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Laser Induced Breakdown Spectroscopy (LIBS)

Concepts, Instrumentation, Data Analysis and Applications, 2 Volume Set

Singh, Vivek K. / Tripathi, Durgesh K. / Deguchi, Yoshihiro / Wang, Zhenzhen (Editor)


1. Edition March 2023
1008 Pages, Hardcover
Wiley & Sons Ltd

ISBN: 978-1-119-75840-2
John Wiley & Sons

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Laser Induced Breakdown Spectroscopy (LIBS)

Essential resource covering the field of LIBS, with respect to its fundamentals, established and novel applications, and future prospects

Laser Induced Breakdown Spectroscopy (LIBS), presents in two comprehensive volumes a thorough discussion of the basic principles of the method, including important recently available data which can lead to a better characterization of the LIBS plasma. This extensive work contains detailed discussions on the lasers, spectrometers, and detectors that can be used for LIBS apparatuses and describes various instrumentation, ranging from basic setups to more advanced configurations.

As a modern resource, the work includes the newest advances and capabilities of LIBS instruments, featuring the recent developments of Dual-Pulse LIBS, Femtosecond LIBS, and Micro-LIBS as well as their applications. Throughout, the contributions discuss the analytical capabilities of the method in terms of detection limits, accuracy, and precision of measurements for a variety of samples. Lastly, an extensive range of applications is presented, including food technology, environmental science, nuclear reactors, nanoscience and nanotechnology, and biological and biomedical developments.

Sample topics covered within the work include:
* iagnostics of laser induced plasma (LIP): LIBS plasma and its characteristics, factors affecting the LIBS plasma, methods of enhancing LIBS sensitivity, and LTE/non-LTE plasmas
* Instrumental developments in LIBS: light collection system and spectral detection systems, handheld LIBS, deep sea LIBS, and industrial sorters and analyzers
* Femtosecond laser ablation: laser-matter interaction, laser absorption, energy transport, ablation mechanisms and threshold, and plasma characterization
* Micro-analysis and LIBS imaging: microjoule laser sources, scaling libs to microjoule energies, micrometer scaling, advanced applications, and future prospects

Spectroscopic and analytical scientists working with LIBS will find this wide-ranging reference immensely helpful in developing LIBS instrumentation and applications. Researchers and students in natural sciences and related programs of study will be able to use the work to acquire foundational knowledge on the method and learn about cutting-edge advancements being made in the field.

Volume 1

Preface xix

Part I Fundamental Aspects of LIBS and Laser-Induced Plasma 1

1 Nanosecond and Femtosecond Laser-Induced Breakdown Spectroscopy: Fundamentals and Applications 3
K. M. Muhammed Shameem, Swetapuspa Soumyashree, P. Madhusudhan, Vinitha Nimma, Rituparna Das, Pranav Bhardwaj, Prashant Kumar and Rajesh K. Kushawaha

1.1 Introduction 3

1.2 LIBS: ns-LIBS and fs-LIBS 5

1.3 Plasma-Plume Dynamics 10

1.4 Filamentation 14

1.5 Signal-Enhancing Strategies in LIBS 17

1.6 Applications 20

1.7 Summary 21

2 Elementary Processes and Emission Spectra in Laser-Induced Plasma 33
V. Gardette, Z. Salajkova, M. Dell'Aglio and A. De Giacomo

2.1 Introduction 33

2.2 Laser-Ablation Mechanism 33

2.3 Plasma Characteristics and Elementary Processes 35

2.4 Plasma in Thermodynamic Equilibrium 37

2.5 Plasma Emission Features 39

2.6 Conclusion 41

3 Diagnostics of Laser-Induced Plasma 45
Charles Ghany, Kyung-Min Lee, Herve K. Sanghapi and Vivek K. Singh

3.1 Introduction 45

3.2 LIBS Plasmas and Its Characteristics 46

3.3 Factors Affecting the LIBS Plasma 49

3.4 Methods of Enhancing LIBS Sensitivity 51

3.5 LTE Plasmas and Non-LTE Plasmas 52

3.6 Laser-Plasma Expansion in Gas and Liquids: Modeling and Validation 54

3.7 Chemistry in Laser Plasmas (Biological, Medical, and Isotopic Applications) 57

3.8 Conclusion 58

4 Double and Multiple Pulse LIBS Techniques 65
Francesco Poggialini, Asia Botto, Beatrice Campanella, Simona Raneri, Vincenzo Palleschi and Stefano Legnaioli

