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This chapter (Laser‐Induced Breakdown Spectroscopy (LIBS)) is a contribution to the Geostandards and Geoanalytical Research Handbook of Rock and Mineral Analysis – an online textbook that is a fully revised and updated edition of A Handbook of Silicate Rock Analysis (P. J. Potts, 1987, Blackie, Glasgow). Chapter 13 (from Section 3 of the handbook dealing with microbeam techniques) provides first a history of the development of laser‐induced breakdown spectroscopy, and of the LIBS process, followed by an examination of the fundamental principles of LIBS and its instrumentation. Discussion is then provided on the preparation of sample material, LIBS matrix effects and signal processing. Different modes of compositional analysis that can be tackled by LIBS are described, including quantitative measurement (covering isotope measurements), compositional mapping, depth profiling and the determination of physical properties of geological materials. The recent tandem coupling of LIBS with laser ablation ICP‐MS instrumentation is explored. Finally, a suite of examples of LIBS analyses of silicate rocks and minerals is provided, demonstrating the utility of this measurement principle in rapid compositional assessment, detailed petrological studies and microgeochemical mapping. [ABSTRACT FROM AUTHOR]

Laser-induced breakdown spectroscopy (LIBS) is a type of optical emission spectroscopy capable of rapid, simultaneous multi-element analysis. LIBS is effective for the analysis of atmospheric gases, geological fluids, and a broad spectrum of minerals, rocks, sediments, and soils both in and outside the traditional laboratory setting. With the recent introduction of commercial laboratory systems and handheld analyzers for use outside the laboratory for real-time in situ analysis in the field, LIBS is finding increasing application across the geosciences. This article first overviews the LIBS technique and then reviews its application in the domain of mineral exploration and ore processing, where LIBS offers some unique capabilities. [ABSTRACT FROM AUTHOR]

With the recent introduction of handheld instruments for field use, laser-induced breakdown spectroscopy (LIBS) is emerging as a practical technology for real-time in situ geochemical analysis in the field. LIBS is a form of optical emission spectroscopy that is simultaneously sensitive to all elements with a single laser shot so that a broadband LIBS spectrum can be considered a diagnostic geochemical fingerprint. Sets of LIBS spectra were collected for seven obsidian centers across north-central California, with data processed using multivariate statistical analysis and pattern recognition techniques. Although all obsidians exhibit similar bulk compositions, different regional obsidian sources were effectively discriminated via partial least squares discriminant analysis. Obsidian artifacts from seven archaeological sites were matched to their putative sources with a high degree of confidence. [ABSTRACT FROM AUTHOR]

Laser-induced breakdown spectroscopy (LIBS) is a technology for compositional analysis that is particularly effective for light elements, particularly Li, which is a critical commodity for emerging green technologies. This study undertook analysis by handheld LIBS of muscovite from the drill core, outcrop, and soil on the Carolina Lithium Prospect (CLP) in Gaston County, North Carolina (USA), which lies within the Carolina Tin-Spodumene Belt (CTSB). Abundances of the alkali elements Li, K, and Rb were determined for more than 130 muscovites from the Li-rich pegmatites to track the degree of pegmatite fractionation as a pathfinder for spodumene mineralization. Across the CTSB and including the CLP, muscovite Li contents vary over an order of magnitude, ranging from 0.04 to 0.74 wt. %, with their K/Rb ratios varying between 63 and 8, features that together document the highly evolved character of pegmatites within the CTSB district. On average, muscovite Li contents are greater in spodumene-bearing pegmatites at 0.21 ± 0.12 wt. % than for common quartz-feldspar pegmatites at 0.14 ± 0.08 wt. %. Although overlapping substantially in the middle portions of their distributions, muscovite K/Rb ratios are biased toward low values for spodumene-bearing pegmatites (X - = 21 ± 6) compared to those for quartz-feldspar pegmatites (X - = 33 ± 9). This study provides a framework for the use of LIBS analysis of muscovite in outcrop, drill core, and soil samples as an analytical tool for in-field and on-site geochemical analysis during Li pegmatite exploration and prospect evaluation. [ABSTRACT FROM AUTHOR]

Featured Application: Chemical analysis of soil samples using handheld spectroscopic instruments was performed to investigate if classification accuracy is enhanced through multianalyzer data fusion. The ability to rapidly conduct in-situ chemical analysis of multiple samples of soil and other geological materials in the field offers many advantages over a traditional approach that involves collecting samples for subsequent examination in the laboratory. This study explores the application of complementary spectroscopic analyzers and a data fusion methodology for the classification/discrimination of >100 soil samples from sites across the United States. Commercially available, handheld analyzers for X-ray fluorescence spectroscopy (XRFS), Raman spectroscopy (RS), and laser-induced breakdown spectroscopy (LIBS) were used to collect data both in the laboratory and in the field. Following a common data pre-processing protocol, principal component analysis (PCA) and partial least squares discriminant analysis (PLSDA) were used to build classification models. The features generated by PLSDA were then used in a hierarchical classification approach to assess the relative advantage of information fusion, which increased classification accuracy over any of the individual sensors from 80-91% to 94% and 64-93% to 98% for the two largest sample suites. The results show that additional testing with data sets for which classification with individual analyzers is modest might provide greater insight into the limits of data fusion for improving classification accuracy. [ABSTRACT FROM AUTHOR]

