LASER-INDUCED BREAKDOWN; PLASMA-MASS SPECTROMETRY; RESOLUTION CONTINUUM SOURCE; PARTICLE ICP-MS; RAY-FLUORESCENCE SPECTROMETRY; MULTI-ANALYTICAL APPROACH; OPTICAL-EMISSION SPECTROSCOPY; LI-ION BATTERIES; ELECTRON-PARAMAGNETIC-RESONANCE; ELEMENTAL IMPURITIES ANALYSIS

This ASU review focuses on developments in applications of atomic spectrometry to the characterisation of metals, chemicals and materials. It is difficult to identify research trends solely from an annual review of the literature, but a certain perspective can be obtained from examining the developments described in recent years in this ASU review series. It is, for example, evident that there has been a decline in truly novel applications for the analysis of chemicals, perhaps indicative of the fact that, for most sample types, there is now an abundance of methods available in the literature. Those papers that have appeared in the year under review have either focused on specific problems not yet fully addressed (e.g. determination of Si in gasoline) or on incremental development of well-established approaches to sample preparation or measurement. Nevertheless, there has been a very noticeable increase in activity in relation to publication of methods for the characterisation of pharmaceuticals. This is directly linked to changes in the US Pharmacopeia requirements for registration of pharmaceuticals for human use that require assessments to be made for trace element content. Laser-induced breakdown spectrometry is becoming widely employed for applications involving the characterisation of a wide variety of metals, materials and other solid sample types. Efforts are being made to overcome the perceived weaknesses of the technique, such as lack of sensitivity, elemental fractionation, accuracy and/or precision. Advances have been made, for example, using dual-pulse lasers to improve sensitivity, or by employing chemometrics methods with full spectrum data to improve the robustness of calibration. Many of these reported LIBS developments draw from, and have relevance for, applications involving LA-ICP-MS, which continues to be a popular means of generating highly sensitive lateral and depth profiling and bulk compositional information for a wide range of materials and solids. The use of field portable instrumentation for in situ analysis continues grow, with LIBS and XRF techniques amongst those most frequently cited. The development of such instrumentation has had a substantial impact in the examination of cultural heritage artefacts, especially in relation to paintings, wall murals and other objects of unique historical value. The latter area of application has also seen continued use of combinations of surface (SIMS, XPS, SEM-EDS, PIXE, GD and laserablation methods) and bulk (ICP-OES, ICP-MS, AAS, XRF) analysis techniques to reveal details of objects that would not otherwise be identified (for example preparatory sketches hidden under original works of art or materials provenance). This trend towards using a multi-technique based approach has also been apparent in the characterisation of multi-layer or heterogeneous organic and inorganic materials and metals. Finally, methods for the analysis of nanoparticles and nanostructures have been reported, based primarily on single particle (SP)-ICP-MS and flow field flow fractionation (A4F). The investigation of methods of drift correction, the use of flow injection and isotope dilution methodologies in combination with SP-ICP-MS are indicative of the further development of this field.

DEPTH-PROFILE ANALYSIS; VACUUM-ULTRAVIOLET; SURFACE-ANALYSIS; STEEL ANALYSIS; DISCHARGE; SPECTROMETRY; ABLATION; SAMPLES; LIBS; QUANTIFICATION