4.1 Introduction 65

4.2 Double-Pulse LIBS: Geometries and Configurations 67

4.3 Signal Enhancement in DP-LIBS: Principles and Theory 77

4.4 Applications of DP-LIBS 80

4.5 Conclusions 83

5 Calibration-Free Laser-Induced Breakdown Spectroscopy 89
Jörg Hermann

5.1 Introduction 89

5.2 Validity Conditions of the Physical Model 90

5.3 Methods of Calibration-Free Measurements 98

5.4 Critical Review of Analytical Performance 107

5.5 Conclusion 115

Part II Molecular LIBS and Instrumentation Developments 123

6 Molecular Species Formation in Laser-Produced Plasma 125
K. M. Muhammed Shameem, Swetapuspa Soumyashree, P. Madhusudhan, Vinitha Nimma, Rituparna Das, Pranav Bhardwaj and Rajesh K. Kushawaha

6.1 Introduction 125

6.2 Atmospheric Contribution in LIBS Spectra 127

6.3 CN and C2 Molecular Formation in LIP 127

6.4 Summary 134

7 Recent Developments in Standoff Laser-Induced Breakdown Spectroscopy 137
Linga Murthy Narlagiri and Venugopal Rao Soma

7.1 Introduction 137

7.2 Laser Systems Used 137

7.3 Instrumentation in Standoff LIBS 138

7.4 Gated and Non-Gated CCDs/Spectrometers 139

7.5 Experimental Setup 139

7.6 Reviews on Standoff LIBS 140

7.7 Studies in Standoff LIBS 140

7.8 Variants in Standoff LIBS 146

7.9 Machine-Learning for Data Analysis in Standoff Mode 149

7.10 Advancements in Standoff LIBS Methods 150

7.11 Ongoing Study at ACRHEM, University of Hyderabad 153

7.12 Conclusions and Outlook 158

8 Nanoparticle-Enhanced Laser-Induced Breakdown Spectroscopy 165
Zita Salajková, Marcella Dell'Aglio, Vincent Gardette and Alessandro De Giacomo

8.1 Introduction 165

8.2 Fundamentals 166

8.3 Applications 174

8.4 Conclusion 179

9 Nanoparticle-Enhanced Laser-Induced Breakdown Spectroscopy for Sensing Applications 183
Linga Murthy Narlagiri and Venugopal Rao Soma

9.1 Introduction 183

9.2 Previous Reviews 183

9.3 Experimental Setup 184

9.4 Enhancement Via Different Conditions 185

9.5 Perspectives on the Mechanism(s) of Enhancement 191

9.6 Variations in NE-LIBS 199

9.7 Beyond NE-LIBS 200

9.8 Further Application of Nanoparticles in LIBS 202

9.9 Ongoing Study in the Lab 203

9.10 Conclusions 204

Part III Data Analysis and Chemometrics in LIBS 211

10 Full-Spectrum Multivariate Analysis of LIBS Data 213
Catherine E. McManus and Nancy J. McMillan

10.1 Introduction 213

10.2 Full-Spectrum Multivariate Analysis 215

10.3 Analysis of Geologic Samples 216

10.4 Identification of Pharmaceuticals 218

10.5 Conclusions 224

11 Chemometrics for Data Analysis 229
Manoj Kumar Gundawar and Rajendhar Junjuri

11.1 Introduction 229

11.2 Data 230

11.3 Machine Learning 231

11.4 Classification of the Data 236

11.5 Conclusion 237

12 Chemometric Processing of LIBS Data 241
J. El Haddad, A. Harhira, E. Képes, J. Vrábel, J. Kaiser and P. Po?ízka

12.1 Introduction 241

12.2 Exploratory Analysis Methods for Visualization 243

12.3 Quantitative Analysis Methods 249

12.4 Classification 254

12.5 Data Preprocessing 257

12.6 Validation and Generalization 261

12.7 Conclusions 268

13 How Chemometrics Allowed the Development of LIBS in the Quantification and Detection of Isotopes: A Case Study of Uranium 277
Carlos A. Rinaldi, Norberto Boggio and Juan Vorobioff

13.1 Introduction 277

13.2 The LIBS Method 278

13.3 Detection and Quantification 279

13.4 Chemometrics Solution 279

13.5 Conclusions 285

14 Application of Multivariate Analysis to the Problem of the Provenance of Gem Stones (Ruby, Sapphire, Emerald, Diamond) 287
Nancy J. McMillan and Catherine E. McManus

14.1 Introduction 287

14.2 Gem Mineral Genesis 289

14.3 Laser-Induced Breakdown Spectroscopy and Multivariate Analysis 293

14.4 Gem Provenance Studies 294

14.5 Conclusions 300

15 Machine Learning in the Context of Laser-Induced Breakdown Spectroscopy 305
E. Képes, J. Vrábel, J. El Haddad, A. Harhira, P. Po?ízka and J. Kaiser