Abstract Microcrystalline igneous rocks of volcanic origin, such as basalt or rhyolite, were a common source of prehistoric stone tools. This study explores the use of laser-induced breakdown spectroscopy (LIBS) as part of an effort to develop analytical tools to examine geological materials of archaeological interest. LIBS is a method of atomic emission spectroscopy capable of providing rapid, in situ elemental analysis of any material with minimal to no sample preparation. We have utilized both a bespoke laboratory system and a commercial handheld analyzer to acquire broadband LIBS emission spectra for fresh and unaltered volcanic samples of varying age and composition from two tectonic settings. The distinguishing chemical characteristics of the different volcanic regions and centers were identified and their sources differentiated through multivariate chemometric analysis. Classification and discrimination has been achieved with a high degree of success using a pattern recognition approach. These results suggest that the provenance of stone artifacts may be identified in the field using handheld LIBS through the use of algorithmic matching of LIBS emission spectra against a sufficiently robust and representative database previously prepared by analysis of samples of known origin. [ABSTRACT FROM AUTHOR]

A broad suite of geological materials was studied a using a handheld laser-induced breakdown spectroscopy ( LIBS) instrument. Because LIBS is simultaneously sensitive to all elements, the full broadband emission spectrum recorded from a single laser shot provides a 'chemical fingerprint' of any material - solid, liquid or gas. The distinguishing chemical characteristics of the samples analysed were identified through principal component analysis ( PCA), which demonstrates how this technique for statistical analysis can be used to identify spectral differences between similar sample types based on minor and trace constituents. Partial least squares discriminant analysis ( PLSDA) was used to distinguish and classify the materials, with excellent discrimination achieved for all sample types. This study illustrates through four examples (carbonate minerals and rocks, the oxide mineral pair columbite-tantalite, the silicate mineral garnet and native gold) how portable, handheld LIBS analysers can be used for real-time chemical analysis under simulated field conditions for element or mineral identification, plus such applications as stratigraphic correlation, provenance determination and natural resource exploration. [ABSTRACT FROM AUTHOR]

Abstract: Applications of laser-induced breakdown spectroscopy (LIBS) have been growing rapidly and continue to be extended to a broad range of materials. This paper reviews recent application of LIBS for the analysis of geological and environmental materials, here termed "GEOLIBS" . Following a summary of fundamentals of the LIBS analytical technique and its potential for chemical analysis in real time, the history of the application of LIBS to the analysis of natural fluids, minerals, rocks, soils, sediments, and other natural materials is described. [Copyright &y& Elsevier]

Abstract: A large suite of natural carbonate, fluorite and silicate geological materials was studied using laser-induced breakdown spectroscopy (LIBS). Both single- and double-pulse LIBS spectra were acquired using close-contact benchtop and standoff (25 m) LIBS systems. Principal components analysis (PCA) and partial least squares discriminant analysis (PLS-DA) were used to identify the distinguishing characteristics of the geological samples and to classify the materials. Excellent discrimination was achieved with all sample types using PLS-DA and several techniques for improving sample classification were identified. The laboratory double-pulse LIBS system did not provide any advantage for sample classification over the single-pulse LIBS system, except in the case of the soil samples. The standoff LIBS system provided comparable results to the laboratory systems. This work also demonstrates how PCA can be used to identify spectral differences between similar sample types based on minor impurities. [Copyright &y& Elsevier]

Abstract: Laser-induced breakdown spectroscopy (LIBS) provides an alternative chemical analytical technique that obviates the issues of sample preparation and sample destruction common to most laboratory-based analytical methods. This contribution explores the capability of LIBS analysis to identify carbonate and silicate minerals rapidly and accurately. Fifty-two mineral samples (18 carbonates, 9 pyroxenes and pyroxenoids, 6 amphiboles, 8 phyllosilicates, and 11 feldspars) were analyzed by LIBS. Two composite broadband spectra (averages of 10 shots each) were calculated for each sample to produce two databases each containing the composite LIBS spectra for the same 52 mineral samples. By using correlation coefficients resulting from the regression of the intensities of pairs of LIBS spectra, all 52 minerals were correctly identified in the database. If the LIBS spectra of each sample were compared to a database containing the other 51 minerals, 65% were identified as a mineral of similar composition from the same mineral family. The remaining minerals were misidentified for two reasons: 1) the mineral had high concentrations of an element not present in the database; and 2) the mineral was identified as a mineral with similar elemental composition from a different family. For instance, the Ca–Mg carbonate dolomite was misidentified as the Ca–Mg silicate diopside. This pilot study suggests that LIBS has promise in mineral identification and in situ analysis of minerals that record geological processes. [Copyright &y& Elsevier]