This review is focused on a comparison of LIBS with the two most common plasma Optical Emission Spectroscopy (OES) techniques for analysis of metals; spark OES and glow discharge (GD) OES. It is shown that these two techniques have only minor differences in analytical performance. An important part of the paper reviews a direct comparison of the analytical figures of merit for bulk analysis of steels using spark and LIBS sources. The comparison was carried out using one instrument with interchangeable sources, eliminating differences related to the optical system and detectors. It was found that the spark provides slightly better analytical figures of merit. The spark analysis is considerably faster, the simple design of the spark stand has enabled complete automation, both properties of great importance in the metallurgical industry for routine analysis. The analysis of non-metallic inclusions (NMI) with spark and LIBS is presented, in the case of the spark this has become known as Pulse Distribution Analysis (FDA). A very significant difference between the techniques is that the electrical spark typically evaporates similar to 100 times more material than a single laser pulse, resulting in complete evaporation of an NMI present in the evaporated metal. The major advantage of LIBS is that it is localised with very good lateral resolution. The major advantages of spark is that it is much faster (can be done simultaneous with the bulk analysis) and easier to quantify. Compositional Depth Profiling (CDP) is compared for GD-OES and LIBS. It is shown that for applications where GD-OES is well suited, e.g. coated metallic sheet, GD-OES still performs slightly better than LIBS. Similar to the case of NMI analysis, the major advantage of LIBS is the great lateral resolution. This allows elemental surface mapping, as well as CDP of very small areas on pm scale. One further advantage of LIBS is that samples of almost any material, shape and size can be analysed, whereas GD-OES has only limited capabilities for non-flat and small samples. A general conclusion of this review is that LIBS is not likely to replace spark and GD-OES in the foreseeable future, for applications where these techniques are well suited. On the other hand several new applications, particularly in the field of on-line monitoring of industrial processes, are making great inroads for LIBS in the metallurgical and manufacturing industries. (C) 2017 Elsevier B.V. All rights reserved.

Laser-induced breakdown spectroscopy; LIBS; Calibration-free LIBS; Limit of detection; Analytical sensitivity; Calibration; Spatial heterodyne spectroscopy;QUANTITATIVE-ANALYSIS; ELEMENTAL ANALYSIS; PLANT MATERIALS; MOISTURE-CONTENT; CARBON CONTENT; LIBS; COAL; IDENTIFICATION; SOIL; METHODOLOGY

The goal of this review article is to provide a description of recent and novel laser-induced breakdown spectroscopy (LIBS) applications and developments, especially those discussed during the NASLIBS Conference, held during SciX in Providence, RI, in September 2015. This topic was selected in view of the numerous recent overall review papers that have successfully given a broad view of the current understanding of laser-material interactions and plasma development and have also discussed the wide landscape of analytical applications of LIBS. This paper is divided into sections that focus on a few of the many applications under development in the LIBS community. We provide a summary of updates to calibration-free LIBS (CF-LIBS) and associated developments using plasma characteristics to improve quantification in LIBS output, both in a dedicated section and as applications are discussed. We have also described the most recent publications studying the sources, generation, and use of molecular features in LIBS, including those naturally present in the spectra of organic materials, and those induced with the addition of salts to enable the measurement of halogens, not typically present in LIBS signals. In terms of development of applications of LIBS, we focused on the use of LIBS for indirect measurements such as pH and degree of humification in soil and heating value in coal. We also reviewed the extant literature on LIBS analysis of agricultural materials, coal, minerals, and metals. Finally, we discuss the nascent developments of spatially heterodyne spectroscopy, a method that seeks to circumnavigate a serious drawback of most spectrometers - very small optical throughput - through the use of interferometers.

Laser-induced breakdown spectroscopy; LIBS; elemental identification; wavelength similarity coefficient;SEARCH ALGORITHMS; SPECTROSCOPY; PLASMA; LIBRARY

This work proposes a method to perform elemental identification on plasmas produced using the laser-induced breakdown spectroscopy (LIBS) technique. The method is based on the preservation of the relative relevance of the spectral line emission intensities, which is lost during the parametric correlation procedure, by the introduction of a similitude coefficient called wavelength similarity coefficient. Furthermore, it was shown that for identification purposes, a simplified plasma model is sufficient to predict adequately the relative emission intensities in LIBS plasmas. As a result, it is possible to automatically identify the species with high emission signals, while trace detection is also possible by relaxing search conditions, although manual refinement is still required.

