Application of laser-induced breakdown spectroscopy (libs) in industrial processes and archaeology

RESUMEN: La espectroscopía de ablación inducida por láser (LIBS) es una técnica de análisis elemental basada en la ablación de un material y la formación de un plasma por la acción de un pulso láser de energía alta que interacciona sobre un material objetivo. El análisis mediante espectroscopía de la luz emitida por ese plasma permite la caracterización del material por medio de la identificación de las líneas de emisión características de los elementos que conforman la muestra. En la presente tesis se utiliza la técnica LIBS en dos campos de aplicación distintos. Por un lado, se han analizado los metales adsorbidos en resinas quelantes usadas en gestión de residuos de procesos industriales. Por otro lado, la aplicación de LIBS en ejemplares arqueológicos de moluscos marinos ha permitido establecer una relación entre su composición y la temperatura del agua del mar.ABSTRACT: Laser-induced breakdown spectroscopy (LIBS) is an elemental analysis technique based on the ablation of a small portion of sample material and the formation of plasma by a high-energy laser pulse interacting with a target material. The spectroscopic analysis of the light emitted by this plasma allows the characterization of the material by identifying the characteristic emission lines of the elements present in the sample. In this thesis the LIBS technique is used in two different fields of application. On the one hand, the metals adsorbed on chelating resins used in waste management of industrial processes have been analyzed. On the other hand, the application of LIBS in archaeological specimens of marine mollusks has allowed us to establish a relationship between their composition and the temperature of the sea water

Using Mg/Ca ratios from the limpet Patella depressa Pennant, 1777 measured by laser-induced breakdown spectroscopy (LIBS) to reconstruct paleoclimate

Measurement of the elemental composition of shells is increasingly emerging as an avenue for obtaining high-resolution insights into paleoclimate and past seasonality. Several studies have shown significant correlations between Mg/Ca ratios measured on shell carbonate and the sea surface temperature (SST) within which this carbonate was precipitated. However, other investigations have reported large variability in this relationship between species. Therefore, further studies, including taxa previously not considered are still required in order to validate these new species as suitable climate proxies. Here, we measured Mg/Ca ratios for limpet Patella depressa Pennant, 1777 samples live-collected in northern Spain for the first time. The elemental ratio was measured using laser-induced breakdown spectroscopy (LIBS), a technique that significantly decreases the time required for sample preparation and increases the number of shells that can be analyzed. In this study, calibration-free LIBS (CF-LIBS) methods were applied to estimate molar concentrations of chemical elements on biogenic calcium carbonate. The Mg/Ca ratio evolution along the shell growth axis was compared with stable oxygen isotope (δ18O) profiles obtained from these same limpets and the SST at the place where the mollusk grew to determine if the sequences obtained correctly reflected environmental conditions during the life-span of the mollusk. The results showed a significant correlation between Mg/Ca ratio series and both δ18O profiles and SST, highlighting the paleoenvironmental and archaeological potential of LIBS analyses on this mollusk species that is frequently found in archaeological contexts in the western Europe.This research was performed as part of the projects HAR2016-75605-R, HAR2017-86262-P and PID2019-107270RB-C21/AEI/10.13039/501100011033, funded by the Spanish Ministry of Economy and Competitiveness, MINECO. During the development of this research A.G.E was funded by the Basque Country Postdoctoral Program through a postdoctoral grant (POS_2020_2_0032). This study has also been supported by the Prehistoric Research Consolidated Group of the Basque Country University (IT-1223-19), funded by the Basque Country Government. P.R. is funded by the Max Planck Society

Comparison of Mg/Ca concentration series from Patella depressa limpet shells using CF-LIBS and LA-ICP-MS