15.1 Introduction 305

15.2 Fundamental Concepts of Machine Learning 306

15.3 Decision Trees and Related Ensemble Methods 307

15.4 Support Vector Machines 311

15.5 Artificial Neural Networks 314

15.6 Unsupervised Learning 318

15.7 Self-Organizing Maps 319

15.8 Concluding Remarks 320

16 Analysis of LIBS Data from Coal and Biomass Using Artificial Intelligence Techniques 331
Carlos E. Romero and Robert De Saro

16.1 Introduction 331

16.2 LIBS Coal and Biomass Laboratory Experimental Results 334

16.3 Application of Artificial Intelligence Techniques to LIBS Spectral Data 337

16.4 Conclusions 349

Part IV Special Topics and Comparison with Other Methods 353

17 Lasing in Optically Pumped Laser-Induced Plasma 355
Lev Nagli, Michael Gaft and Yosef Raichlin

17.1 Introduction 355

17.2 Experimental Setups and Samples 357

17.3 Lasing Effects in a LIP Plume; 13 th Group Elements 360

17.4 Polarization of the LIPLs: the UV-VIS Generation 370

17.5 External Magnetic Field Effects 376

17.6 Fourteenth GROUP Elements LIPL (Ground-State Configuration 4s²np 23P0 , n = 4,5,6) 377

17.7 LIPLs Tunability 379

17.8 Conclusions 382

18 LIBS Analysis of Optical Surfaces and Thin Films 387
Christoph Gerhard and Jörg Hermann

18.1 Introduction 387

18.2 Sensitivity-Improved Calibration-Free LIBS 389

18.3 Analysis of Optical Materials and Surfaces 392

18.4 Elemental Analysis of Thin Films 395

18.5 Conclusion 407

19 LIBS Detection of Rare-Earth Elements and Comparison with Other Techniques 415
Yashashchandra Dwivedi

19.1 Introduction 415

19.2 Importance of Rare Earth 416

19.3 Technological Challenges 417

19.4 Detection of RE Using LIBS 418

19.5 Detection of RE Using Other Techniques 423

20 Marine Biofouling Analysis by Laser-Induced Breakdown Spectroscopy 431
Della Thomas

20.1 Introduction 431

20.2 Biofouling Sample Preparation 431

20.3 Experimental LIBS Setup 432

20.4 Analysis and Discussion 432

20.5 Biomineralization and Elemental Mapping Studies 437

20.6 LIBS Spectra for Biofouling Sample 437

20.7 LIBS Spatial Elemental Mapping 440

20.8 Conclusion 444

21 Hyphenated LIBS Techniques 447
U. K. Adarsh, V. S. Dhanada, Santhosh Chidangil and V. K. Unnikrishnan

21.1 Introduction 447

21.2 Why Hyphenate Spectroscopic Methods? 449

21.2.1 Significance 449

21.2.2 Developmental Strategies 451

21.2.3 Hyphenated LIBS Systems 452

21.3 Conclusion and Future Directions 457

22 Comparison of LIBS with Other Analytical Techniques 461
Muhammad Aslam Baig, Rizwan Ahmed and Zeshan Adeel Umar

22.1 Introduction 461

22.2 Quantitative Analysis by LIBS 462

22.3 Laser-Ablation Time-of-Flight Mass Spectrometry 476

22.4 Conclusion 482

23 Combining Laser-Induced Breakdown Spectroscopy and Raman Spectroscopy: Instrumentation and Applications 487
Vasily N. Lednev

23.1 Introduction 487

23.2 Instrumentation 489

23.3 Applications 502

23.4 Conclusions 520

Acknowledgments 521

References 521

Volume 2

Preface xix

Part V Novel Applications of LIBS 531

24 Application of LIBS to the Analysis of Metals 533
Francesco Poggialini, Asia Botto, Beatrice Campanella, Vincenzo Palleschi, Simona Raneri and Stefano Legnaioli

25 LIBS Analysis of Metals Under Extreme Conditions 551
Mohamed Abdel-Harith and Raghda Hosny El-Saeid

26 LIBS Applications to Liquids and Solids in Liquids 559
Chet R. Bhatt, Daniel Hartzler, Jinesh Jain and Dustin L. McIntyre

27 Coal Analysis by Laser-Induced Breakdown Spectroscopy 581
Shunchun Yao

28 Application of LIBS to Terrestrial Geological Research 593
Giorgio S. Senesi and Russell S. Harmon

29 Plastic Waste Identification Using Laser-Induced Breakdown Spectroscopy 615
Rajendhar Junjuri and Manoj Kumar Gundawar

