Spectral Line Widths 34

2.1.3 Plasma Opacity 37

2.1.4 Temperature and Thermodynamic Equilibrium 38

2.2 Laser-Induced Breakdown 46

2.2.1 Breakdown in Gases 46

2.2.2 Post-Breakdown Phenomena in Gases 48

2.2.3 Breakdown in and on Solids, Aerosols, and Liquids 48

2.2.4 Post-Breakdown Phenomena on Solid Surfaces 50

2.3 Laser Ablation from Surfaces and Aerosols 53

2.4 Nanosecond and Femtosecond Double- or Multiple-Pulse LIBS 58

2.5 Summary 63

2.6 Problems 63

References 64

3 LIBS Apparatus Fundamentals 69

3.1 Basic LIBS Apparatus 69

3.2 Lasers 70

3.2.1 Laser Fundamentals 70

3.2.2 Types of Lasers 72

3.2.3 Properties of Laser Light Important for LIBS 76

3.2.4 Generation of Additional Wavelengths 78

3.2.5 Double-Pulse Operation 78

3.3 Optical Systems 80

3.3.1 Focusing and Light Collection 80

3.3.2 Lenses 82

3.3.3 Fiber Optic Cables 82

3.4 Methods of Spectral Resolution 86

3.4.1 Introduction 86

3.4.2 Spectral Resolution Devices 88

3.5 Detectors 102

3.6 Detection System Calibrations 109

3.6.1 Wavelength Calibration 109

3.6.2 Spectral Response Calibration 110

3.7 Timing Considerations 114

3.8 Methods of LIBS Deployment 115

3.9 Problems 117

References 118

4 LIBS Analytical Figures of Merit and Calibration 123

4.1 Introduction 123

4.2 Basics of a LIBS Measurement 123

4.3 Precision 129

4.4 Calibration 131

4.4.1 Calibration Curves 131

4.4.2 Calibration Standards 138

4.4.3 Calibration-Free LIBS 140

4.5 Detection Limit 144

4.6 Accuracy 144

4.7 Problems 146

References 148

References for Detection Limits 150

5 Qualitative LIBS Analysis 151

5.1 Introduction 151

5.2 Identifying Elements 151

5.3 Material Identification 156

5.4 Process Monitoring 159

5.4.1 Introduction 159

5.4.2 Experimental 162

5.4.3 Results 163

5.4.4 Conclusions 169

5.5 Material Sorting/Distingu…