Laser-induced breakdown spectroscopy (LIBS), which has recently emerged as tool for geochemical analysis outside the traditional laboratory setting, is an ideal tool for Li exploration because it is the only technique that can measure Li in minerals, rocks, soils, and brines in-situ in the field. In addition to being used in many products essential to modern life, Li is a necessary element for a reduced carbon future and Li–Cs–Ta (LCT) granitic pegmatites are an important source of Li. Such pegmatites can have varying degrees of enrichment in Li, Rb, Cs, Be, Sn, Ga, Ta>Nb, B, P, and F. We focus here on the LCT pegmatites of the Carolina Tin-Spodumene Belt (CTSB) situated in the Kings Mountain Shear Zone, which extends from South Carolina into North Carolina. The CTSB hosts both barren and fertile pegmatites, with Li-enriched pegmatites containing spodumene, K-feldspar, albite, quartz, muscovite, and beryl. We illustrate how handheld LIBS analysis can be used for real-time Li analysis in the field at a historically important CTSB pegmatite locality in Gaston County, N.C. in four contexts: (i) elemental detection and identification; (ii) microchemical mapping; (iii) depth profiling; and (iv) elemental quantitative analysis. Finally, as an example of a practical exploration application, we describe how handheld LIBS can be used to measure K/Rb ratios and Li contents of muscovite and rapidly determine the degree of pegmatite fractionation. This study demonstrates the potential of handheld LIBS to drastically reduce the time necessary to acquire geochemical data relevant to acquiring compositional information for pegmatites during a Li pegmatite exploration program. [ABSTRACT FROM AUTHOR]

Laser-induced breakdown spectroscopy (LIBS) is a form of optical emission spectroscopy that can be used for the rapid analysis of geological materials in the field under ambient environmental conditions. We describe here the innovative use of handheld LIBS for the in situ analysis of rock varnish. This thinly laminated and compositionally complex veneer forms slowly over time on rock surfaces in dryland regions and is particularly abundant across the Mojave Desert climatic region of east-central California (USA). Following the depth profiling examination of a varnished clast from colluvial gravel in Death Valley in the laboratory, our in situ analysis of rock varnish and visually similar coatings on rock surfaces was undertaken in the Owens and Deep Spring valleys in two contexts, element detection/identification and microchemical mapping. Emission peaks were recognized in the LIBS spectra for the nine elements most abundant in rock varnish—Mn, Fe, Si, Al, Na, Mg, K, Ca and Ba, as well as for H, Li, C, O, Ti, V, Sr and Rb. Focused follow-up laboratory and field studies will help understand rock varnish formation and its utility for weathering and chronological studies. [ABSTRACT FROM AUTHOR]

Laser-induced breakdown spectroscopy (LIBS) is a simple and straightforward technique of atomic emission spectroscopy that can provide multi-element detection and quantification in any material, in-situ and in real time because all elements emit in the 200–900 nm spectral range of the LIBS optical emission. This study evaluated two practical applications of LIBS—validation of labels assigned to garnets in museum collections and discrimination of LCT (lithium-cesium-tantalum) and NYF (niobium, yttrium and fluorine) pegmatites based on garnet geochemical fingerprinting, both of which could be implemented on site in a museum or field setting with a handheld LIBS analyzer. Major element compositions were determined using electron microprobe analysis for a suite of 208 garnets from 24 countries to determine garnet type. Both commercial laboratory and handheld analyzers were then used to acquire LIBS broadband spectra that were chemometrically processed by partial least squares discriminant analysis (PLSDA) and linear support vector machine classification (SVM). High attribution success rates (>98%) were obtained using PLSDA and SVM for the handheld data suggesting that LIBS could be used in a museum setting to assign garnet type quickly and accurately. LIBS also identifies changes in garnet composition associated with increasing mineral and chemical complexity of LCT and NYF pegmatites. [ABSTRACT FROM AUTHOR]