30 Cultural Heritage Applications of Laser-Induced Breakdown Spectroscopy 623
Duixiong Sun and Yaopeng Ying

31 Nuclear Applications of Laser-Induced Breakdown Spectroscopy 643
Gábor Galbács and Éva Kovács-Széles

32 Applications of Laser-Induced Breakdown Spectroscopy for Trace Detection in Explosives 667
Qianqian Wang and Geer Teng

33 Geochemical Fingerprinting Using Laser-Induced Breakdown Spectroscopy 683
Pengju Xing and Zhenli Zhu

34 Laser-Induced Breakdown Spectroscopy for the Analysis of Chemical and Biological Hazards 701
Lianbo Guo

35 Development of a Simple, Low-Cost, and On-Site Deployable LIBS Instrument for the Quantitative Analysis of Edible Salts 715
Sandeep Kumar, Hyang Kim, Jeong Park, Kyung-Sik Ham, Song-Hee Han, Sang-Ho Nam and Yonghoon Lee

36 Bioimaging in Laser-Induced Breakdown Spectroscopy 729
Pavlina Modlitbová, Pavel Po?ízka and Jozef Kaiser

37 Laser-Induced Breakdown Spectroscopy for the Identification of Bacterial Pathogens 745
Somenath Ghatak, Gaurav Sharma, Prashant Kumar Rai, Suman Yadav and Geeta Watal

38 Phase-Selective Laser-Induced Breakdown Spectroscopy of Metal-Oxide Nanoaerosols 755
Gang Xiong and Stephen D. Tse

39 Laser-Induced Breakdown Spectroscopy for the Analysis of Cultivated Soil 767
R. K. Aldakheel, M. A. Gondal and M. A. Almessiere

40 Laser-Induced Breakdown Spectroscopy in Food Sciences 781
J. Naozuka and A. P. Oliveira

41 Capabilities and Limitations of Laser-Induced Breakdown Spectroscopy for Analyzing Food Products 807
R. K. Aldakheel, M. A. Gondal and M. A. Almessiere

42 Laser-Induced Breakdown Spectroscopy and Its Application Perspectives in Industry and Recycling 823
Reinhard Noll

43 Development of Laser-Induced Breakdown Spectroscopy for Application to Space Exploration 851
Zhenzhen Wang and Han Luo

44 Femtosecond Laser-Induced Breakdown Spectroscopy of Complex Materials 863
Mathi Pandiyathuray

45 Application of LIBS for the Failure Characteristics Prediction of Heat-Resistant Steel 883
Meirong Dong, Junbin Cai, Shunchun Yao and Jidong Lu

46 Scope for Future Development in Laser-Induced Breakdown Spectroscopy 939
Yoshihiro Deguchi

Index 947
Vivek Kumar Singh is an Associate Professor in Department of Physics of Lucknow University, India. He has worked extensively on applications of XRF, LIBS, TOF-SIMS, and FTIR Spectroscopy for the study of numerous kinds of biological specimens such as gallstones, kidney stones, teeth, bones, plants, salts and others. Dr Singh is the recipient of the prestigious award of Raman Fellowship by UGC, Government of India.

Durgesh Kumar Tripathi, D.Phil., is Assistant Professor at Amity Institute of Organic Agriculture, Amity University, Uttar Pradesh, India. He has been the recipient of the prestigious UGC-DS-Kothari Post-Doctoral Fellowship from Centre of Advanced Study in Botany, BHU, India, and the Tony B. Academic Award, 2017, Washington DC, USA

Yoshihiro Deguchi began his career in laser diagnostics with BE, ME, and DE degrees from Toyohashi University of Technology in 1985, 1987, and 1990. He moved to Tokushima University as a full professor in 2010. Professor Deguchi has published research papers on the industrial applications of laser diagnostics and is one of the leading engineers to put laser diagnostics into practical use, especially in large scale plants.

Zhenzhen Wang is an Associate Professor at Xi'an Jiaotong University, in the Department of Thermal Power and Control Engineering in the School of Energy and Power Engineering. Her research interests are the laser diagnostics, measurement, and optimal control of thermal power plants, especially the developed applications of laser-induced breakdown spectroscopy (LIBS), laser breakdown time-of-flight mass spectrometry (LB-TOFMS), and tunable diode laser absorption spectroscopy (TDLAS).

V. K. Singh, Lucknow University, India; D. K. Tripathi, Amity University, Uttar Pradesh, India; Y. Deguchi, Tokushima University, Japan; Z. Wang, Xi'an Jiaotong University, China