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Publications

Publications by Diana Filipa Guimarães

2022

Effects of Pulse Duration in Laser-induced Breakdown Spectroscopy

Authors
Ferreira, MFS; Silva, NA; Guimarães, D; Martins, RC; Jorge, PAS;

Publication
U.Porto Journal of Engineering

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.

2022

Special issue on biological and biomedical applications of X-ray spectrometry

Authors
Pessanha, S; Silva, AL; Guimaraes, D;

Publication
X-RAY SPECTROMETRY

Abstract

2022

Towards robust calibration models for laser-induced breakdown spectroscopy using unsupervised clustered regression techniques

Authors
Silva N.A.; Capela D.; Ferreira M.; Gonçalves F.; Lima A.; Guimarães D.; Jorge P.A.S.;

Publication
Results in Optics

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.

2022

Comprehensive comparison of linear and non-linear methodologies for lithium quantification in geological samples using LIBS

Authors
Ferreira, MFS; Capela, D; Silva, NA; Goncalves, F; Lima, A; Guimaraes, D; Jorge, PAS;

Publication
SPECTROCHIMICA ACTA PART B-ATOMIC SPECTROSCOPY

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.

2025

Tracing the Geochemical History of Eocene Fish Using X-ray Fluorescence

Authors
R Pereira, L; Braçais, M; Capela, D; Silva, NA; Jorge, AS; Guerner, A; Silva, SO; Frazão, O; Guimarães, D;

Publication
EPJ Web of Conferences

Abstract
A study of an Eocene fish fossil using portable XRF revealed distinct geochemical differences between the fossil and surrounding sediment. Elements like uranium, yttrium, arsenic, and phosphorus were found only in the fossil, while calcium and iron appeared in both regions. These patterns point to selective elemental incorporation during early fossilization and diagenesis processes. The results highlight XRF's usefulness in verifying fossil authenticity, provenance and understanding the chemical processes during fossilization. © 2025 Elsevier B.V., All rights reserved.

2025

K-Feldspar Geochemistry as an Indicator of Lithium Mineralization in the Barroso-Alvão Aplite-Pegmatite Field, Northern Portugal

Authors
Filipa Dias; Ricardo Ribeiro; Filipe Gonçalves; Alexandre Lima; Encarnación Roda-Robles; Tânia Martins; Diana Guimarães;

Publication
The Canadian Journal of Mineralogy and Petrology

Abstract
Abstract Inductively coupled plasma-mass spectrometry analysis was conducted to examine the geochemical composition of K-feldspars from various aplite-pegmatites in the Barroso-Alvão field, focusing on the differences between Li-rich and Li-barren aplite-pegmatites. The study revealed significant variations in the concentrations of minor and trace elements (Rb, Tl, Li, Ga, Pb, Cs, Ba, Be, Ta, and Sn) present in the K-feldspars of Li-barren, spodumene-rich, and petalite-rich aplite-pegmatites. The data also indicate a geographical trend in both mineralogy and geochemistry across the aplite-pegmatites of the Barroso-Alvão field. Li-barren aplite-pegmatites are more concentrated in the southeast, spodumene-rich dominate the center, and petalite-rich varieties are more common in the northwest. Additionally, portable X-ray fluorescence analysis was performed on the crystals of the same samples to evaluate the feasibility of in situ geochemical analysis of K-feldspars, aiming to determine whether an aplite-pegmatite can be quickly identified as Li-rich. This approach seeks to provide a rapid field assessment of whether an aplite-pegmatite justifies further exploration for Li mining. Notably, the trace amounts of Li, Sn, P, and Ta found in K-feldspars are likely due to mineral inclusions of spodumene, cassiterite, apatite, and columbite–tantalite minerals, as observed petrographically in one of these Li-rich aplite-pegmatites.

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