■ CONTENTS General Information: Books, Reviews, and Conferences 640 Fundamentals 641 Interaction of Laser Beam with Matter 641 Factors Affecting Laser Ablation and LaserInduced Plasma Formation 642 Influence of Target on the Laser-Induced Plasmas 642 Influence of Laser Parameters on the LaserInduced Plasmas 643 Laser Wavelength (λ) 643 Laser Pulse Duration (τ) 643 Laser Pulse Energy (E) 645 Influence of Ambient Gas on the Laser-Induced Plasmas 645 LIBS Methods 647 Double Pulse LIBS 647 Femtosecond LIBS 651 Resonant LIBS 652 Ranging Approaches 652 Applications 654 Surface Inspection, Depth Profiling, and LIBS Imaging 654 Cultural Heritage 654 Industrial Analysis 655 Environmental Monitoring 656 Biomedical and Pharmaceutical Analysis 658 Security and Forensics 659 Analysis of Liquids and Submerged Solids 660 Space Exploration and Isotopic Analysis 662 Space Exploration 662 Isotopic Analysis 662 Conclusions and Future Outlook 663 Author Information 664 Corresponding Author 664 Notes 664 Biographies 664 Acknowledgments 664 References 664

Laser-induced breakdown spectroscopy.

Laser induced breakdown spectroscopy (LIBS) is basically an emission spectroscopy technique where atoms and ions are primarily formed in their excited states as a result of interaction between a tightly focused laser beam and the material sample. The interaction between matter and high-density photons generates a plasma plume, which evolves with time and may eventually acquire thermodynamic equilibrium. One of the important features of this technique is that it does not require any sample preparation, unlike conventional spectroscopic analytical techniques. Samples in the form of solids, liquids, gels, gases, plasmas and biological materials (like teeth, leaf or blood) can be studied with almost equal ease.LIBS has rapidly developed into a major analytical technology with the capability of detecting all chemical elements in a sample, of real- time response, and of close-contact or stand-off analysis of targets. The present book has been written by active specialists in this field, it includes the basic principles, the latest developments in instrumentation and the applications of LIBS. It will be useful to analytical chemists and spectroscopists as an important source of information and also to graduate students and researchers engaged in the fields of combustion, environmental science, and planetary and space exploration. It features: recent research work, possible future applications and LIBS Principles.

Chapter 12 – Laser-Induced Breakdown Spectroscopy: Advanced Analytical Technique

Local Thermodynamic Equilibrium in Laser-Induced Breakdown Spectroscopy: Beyond the McWhirter criterion

Characterization of laser induced plasmas by optical emission spectroscopy: A review of experiments and methods

The ChemCam instrument suite on the Mars Science Laboratory (MSL) rover Curiosity provides remote compositional information using the first laser-induced breakdown spectrometer (LIBS) on a planetary mission, and provides sample texture and morphology data using a remote micro-imager (RMI). Overall, ChemCam supports MSL with five capabilities: remote classification of rock and soil characteristics; quantitative elemental compositions including light elements like hydrogen and some elements to which LIBS is uniquely sensitive (e.g., Li, Be, Rb, Sr, Ba); remote removal of surface dust and depth profiling through surface coatings; context imaging; and passive spectroscopy over the 240–905 nm range. ChemCam is built in two sections: The mast unit, consisting of a laser, telescope, RMI, and associated electronics, resides on the rover’s mast, and is described in a companion paper. ChemCam’s body unit, which is mounted in the body of the rover, comprises an optical demultiplexer, three spectrometers, detectors, their coolers, and associated electronics and data handling logic. Additional instrument components include a 6 m optical fiber which transfers the LIBS light from the telescope to the body unit, and a set of onboard calibration targets. ChemCam was integrated and tested at Los Alamos National Laboratory where it also underwent LIBS calibration with 69 geological standards prior to integration with the rover. Post-integration testing used coordinated mast and instrument commands, including LIBS line scans on rock targets during system-level thermal-vacuum tests. In this paper we describe the body unit, optical fiber, and calibration targets, and the assembly, testing, and verification of the instrument prior to launch.

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The ChemCam Instrument Suite on the Mars Science Laboratory (MSL) Rover: Body Unit and Combined System Tests

In laser-induced breakdown spectroscopy (LIBS), a focused laser pulse is used to ablate material from a surface and form a laser plasma that excites the vaporized material. Geometric factors, such as the distance between the sample and the focusing lens and the method of collecting the plasma light, can greatly influence the analytical results. To obtain the best quantitative results, one must consider this geometry. Here we report the results of an investigation of the effect of sampling geometry on LIBS measurements. Diagnostics include time-resolved spectroscopy and temporally and spectrally resolved imaging using an acousto-optic tunable filter (AOTF). Parameters investigated include the type of lens (cylindrical or spherical) used to focus the laser pulse onto the sample, the focal length of the lens (75 or 150 mm), the lens-to-sample distance (LTSD), the angle-of-incidence of the laser pulse onto the sample, and the method used to collect the plasma light (lens or fiber-optic bundle). From these studies, it was found that atomic emission intensities, plasma temperature, and mass of ablated material depend strongly on the LTSD for both types of lenses. For laser pulse energies above the breakdown threshold for air, these quantities exhibit symmetric behavior about an LTSD approximately equal to the back focal length for cylindrical lenses and asymmetric behavior for spherical lenses. For pulse energies below the air breakdown threshold, results obtained for both lenses display symmetric behavior. Detection limits and measurement precision for the elements Be, Cr, Cu, Mn, Pb, and Sr, determined with the use of 14 certified reference soils and stream sediments, were found to be independent of the lens used. Time-resolved images of the laser plasma show that at times >5 μs after plasma formation a cloud of emitting atoms extends significantly beyond the centrally located, visibly white, intense plasma core present at early times (<0.3 μs). It was determined that, by collecting light from the edges of the emitting cloud, one can record spectra using an ungated detector (no time resolution) that resemble closely the spectra obtained from a gated detector providing time-resolved detection. This result has implications in the development of less expensive LIBS detection systems.