The elemental composition of marine mollusk shells can offer valuable information about environmental conditions experienced by a mollusk during its lifespan. Previous studies have shown significant correlations between Mg/Ca concentration ratios measured on biogenic carbonate of mollusk shells and sea surface temperature (SST). Here we propose the use of Laser-Induced Breakdown Spectroscopy (LIBS) and the validation of the Calibration-Free LIBS (CF-LIBS) approach for the rapid measurement and estimation of Mg/Ca molar concentration profiles within Patella depressa Pennant, 1777 limpet shells. To achieve these objectives, results derived from CF-LIBS methodology are compared with those obtained from an established analytical technique for this purpose, such as Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS). Concentration series obtained with both methodologies show defined temporal patterns and reflect the season-of-capture in each specimen. The results evidence a significant correlation (R2 = 0.63–0.81) between CF-LIBS and LA-ICP-MS Mg/Ca molar concentration profiles within four live-collected P. depressa shells. Averaged error for the molar concentration estimated with CF-LIBS was lower than 10% in every specimen. The comparison between the results obtained from two techniques used in this study has allowed us to demonstrate for the first time that Mg/Ca molar concentration measured in biogenic carbonates were accurately inferred using CF-LIBS technique. The CF-LIBS approach validation represents great potential for the rapid and large-scale paleoenvironmental and archaeological analysis of this mollusk species, which is frequently found in archaeological sites.1. Introduction 2. Materials and methods 2.1. Sample preparation 2.2. LA-ICP-MS setup and analyses 2.3. LIBS setup and measurements 2.4. CF-LIBS application 3. Results and discussion 3.1. LA-ICP-MS concentration profiles 3.2. CF-LIBS approach results 3.3. CF-LIBS and LA-ICP-MS comparison 3.4. Implications for paleoclimatology and archaeology 4. Conclusion

Correlations and predictions about viscosity of binary and ternary liquid mixtures

Ingeniería químic

On-line monitoring and defect detection of arc-welding via plasma optical spectroscopy and LIBS

Plasma optical spectroscopy and laser-induced breakdown spectroscopy (both on and off-line) are used in this work to analyze the effects of different perturbations applied to a tungsten inert gas welding process. This approach enables the analysis and comparison of the spectra acquired with the two setups, thus providing more information about the process evolution and dynamics and the resulting chemical composition of the seams. It will be demonstrated that, in agreement with previous studies, the analysis of different elements gives rise to rich information regarding the resulting weld quality, thus enabling the on-line monitoring of arc-welding processes. Elements such as lithium or sodium, not commonly employed in spectroscopic analysis of welding processes, will prove to provide interesting information on surface defects and contamination. Additionally, LIBS 2D scanning of the performed seams will enable a detailed analysis of the resulting elemental distributions.This work is part of the project R+D project PID2019-107270RB-C21 funded by MCIN/ AEI /http://dx.doi.org/10.13039/501100011033

Comparison of light capturing approaches in Laser-Induced Breakdown Spectroscopy (LIBS) for multichannel spectrometers

LIBS technique requires the spectroscopic analysis of the light emitted by a laser-induced plasma plume. One challenge of the different approaches to capture the plasma light emission is the significant shot-to-shot variations of the plume inhomogeneities, position, and morphology. This is even more challenging when multichannel CCD spectrometers are used, because the light should be homogeneously divided among multiple capturing optical fibers (typically up to 8 fibers) with stable spectral efficiency for all channels. Otherwise, any further analysis of the atomic emission spectra involving multiple channels, such as line intensity ratios, Boltzmann plots, or calibration-free LIBS, could be compromised by the morphology-dependent spectral artifacts induced by the collection optics. In this work, we assess the performance of several collection optics in terms of overall capturing efficiency and channel-to-channel variations due to changes in plasma morphology. Results clearly show that this could be an issue even with the approaches with the best spatial homogenization, including optical fibers and Köhler optics.This work was supported by the R + D project PID2019-107270RBC21 (funded by MCIN/AEI10.13039/501100011033) and by Plan Nacional de I + D + and Instituto de Salud Carlos III (ISCIII), Subdirección General de Redes y Centros de Investigación Cooperativa, Ministerio de Ciencia, Innovación y Universidades, Spanish Network for Research in Infectious Diseases (REIPI RD16/0016/0007), CIBERINFEC (CB21/13/00068), CIBER-BBN (BBNGC1601), cofinanced by European Development Regional Fund “A way to achieve Europe”. A. O.-S was financially supported by the Miguel Servet II program (ISCIIICPII17–00011). AGE was supported by the Catalonia Government throughout a Beatriu de Pin´os fellowship (grant number 2020 BP 00240). We thanks Dr. A. Pic´on for providing the pure iron ingot and helpful suggestions to improve the experimental setup

Split regeneration of chelating resins for the selective recovery of nickel and copper

