Miguel Soares Ferreira

Abstract
Laser-induced breakdown spectroscopy is a spectroscopic technique that allows for fast elemental mapping of heterogeneous samples. Yet, detailed maps need high-resolution sampling grids, which can turn the task into a time-consuming process and can increase sample damage. In this work, we present the implementation of an imaged-based intelligent mesh algorithm that makes use of superpixel segmentation to optimize elemental mapping processes. Our results show that the approach can increase the elemental mapping resolution and decrease acquisition times, fostering opportunities for applications that benefit from minimal sample damage such as heritage analysis, or timely analysis such as industrial applications. © 2022 The Author(s)

Abstract
Imaging the spatial distribution of chemical elements at a sample surface is a common application of laserinduced breakdown spectroscopy with vast scientific and technological applications. Yet, typical imaging solutions only explore the creation of two-dimensional maps, which can limit the interpretability of the results and further diagnostics in three-dimensional settings. Within this context, this work explores the combination of spectral imaging techniques and photogrammetry to deploy a versatile solution for the creation of threedimensional spectral imaging models. First, by making use of a numerical algorithm that is able to match features in the spectral image with those of the three-dimensional model, we show how to match the mesh from distinct sensor modalities. Then, we describe a possible visualization workflow, making use of dedicated photogrammetry and visualization software to easily deploy interactive models. Overall, the results demonstrate the versatility of our approach and pave for the development of novel spectral imaging diagnostic strategies that are able to deliver better qualitative analysis and insight in the three-dimensional space.

Abstract
Laser-induced breakdown spectroscopy (LIBS) is a technique that leverages atomic emission towards element identification and quantification. While the potential of the technology is vast, it still struggles with obstacles such as the variability of the technique. In recent years, several methods have exploited modifications to the standard implementation to work around this problem, mostly focused on the laser side to increase the signal-to-noise ratio of the emission. In this paper, we explore the effect of pulse duration on the detected signal intensity using a tunable LIBS system that consists of a versatile fiber laser, capable of emitting square-shaped pulses with a duration ranging from 10 to 100 ns. Our results show that, by tuning the duration of the pulse, it is possible to increase the signal-to-noise ratio of relevant elemental emission lines, an effect that we relate with the computed plasma temperature and associated density for the ion species. Despite the limitations of the work due to the low-resolution and small range of the spectrometer used, the preliminary results pave an interesting path towards the design of controllable LIBS systems that can be tailored to increase the signal-to-noise ratio and thus be useful for the deployment of more sensitive instruments both for qualitative and quantitative purposes. © 2022, Universidade do Porto - Faculdade de Engenharia. All rights reserved.

Abstract
One of the caveats of laser-induced breakdown spectroscopy technique is the performance for quantification purposes, in particular when the matrix of the sample is complex or the problem spans over a wide range of concentrations. These two questions are key issues for geology applications including ore grading in mining operations and typically lead to sub-optimal results. In this work, we present the implementation of a class of clustered regression calibration algorithms, that previously search the sample space looking for similar samples before employing a linear calibration model that is trained for that cluster. For a case study involving lithium quantification in three distinct exploration drills, the obtained results demonstrate that building local models can improve the performance of standard linear models in particular in the lower concentration region. Furthermore, we show that the models generalize well for unseen data of exploration drills on distinct rock veins, which can motivate not only further research on this class of methods but also technological applications for similar mining environments.

Abstract
Laser-induced breakdown spectroscopy allows fast chemical analysis of light elements without significant sample preparation, turning it into a promising technique for on-site mining operations. Still, the performance for quantification purposes remains its major caveat, obstructing a broader application of the technique. In this work, we present an extensive comparison of the performances of distinct algorithms for quantification of Lithium in a mining prospection stage, using spectra acquired with both a commercial handheld device and a laboratory prototype. Covering both linear and non-linear methodologies, the results show that, when covering a wide range of concentrations typical on a mining operation, non-linear methodologies manage to achieve errors compatible with a semi-quantitative performance, offering performances better than those obtained with linear methods, which are more affected by saturation and matrix effects. The findings enclosed offer support for future applications in the field and may possibly be generalized for other elements of interest in similar mining environments.