Effect of Sampling Geometry on Elemental Emissions in Laser-Induced Breakdown Spectroscopy

Laser-induced breakdown spectroscopy (LIBS) was used in a blind study to successfully differentiate bacterial pathogens, both species and strain. The pathogens used for the study were chosen and prepared by one set of researchers. The LIBS data were collected and analyzed by another set of researchers. The latter researchers had no knowledge of the sample identities other than that (1) the first five of fifteen samples were unique (not replicates) and (2) the remaining ten samples consisted of two replicates of each of the first five samples. Using only chemometric analysis of the LIBS data, the ten replicate bacterial samples were successfully matched to each of the first five samples. The results of this blind study show it is possible to differentiate the bacterial pathogens Escherichia coli, three clonal methicillin-resistant Staphylococcus aureus (MRSA) strains, and one unrelated MRSA strain using LIBS. This is an important finding because it demonstrates that LIBS can be used to determine bacterial pathogen species within a defined sample set and can be used to differentiate between clonal relationships among strains of a single multiple-antibiotic-resistant bacterial species. Such a capability is important for the development of LIBS instruments for use in medical, water, and food safety applications.

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The Use of Laser-Induced Breakdown Spectroscopy for Distinguishing Between Bacterial Pathogen Species and Strains

The rapid detection of biological contaminants, such as Escherichia coli O157:H7 and Salmonella enterica , on foods and food-processing surfaces is important to ensure food safety and streamline the food-monitoring process. Laser-induced breakdown spectroscopy (LIBS) is an ideal candidate technology for this application because sample preparation is minimal and results are available rapidly (seconds to minutes). Here, multivariate regression analysis of LIBS data is used to differentiate the live bacterial pathogens E. coli O157:H7 and S. enterica on various foods (eggshell, milk, bologna, ground beef, chicken, and lettuce) and surfaces (metal drain strainer and cutting board). The type (E. coli or S. enterica) of bacteria could be differentiated in all cases studied along with the metabolic state (viable or heat killed). This study provides data showing the potential of LIBS for the rapid identification of biological contaminants using spectra collected directly from foods and surfaces.

Detection of biological contaminants on foods and food surfaces using laser-induced breakdown spectroscopy (LIBS).

Laser-induced breakdown spectroscopy (LIBS) is a novel method of elemental analysis based on a laser-generated plasma. Pulses from a laser are focused on a sample to atomize a small amount of material resulting in the formation of a microplasma. Because of the high plasma temperature, the resulting atoms are electronically excited to emit light. The plasma light is spectrally resolved and detected to determine the elemental composition of the sample based on the unique emission spectrum of each element. Because of the simplicity of the method, it is suited for analyses that cannot be carried out using conventional methods of atomic emission spectroscopy (AES). This is particularly true for measurements that must be conducted outside of an analytical laboratory. A particular advantage of LIBS is the ability to analyze most types of samples without any preparation. This allows the interrogation of samples in situ, providing rapid measurement capability, permitting the method to be used in the analysis of gases, liquids, and solids in a variety of different sampling configurations. Although LIBS provides sensitive detection for many elements, it is not an ultrasensitive detection technique. In addition, under field conditions, the method typically does not provide the high accuracy and precision offered by laboratory-based methods of AES. Although basically an element detection method, chemometric methods of analysis are being developed to analyze the LIBS spectrum to provide identification of chemical substances (e.g. explosives, pathogens, and chemical agents).

Laser-induced Breakdown Spectroscopy

In this work, the use of laser-induced breakdown spectroscopy (LIBS) to differentiate live pathogens and killed viruses on substrates is investigated. Live pathogens B. anthracis Sterne strain and F. tularensis live vaccine strain were interrogated as lawn and colonies on agar; dilutions on agar; and dilutions on glass slides, and it was found possible to differentiate among all samples. UV killed hantavirusstrains were studied as dilutions on slides and it was also found possible to differentiate among strains. To the best of our knowledge, this is the first study in which LIBS has been used to differentiate virus samples.

Rosalie A. Multari

Papers

Effect of Sampling Geometry on Elemental Emissions in Laser-Induced Breakdown Spectroscopy

The Use of Laser-Induced Breakdown Spectroscopy for Distinguishing Between Bacterial Pathogen Species and Strains

Detection of biological contaminants on foods and food surfaces using laser-induced breakdown spectroscopy (LIBS).

Laser-induced Breakdown Spectroscopy

Use of laser-induced breakdown spectroscopy for the differentiation of pathogens and viruses on substrates