The management of spent acids containing heavy metals has been traditionally carried out by neutralization-precipitation technologies that often fail to provide the required selectivity for metal recovery. This work proposed a split elution process using H2SO4 and NH4OH solutions to regenerate bispicolylamine-based chelating resins (Puromet™ MTS9600) employed in a previous work to separate nickel and copper from spent sulfuric acid effluents. Operation variables namely S/L ratio, concentration of the regeneration agents and process configuration were analysed to select the best conditions to optimize the metal unloading and their selective recovery in independent solutions. It was found that 43% of nickel was eluted from the resin by H2SO4 2.0 M and recovered with purities of 98% while 47% of copper was desorbed with NH4OH 2.0 M and recovered with purities of 97%. The long-term assessment evidenced that copper removal and metal recovery were not affected after 10 adsorption-regeneration cycles, while the nickel adsorption efficacy decreased about 10%.This research was developed in the framework of the projects CTM2017-87740-R (Spanish Ministry of Science, Innovation and Universities), RTI2018-093310-B-I00 (Spanish Ministry of Science, Innovation and Universities), TEC2016-76021-C2-2-R) (AEI/FEDER, UE & PID2019-107270RB-C21/AEI/10.13039/501100011033), and grant BES-2017-080076

Comparison of Mg/Ca concentration series from Patella depressa limpet shells using CF-LIBS and LA-ICP-MS

The elemental composition of marine mollusk shells can offer valuable information about environmental conditions experienced by a mollusk during its lifespan. Previous studies have shown significant correlations between Mg/Ca concentration ratios measured on biogenic carbonate of mollusk shells and sea surface temperature (SST). Here we propose the use of Laser-Induced Breakdown Spectroscopy (LIBS) and the validation of the Calibration-Free LIBS (CF-LIBS) approach for the rapid measurement and estimation of Mg/Ca molar concentration profiles within Patella depressa Pennant, 1777 limpet shells. To achieve these objectives, results derived from CF-LIBS methodology are compared with those obtained from an established analytical technique for this purpose, such as Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS). Concentration series obtained with both methodologies show defined temporal patterns and reflect the season-of-capture in each specimen. The results evidence a significant correlation (R2 = 0.63-0.81) between CF-LIBS and LA-ICP-MS Mg/Ca molar concentration profiles within four live-collected P. depressa shells. Averaged error for the molar concentration estimated with CF-LIBS was lower than 10% in every specimen. The comparison between the results obtained from two techniques used in this study has allowed us to demonstrate for the first time that Mg/Ca molar concentration measured in biogenic carbonates were accurately inferred using CF-LIBS technique. The CF-LIBS approach validation represents great potential for the rapid and large-scale paleoenvironmental and archaeological analysis of this mollusk species, which is frequently found in archaeological sites.This research was performed as part of the projects HAR2016-75605-R and HAR2017-86262-P funded by the Spanish Ministry of Economy and Competitiveness, MINECO. This work is also part of the projects PID2019-107270RB-C21 and MCI-21-PID2020-113951-GB-I00 funded by MCIN/AEI/10.13039/501100011033 and FEDER “A way to make Europe”. This investigation was also supported by the Alexander von Humboldt Foundation thought a Humboldt Research Fellowship (no code available). This study is also part of the project PID2021-126937NB-I00 (PALEOCROSS) funded by MCIN/AEI/10.13039/501100011033 and by ERDF "A way of making Europe”. MMM research was funded by predoctoral grant BES-2017-080076 from MINECO. During the development of this research AGE was funded by the Basque Country Postdoctoral Programme (grant number POS_2020_2_0032), by the University of La Rioja through a postdoctoral grant (no code available) and he is currently supported by the Catalonia Postdoctoral Programme through a Beatriu de Pinós fellowship (grant number 2020 BP 00240). This study has also been supported by the Prehistoric Research Consolidated Group of the Basque Country University (IT-1435-22), funded by the Basque Country Government. We would also like to thank the Max Planck Society for funding, as well as the Universidad de Cantabria (UC), Instituto Internacional de Investigaciones Prehistóricas de Cantabria (IIIPC), Grupo de Ingeniería Fotónica (GIF), University of the Basque Country (UPV/EHU) and University of La Rioja (UR) for providing support