Laser-induced breakdown spectroscopy (LIBS) is a simple, straightforward, and versatile form of atomic emission spectroscopy that focuses a rapidly-pulsed laser beam onto a sample to form a plasma containing its constituent elements and then uses spectral analysis of the emitted light to detect the elements present. In theory, LIBS is capable of qualitative, semi-quantitative, and quantitative analysis of all elements in the periodic table. LIBS can be performed in the laboratory or outside in the ambient environment for on-site analysis in situ; LIBS can also be used for rapid microscale compositional imaging. This review first presents a description of the LIBS technique and then discusses and illustrates through a historic literature review how LIBS has been used to analyze gases, natural waters, minerals, rocks, sediments, and soils. Given the persistent need of analytical instrumentation for the rapid chemical analysis of geologic materials in the field, and the capability of LIBS to analyze any type of sample in real time with little to no preparation, there is a vast potential for the routine application of LIBS across a broad spectrum of the geosciences that is as yet only minimally realized. [Display omitted] • LIBS has specific advantages for rapid chemical analysis in the laboratory and the field, plus vast potential for application across geosciences. • LIBS principles, technology, and chemometric methods for data analysis are described. • The applications of LIBS is reviewed for the chemical analysis of different types of geological media. • Recent trends are highlighted for chemical imaging and microscale elemental analysis minerals and rocks by LIBS. [ABSTRACT FROM AUTHOR]

The first part of this review describes laser-induced breakdown spectroscopy (LIBS) instrumentation for in situ measurement outside the laboratory, both prototype instruments and commercially available analyzers that can be operated by a single individual. Two types of devices are described – (i) field-portable type systems consisting of multiple units connected by an umbilical (fp LIBS) and (ii) handheld analyzers (h LIBS). The performance of these two types of LIBS systems is compared with that of its primary competitor technology portable X-ray fluorescence spectroscopy (p XRF). The second part of the article reviews the results of both fp LIBS and h LIBS obtained in both research settings and for practical applications in various sectors where speed of analysis is often crucial. These include compositional screening of natural and manufactured materials, quality control of manufacturing processes, identification of environmental contaminants, biomedical diagnostics, forensic analysis, and hazardous material identification in the industrial, environmental, geological, cultural heritage, agricultural, biological, nuclear and security sectors. The review concludes by highlighting the key trends and challenging future directions in making LIBS technology readily accessible for applications that demand easy portability and fast analysis outside of the laboratory with instruments of compact dimensions and low weight but high performance, crucial features required for any portable device. Unlabelled Image • Overview of field-portable and handheld LIBS instrumentation transportable by a single person. • Field-portable LIBS in non-commercialized suitcase and backpack prototype instrumentation. • Recent commercial handheld LIBS instrumentation. • Applications of field-portable and handheld LIBS in a variety of research and commercial areas. [ABSTRACT FROM AUTHOR]

The mineral exploration industry requires new methods and tools to address the challenges of declining mineral reserves and increasing discovery costs. Laser-induced breakdown spectroscopy (LIBS) represents an emerging geochemical tool for mineral exploration that can provide rapid, in situ, compositional analysis and high-resolution imaging in both laboratory and field and settings. We demonstrate through a review of previously published research and our new results how LIBS can be applied to qualitative element detection for geochemical fingerprinting, sample classification, and discrimination, as well as quantitative geochemical analysis, rock characterization by grain size analysis, and in situ geochemical imaging. LIBS can detect elements with low atomic number (i.e., light elements), some of which are important pathfinder elements for mineral exploration and/or are classified as critical commodities for emerging green technologies. LIBS data can be acquired in situ, facilitating the interpretation of geochemical data in a mineralogical context, which is important for unraveling the complex geological history of most ore systems. LIBS technology is available as a handheld analyzer, thus providing a field capability to acquire low-cost geochemical analyses in real time. As a consequence, LIBS has wide potential to be utilized in mineral exploration, prospect evaluation, and deposit exploitation quality control. LIBS is ideally suited for field exploration programs that would benefit from rapid chemical analysis under ambient environmental conditions. [ABSTRACT FROM AUTHOR]

Abstract: Laser-induced breakdown spectroscopy (LIBS) offers a means of rapidly distinguishing different geographic sources for a mineral because the LIBS plasma emission spectrum provides information on the chemical composition (i.e. geochemical fingerprint) of a geomaterial. An application of this approach with potentially significant commercial and political importance is the spectral fingerprinting of “conflict minerals” such as columbite–tantalite (“coltan”). Following a successful pilot study of a columbite–tantalite suite from North America, a more geographically diverse set of 57 samples from 37 locations around the world was analyzed using a commercially available LIBS system. The LIBS spectra were analyzed using advanced multivariate statistical signal processing techniques. Partial least squares discriminant analysis (PLSDA) resulted in a correct place-level geographic classification at success rates above 90%. The possible role of rare-earth elements (REEs) as a factor contributing to the high levels of sample discrimination was explored. These results provide additional evidence that LIBS has the potential to be utilized in the field as a real-time screening tool to discriminate between columbite–tantalite ores of different provenance. [Copyright &y& Elsevier]