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.

A flowing atmospheric pressure afterglow as an ion source coupled to a differential mobility analyzer for volatile organic compound detection.

Atmospheric pressure glow discharges have been widely used in the last decade as ion sources in ambient mass spectrometry analyses. Here, an in-house flowing atmospheric pressure afterglow (FAPA) has been developed as an alternative ion source for differential mobility analysis (DMA). The discharge source parameters (inter-electrode distance, current and helium flow rate) determining the atmospheric plasma characteristics have been optimized in terms of DMA spectral simplicity with the highest achievable sensitivity while keeping an adequate plasma stability and so the FAPA working conditions finally selected were: 35 mA, 1 L min(-1) of He and an inter-electrode distance of 8 mm. Room temperature in the DMA proved to be adequate for the coupling and chemical analysis with the FAPA source. Positive and negative ions for different volatile organic compounds were tested and analysed by FAPA-DMA using a Faraday cup as a detector and proper operation in both modes was possible (without changes in FAPA operational parameters). The FAPA ionization source showed simpler ion mobility spectra with narrower peaks and a better, or similar, sensitivity than conventional UV-photoionization for DMA analysis in positive mode. Particularly, the negative mode proved to be a promising field of further research for the FAPA ion source coupled to ion mobility, clearly competitive with other more conventional plasmas such as corona discharge.

Use of radiofrequency power to enable glow discharge optical emission spectroscopy ultrafast elemental mapping of combinatorial libraries with nonconductive components: nitrogen-based materials.

Combinatorial chemistry and high-throughput techniques are an efficient way of exploring optimal values of elemental composition. Optimal composition can result in high performance in a sequence of material synthesis and characterization. Materials combinatorial libraries are typically encountered in the form of a thin film composition gradient which is produced by simultaneous material deposition on a substrate from two or more sources that are spatially separated and chemically different. Fast spatially resolved techniques are needed to characterize structure, composition, and relevant properties of these combinatorial screening samples. In this work, the capability of a glow discharge optical emission spectroscopy (GD-OES) elemental mapping system is extended to nitrogen-based combinatorial libraries with nonconductive components through the use of pulsed radiofrequency power. The effects of operating parameters of the glow discharge and detection system on the achievable spatial resolution were investigated as it is the first time that an rf source is coupled to a setup featuring a push-broom hyperspectral imaging system and a restrictive anode tube GD source. Spatial-resolution optimized conditions were then used to characterize an aluminum nitride/chromium nitride thin-film composition spread. Qualitative elemental maps could be obtained within 16.8 s, orders of magnitude faster than typical techniques. The use of certified reference materials allowed quantitative elemental analysis maps to be extracted from the emission intensity images. Moreover, the quantitative procedure allowed correcting for the inherent emission intensity inhomogeneity in GD-OES. The results are compared to quantitative depth profiles obtained with a commercial GD-OES instrument.

Critical evaluation of the potential of radiofrequency pulsed glow discharge-time-of-flight mass spectrometry for depth-profile analysis of innovative materials.

The combination of radiofrequency pulsed glow discharge (RF-PGD) analytical plasmas with time-of-flight mass spectrometry (TOFMS) has promoted the applicability of this ion source to direct analysis of innovative materials. In this sense, this emerging technique enables multi-elemental depth profiling with high depth resolution and sensitivity, and simultaneous production of elemental, structural, and molecular information. The analytical potential and trends of this technique are critically presented, including comparison with other complementary and well-established techniques (e.g. SIMS, GD-OES, etc.). An overview of recent applications of RF-PGD-TOFMS is given, including analysis of nano-structured materials, coated-glasses, photovoltaic materials, and polymer coatings.

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.

Thickness determination of subnanometer layers using laser ablation inductively coupled plasma mass spectrometry.

Laser ablation inductively coupled plasma mass spectrometry has been applied to determine the thickness of subnanometer (subnm) metallic layers. Metallic Nd was deposited onto Si wafers with 0.5, 1, 3, and 6 nm thickness and covered by a 10 nm Al coating. Integrated ion signals corresponded to the layer thickness, indicating that external calibration provides accurate data. Utilizing sensitivity ratios obtained from ablation of a glass standard reference material (SRM) and the Al layer as reference, the deviations between prepared and measured layer thickness were less than 10%. A further attempt was made to determine the layer thickness with the absolute sensitivity obtained from ablation of a glass SRM. The approach also yielded a linear correlation between determined and actual layer thickness, but bias and interday variability were significantly higher. This is assumed to result from imprecise determination of the crater size when ablating the glass SRM. This study shows that subnm layers of metals can be analyzed for their thickness either using reference materials of identical composition or using sensitivity ratios when one layer can be used as a reference. Absolute determination of the layer thickness is less accurate but can circumvent the lack of reference materials of similar composition.