Laser-induced breakdown spectroscopy; LIBS; lens-to-sample distance; sample positioning; repeatability;

A simple device based on two commercial laser pointers is described to assist in the analysis of samples that present uneven surfaces and/or irregular shapes using laser-induced breakdown spectroscopy (LIBS). The device allows for easy positioning of the sample surface at a reproducible distance from the focusing lens that conveys the laser pulse to generate the micro-plasma in a LIBS system, with reproducibility better than +/- 0.2 mm. In this way, fluctuations in the fluence (J cm(-2)) are minimized and the LIBS analytical signals can be obtained with a better precision even when samples with irregular surfaces are probed.

Laser-induced breakdown spectroscopy; LIBS; self-absorption; curve-of-growth; COG;INDUCED PLASMA; GROWTH; CURVES

Laser-induced breakdown spectroscopy (LIBS) is a widely used laser spectroscopic technique in various fields, such as material science, forensic science, biological science, and the chemical and pharmaceutical industries. In most LIBS work, the analysis is performed using radiative transitions from atomic emissions. In this study, the plasma temperature and the product Nl (the number density N and the absorption path length l) were determined to evaluate the optical depths and the self-absorption of Sr and Al lines. A binary mixture of strontium nitrate and aluminum oxide was used as a sample, consisting of variety of different concentrations in powder form. Laser-induced breakdown spectroscopy spectra were collected by varying various parameters, such as laserenergy, gate delay time, and gate width time to optimize the LIBS signals. Atomic emission from Sr and Al lines, as observed in the LIBS spectra of different sample compositions, was used to characterize the laser induced plasma and evaluate the optical depths and self-absorption of LIBS.

LIBS; Variation; Experimental design; Normalization; Statistics;INDUCED BREAKDOWN SPECTROSCOPY; FLOAT GLASS; SPECTROMETRY; DISCRIMINATION

Laser Induced Breakdown Spectroscopy (LIBS) is an analytical chemistry technique that has the potential to identify and measure the elements in a substance of interest. LIBS is applicable for any phase (solid, liquid or gas). LIBS has gained importance in the fields of material identification, biomedical science, forensics, military, art and archaeology in the recent years. In spite of its many advantages over other instruments, it has a few drawbacks such as poor precision and repeatability. That is, different spectra may be observed for the same sample over successive runs. This indicates poor precision of the instrument. This paper presents an experiment designed to investigate the claim that there is higher variation in the experiments conducted on different days as compared to the experiments conducted on the same day. This study examines the variability in the spectra between the runs on the same day, and the variability between runs on different days using samples from a standard reference glass, and discusses the conclusions that can be drawn from the results. (C) 2017 Elsevier B.V. All rights reserved.

PARTICLE-ICP-MS; RAMAN-SPECTROSCOPY; NANOPARTICLES; SILVER

Analytical spectroscopy is a mature field, but advances in instrumentation, measurement, and sample preparation techniques continue to be made. Much recent development has seen a heavy emphasis toward techniques and instrumentation that allow for noninvasive, in situ, and in vivo procedures while still retaining a high degree of sensitivity. This article will review some of this progress over the past two to three years across five major spectroscopic fields: Raman, laser-induced breakdown spectroscopy, X-ray fluorescence, infrared, and inductively coupled plasma techniques.

SINGLE; INSTRUMENT; LIBS

This paper reports the development of a compact double-pulse laser system to enhance laser induced breakdown spectroscopy (LIBS) for field applications. Pumped by high-power vertical-surface emitting lasers, the laser system that produces 16 ns pulse at 12 mJ/pulse with total weight less than 10 kg is developed. The inter-pulse delay can be adjusted from 0 mu s with 0.5 mu s increment. Several LIBS experiments were carried out on NIST standard aluminum alloy samples. Comparing with the single-pulse LIBS, up to 9 times enhancement in atomic emission line was achieved with continuum background emission reduced by 70%. This has led to up to 10 times improvement in the limit of detection. Signal stability was also improved by 128% indicating that a more robust and accurate LIBS measurement can be achieved using a compact double-pulse laser system. This paper presents a viable and field deployable laser tool to dramatically improve the sensitivity and applicability of LIBS for a wide array of applications. Published by AIP Publishing.

