Handbook of Laser-Induced Breakdown Spectroscopy (eBook)

David A. Cremers, Applied Research Associates Inc, Albuquerque, NM, USA Leon J. Radziemski , Tucson, AZ, USA

Preface xi

Acronyms, Constants, and Symbols xv

1 Introduction 1

1.1 Atomic Optical Emission Spectrochemistry (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

2.2 Laser-Induced Breakdown 46

2.3 Laser Ablation from Surfaces and Aerosols 53

2.4 Nanosecond and Femtosecond Double- or Multiple-Pulse LIBS58

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

3.3 Optical Systems 80

3.4 Methods of Spectral Resolution 86

3.5 Detectors 102

3.6 Detection System Calibrations 109

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 Calibration123

4.1 Introduction 123

4.2 Basics of a LIBS Measurement 123

4.3 Precision 129

4.4 Calibration 131

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

5.5 Material Sorting/Distinguishing 169

5.6 Site Screening Using LIBS 177

5.7 Semiquantitative Analysis 178

5.8 Problems 180

References 182

6 Quantitative LIBS Analysis 185

6.1 Introduction 185

6.2 Effects of Sampling Geometry 185

6.3 Other Sampling Considerations 189

6.4 Incomplete Vaporization and Ablation Stoichiometry 193

6.5 Use of Internal Standardization 194

6.6 Chemical Matrix Effects 196

6.7 Example of LIBS Measurement: Impurities inLithium-Containing Solutions 198

6.8 Example of LIBS Measurement: Detection of Materials onSwipes 206

6.9 Reported Figures of Merit for LIBS Measurements andComparison with Standard Methods 211

6.10 Enhancing Quantitative Analysis via Sophisticated SignalProcessing 219

6.11 Conclusions 220

References 221

7 Chemometric Analysis in LIBS 223

7.1 Introduction 223

7.2 Chemometric Terms 227

7.3 Chemometric Analysis/Model Development 232

7.4 Summary 241

References 241

8 Remote LIBS Measurements 257

8.1 Introduction 257

8.2 Conventional Open-Path LIBS 259

8.3 Standoff LIBS Using Femtosecond Pulses 270

8.4 Fiber Optic LIBS 276

References 284

9 Selected LIBS Applications 289

9.1 Introduction 289

9.2 LIBS and the CBRNE Threats 289

9.3 LIBS Analysis of Liquids and Solids in Liquids 297

9.4 Transportable LIBS Instrument for Stand-off Analysis 303

9.5 LIBS for Space Applications 313

References 325

A Safety Considerations in LIBS 333

B Major LIBS References 337

C Detection Limits from the Literature 341

D Examples of LIBS Spectra 377

E Solutions to Problems 387

Index 397