Laser-induced breakdown spectroscopy (LIBS) is a technique that provides an accurate in situ quantitative chemical analysis and, thanks to the developments in new spectral processing algorithms in the last decade, has achieved a promising performance as a quantitative chemical analyzer at the atomic level. These possibilities along with the fact that little or no sample preparation is necessary have expanded the application fields of LIBS. In this paper, we review the state of the art of this technique, its fundamentals, algorithms for quantitative analysis or sample classification, future challenges, and new application fields where LIBS can solve real problems.
A new technique is presented in this paper for the analysis of welding process emission spectra to accurately estimate in real-time the plasma electronic temperature. The estimation of the electronic temperature of the plasma, through the analysis of the emission lines from multiple atomic species, may be used to monitor possible perturbations during the welding process. Unlike traditional techniques, which usually involve peak fitting to Voigt functions using the Levenberg–Marquardt recursive method, sub-pixel algorithms are used to more accurately estimate the central wavelength of the peaks. Three different sub-pixel algorithms will be analysed and compared, and it will be shown that the LPO (linear phase operator) sub-pixel algorithm is a better solution within the proposed system. Experimental tests during TIG-welding using a fibre optic to capture the arc light, together with a low cost CCD-based spectrometer, show that some typical defects associated with perturbations in the electron temperature can be easily detected and identified with this technique. A typical processing time for multiple peak analysis is less than 20 ms running on a conventional PC.
Biogenic carbonate mollusc shells have the unique property of being a durable material found in many archaeological and geological sites, recording in their shell chemical composition the ambient environmental conditions during the mollusc's lifespan. In particular, mollusc shell Mg/Ca ratios have been suggested to be related to seawater temperature, although such a relationship is controversial and appears to be species-and even location-specific. This study investigates the use of Laser-Induced Breakdown Spectroscopy (LIBS) for the rapid 2 measurement of Mg/Ca profiles within Patella vulgata shells, via comparison with one established analytical technique that is most often used for this purpose, ICP-OES. LIBS offers some advantages over other spectrometric techniques, including ICP-OES, the latter requiring initial micromilling of sample powders. LIBS offers faster measurement, reduced sample preparation, easier automation and less complex and lower cost instrumentation. A high correlation is evident between LIBS and ICP-OES Mg/Ca profiles within four archaeological P. vulgata shells, as well as strong similarities between LIBS measurements made in two different areas of each P. vulgata shell (i.e. the apex and a more conventional transect along the axis of shell growth). Validation of the LIBS technique for determination of Mg/Ca profiles within P. vulgata shells has implications for archaeological studies, because a greater number of shell specimens sampled from each archaeological site and chronological level can be measured, thereby improving the statistical robustness of data interpretation and conclusions. One example archaeological application that would benefit from application of the LIBS technique is identification of the season-of-capture of marine molluscs as a food resource for prehistoric societies.
A new plasma spectroscopy analysis technique based on the generation of synthetic spectra by means of optimization processes is presented in this paper. The technique has been developed for its application in arc-welding quality assurance. The new approach has been checked through several experimental tests, yielding results in reasonably good agreement with the ones offered by the traditional spectroscopic analysis technique.
The chemical composition of mollusk shells offers information about environmental conditions present during the lifespan of the organism. Shells found in geological deposits and in many archeological sites can help to reconstruct past climatic conditions. For example, a correlation has been found between seawater temperature and the amount of some substituent elements (e.g., magnesium, strontium) in the biogenerated calcium carbonate matrix of the shell, although it is very species-specific. Here we propose the use laser-induced breakdown spectroscopy (LIBS) to estimate Mg/Ca ratios in modern specimens of the common limpet Patella vulgata. An automated setup was used to obtain a sequence of Mg/Ca ratios across a sampling path that could be compared with the seawater temperatures recorded during the organism's lifespan. Results using four shells collected in different months of the year showed a direct relationship between the Mg/Ca ratios and the seawater temperature, although the sequences also revealed small-scale (short-term) variability and an irregular growth rate. Nevertheless, it was possible to infer the season of capture and the minimum and maximum seawater temperatures from the LIBS sequences. This fact, along with the reduction in sampling and measurement time compared with other spectrometric techniques (such as inductively coupled plasma mass spectrometry [ICP-MS]), makes LIBS useful in paleoclimatic studies.
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