Microconcentration; Optical spectroscopy; Measurement sensitivity; Portable analytical instrumentation;INDUCED BREAKDOWN SPECTROSCOPY; REAL-TIME MEASUREMENT; ELECTROSTATIC PRECIPITATOR; MASS-SPECTROMETRY; AERODYNAMIC LENS; VIRTUAL IMPACTOR; CONCENTRATOR; PARTICLES; DESIGN; EFFICIENCY

Efficient microconcentration of aerosols to a substrate is essential for effectively coupling the collected particles to microscale optical spectroscopies such as laser-induced or spark microplasma, or micro-Raman or infrared spectroscopies. In this study, we present detailed characterization of a corona-based aerosol microconcentration technique developed previously (Diwakar & Kulkarni, 2012). The method involves two coaxial electrodes separated by a few millimeters, one held at a high electrical potential and the other grounded. The particles are collected on the collection (i. e., ground) electrode from a coaxial aerosol flow in a one-step charge-and-collect scheme using corona discharge and electrical precipitation between the two electrodes. Performance of the corona microconcentration method was determined experimentally by measuring collection efficiency, wall losses, and particle deposition density. An intrinsic spectroscopic sensitivity was experimentally determined for the aerosol microconcentrator. Using this sensitivity, we show that corona-based microconcentration is much superior to alternative methods, including filtration, focused impaction using aerodynamic lens, and spot collection using condensational growth. The method offers unique advantages for compact, hand-held aerosol analytical instrumentation.

Laser-induced breakdown spectroscopy (LIBS) is a direct and versatile analytical technique that performs the elemental composition analysis based on optical emission produced by laser induced-plasma, with a little or no sample preparation. The performance of the LIBS technique relies on the choice of experimental conditions which must be thoroughly explored and optimized for each application. The main parameters affecting the LIBS performance are the laser energy, laser wavelength, pulse duration, gate delay, geometrical set-up of the focusing and collecting optics. In LIBS quantitative analysis, the gate delay and laser energy are very important parameters that have pronounced impact on the accuracy of the elemental composition information of the materials. The determination of calcium elements in the pelletized samples was investigated and served for the purpose of optimizing the gate delay and laser energy by studying and analyzing the results from emission intensities collected and signal to background ratio (S/B) for the specified wavelengths.

Femtosecond; Laser repetition rate; Limit of detection;INDUCED BREAKDOWN SPECTROSCOPY; NANOSECOND

Experimentally investigated limit of detection Mg, Al, Sr, Pb. depending on the pulse repetition rate femtosecond Ti: Sa laser optical breakdown in aqueous solutions on the surface of the investigated element in the laser pulse duration 60 fs, pulse energy of 1 mJ. The study was conducted for the laser pulse repetition rate of 50 Hz, 150 Hz, 250 Hz. To choose the optimal time delay of registration relative to the laser beam for the following chemicals:: Na, N, Fe, Ca, Mg, Al, Pb, Mn.

Q-SWITCHED NDYAG; EMISSION ENHANCEMENT; OPTICAL-EMISSION; PLASMA; SPARK

In this study, we observed the evolution of the spectral emission intensity of a glass sample with the increase of sample temperature, laser energy, and delay time in femtosecond laser-induced breakdown spectroscopy (fs-LIBS). In the experiment, the sample was uniformly heated from 22 degrees C to 200 degrees C, the laser energy was changed from 0.3 mJ to 1.8 mJ, and the delay time was adjusted from 0.6 mu s to 3.0 mu s. The results indicated that increasing the sample temperature could enhance the emission intensity and reduce the limits of detection, which is attributed to the increase in the ablated mass and the plasma temperature. And the spectral intensity increases with the increase of the laser energy and the delay time, however, the spectral line intensity no longer increases when the laser pulse energy and delay time reach a certain value. This study will lead to a further improvement in the applications of fs-LIBS. Published by AIP Publishing.