Elucidation of the chemical role of the pyroclastic materials on the state of conservation of mural paintings from Pompeii

Pyroclastic strata have always been thought to protect the archaeological remains of the Vesuvian area (Italy), hence allowing their conservation throughout the centuries. In this work, we demonstrate that they constitute a potential threat for the conservation state of the mural paintings of Pompeii. The ions that could be leached from them and the ion‐rich groundwater coming from the volcanic soil/rocks may contribute to salt crystallisation. Thermodynamic modelling not only allowed to predict which salts can precipitate from such leaching events but also assisted the identification of additional sources of sulfates and alkali metals to explain the formation of the sulfates identified in efflorescences from the mural paintings of Pompeii. For the future, fluorine, mainly related to a volcanic origin, can be proposed as a marker to monitor the extent of the impact in the mural paintings of Pompeii in situ

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

Hydrogen effects on copper, zinc and nickel atomic emission lines in argon radiofrequency glow discharge optical emission spectrometry

The effect of hydrogen (0.5%, 1% and 10% v/v) added to the argon plasma gas on the emission spectra of selected atomic lines for copper, zinc and nickel has been studied by radiofrequency glow discharge optical emission spectrometry (rf-GD-OES). Conductive homogeneous samples containing different concentrations of the elements under study in different matrices have been investigated. Results show different trends of the emission intensity lines with increasing hydrogen concentration in the rf-GD, depending on the line characteristics. In most cases, the emission yields of the lines under study did not change or increased when hydrogen was added to the discharge (no decreases were observed). The emission yields of certain lines showed much higher increases than other lines of the same element (for example, lines 213.86 nm of Zn and 231.10 nm of Ni). Our experiments indicate that such notorious increases could be related with the possible decrease of the self-absorption when hydrogen is added to the discharge. Overall, the results obtained for the emission yield changes of certain lines of a given element in different matrices (with different analyte content) showed that while for resonance emission lines very notorious increases are observed, the values for non-resonance lines do not change significantly (specially if the matrices employed are similar)

Mixed-stock and discriminant models use for assessing recruitment sources of estuarine fish populations in la Plata Basin (South America)

The objective of this study was to identify potential recruitment sources of Prochilodus lineatus from freshwater areas (Paraná and Uruguay rivers) to estuarine population of the Río de la Plata Estuary (La Plata Basin, South America), considering young (age-1) and adult (age-7) fish. LA-ICP-MS chemical analysis of the otolith core (nine element:Ca ratios) of an unknown mixed sample from Río de la Plata Estuary (2011 and 2017) was compared with a young-of-year baseline data set (same cohort) and classified into freshwater nurseries (Paraná or Uruguay river) by using maximum classification-likelihood models (MLE and MCL) and quadratic discriminant analysis (QDA). Considering the three models used, the Uruguay River was the most important contributor for both young and adult populations. The young population (2011) was highly mixed with contributions between 31.7 to 68.3%, while the degree of mixing was found to decrease in 2017 (adult fish) from 97.1 to 100% contributions. The three employed methods showed comparable estimates, however, the QDA showed a high similarity with the MCL model, suggesting sensitivity to evaluate small contributions, unlike the MLE method. Our results show the potential application of maximum likelihood mixture models and QDA for determining the relative importance of recruitment sources of fish in estuarine waters of the La Plata Basin.Fil: Avigliano, Esteban. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Parque Centenario. Unidad Ejecutora de Investigaciones en Producción Animal. Universidad de Buenos Aires. Facultad de Ciencias Veterinarias. Unidad Ejecutora de Investigaciones en Producción Animal; ArgentinaFil: Pisonero, Jorge. Universidad de Oviedo; EspañaFil: Bordel, Nerea. Universidad de Oviedo; EspañaFil: Dománico, Alejandro. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas; ArgentinaFil: Volpedo, Alejandra. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Parque Centenario. Unidad Ejecutora de Investigaciones en Producción Animal. Universidad de Buenos Aires. Facultad de Ciencias Veterinarias. Unidad Ejecutora de Investigaciones en Producción Animal; Argentin

An exploratory study of the potential of LIBS for visualizing gunshot residue patterns

The study of gunshot residue (GSR) patterns can assist in the reconstruction of shooting incidences. Currently, there is a real need of methods capable of furnishing simultaneous elemental analysis with higher specificity for the GSR pattern visualization. Laser-Induced Breakdown Spectroscopy (LIBS) provides a multi-elemental analysis of the sample, requiring very small amounts of material and no sample preparation. Due to these advantages, this study aims at exploring the potential of LIBS imaging for the visualization of GSR patterns. After the spectral characterization of individual GSR particles, the distribution of Pb, Sb and Ba over clothing targets, shot from different distances, were measured in laser raster mode. In particular, an array of spots evenly spaced at 800 mum, using a stage displacement velocity of 4 mm/s and a laser frequency of 5 Hz was employed (e.g. an area of 130 × 165 mm2 was measured in less than 3 h). A LIBS set-up based on the simultaneous use of two spectrographs with iCCD cameras and a motorized stage was used. This set-up allows obtaining information from two different wavelength regions (258&-289 and 446&-463 nm) from the same laser induced plasma, enabling the simultaneous detection of the three characteristic elements (Pb, Sb, and Ba) of GSR particles from conventional ammunitions. The ability to visualize the 2D distribution GSR pattern by LIBS may have an important application in the forensic field, especially for the ballistics area.Ministerio de Economía y Competitividad (MINECO

Comparison of the emission of a high-pressure sodium lamp working at 50 Hz and at high frequency

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