Pulsed radiofrequency glow discharge time-of-flight mass spectrometry for nanostructured materials characterization.

Progress in the development of advanced materials strongly depends on continued efforts to miniaturizing their structures; thus, a great variety of nanostructured materials are being developed nowadays. Metallic nanowires are among the most attractive nanometer-sized materials because of their unique properties that may lead to applications as interconnectors in nanoelectronic, magnetic, chemical or biological sensors, and biotechnological labels among others. A simple method to develop self-ordered arrays of metallic nanowires is based on the use of nanoporous anodic alumina (NAA) and self-assembled nanotubular titanium dioxide membranes as templates. The chemical characterization of nanostructured materials is a key aspect for the synthesis optimization and the quality control of the manufacturing process. In this work, the analytical potential of pulsed radiofrequency glow discharge with detection by time-of-flight mass spectrometry (pulsed rf-GD-TOFMS) is investigated for depth profile analysis of self-assembled metallic nanostructures. Two types of nanostructured materials were successfully studied: self-assembled NAA templates filled with arrays of single metallic nanowires of Ni as well as arrays of multilayered Au/FeNi/Au and Au/Ni nanowires and nanotubular titanium dioxide templates filled with Ni nanowires, proving that pulsed rf-GD-TOFMS allows for fast and reliable depth profile analysis as well as for the detection of contaminants introduced during the synthesis process. Moreover, ion signal ratios between elemental and molecular species (e.g., (27)Al(+)/(16)O(+) and (27)Al(+)/(32)O(2)(+)) were utilized to obtain valuable information about the filling process and the presence of possible leaks in the system.

Chemometrics and elemental mapping by portable LIBS to identify the impact of volcanogenic and non-volcanogenic degradation sources on the mural paintings of Pompeii.

Crystallization of soluble salts is a common degradation phenomenon that threatens the mural paintings of Pompeii. There are many elements that contribute to the crystallization of salts on the walls of this archaeological site. Notably, the leachates of the pyroclastic materials ejected in 79 AD by Mount Vesuvius and local groundwater, rich in ions from the erosion of volcanic rocks. Both sources could contribute to increase the concentration of halides (fluorides and chlorides) and other salts in these walls. The distribution of volcanogenic salts and their impact on the conservation of Pompeian mural paintings have however not yet been fully disclosed. In this work, an analytical methodology useful to determine the impact of the main sources of degradation affecting the mural paintings of Pompeii is presented. This methodology combines the creation of qualitative distribution maps of the halogens (CaF and CaCl) and related alkali metals (Na and K) by portable Laser Induced Breakdown Spectroscopy (LIBS) and a subsequent Principal Component Analysis of these data. Such maps, together with the in-situ identification of sulfate salts by portable Raman spectroscopy, provided information about the migration and distribution of volcanogenic halides and the influence of ions coming from additional sources (marine aerosol and modern consolidation mortars). Additionally, the thermodynamic modeling developed using the experimentally determined ionic content of Pompeian rain- and groundwater allowed to determine their specific role in the formation of soluble salts in the mural paintings of Pompeii.

Otoliths as indicators for fish behaviour and procurement strategies of hunter-gatherers in North Patagonia.

This study evaluates the potential use of archaeological otoliths of Genidens barbus (Cuvier and Valenciennes) as a tool to study fish behavior and hunter-gatherers procurement strategies on the North Patagonian coast. The studied samples come from the San Antonio archaeological locality dated at ca. 1000-800 14C yr BP (Late Holocene). To assess whether exposure to fire significantly affects the otolith Sr:Ca and Ba:Ca ratios, burned and unburned modern lapilli otoliths have been analyzed by Laser Ablation Inductively Coupled Plasma Mass Spectrometry and no statistically significant differences were found between the results of both treatments. Core-to-edge chemical time series were carried out on ancient otoliths (ca. 1000 14C yr BP) in order to study the fish life history. Three amphidromous patterns were found for ancient samples. The capture environments and seasons inferred by the otolith edge chemistry and marginal increase, respectively, suggest a location in high salinity water (estuary and sea) in summer. Finally, to estimate the size of archaeological fish, a linear regression between total length and otolith length was constructed using 70 modern catfish otoliths. The size variability (358-610 mm) might indicate the use of non-selective capture techniques, probably nets, by hunter-gatherer groups.

Volatile organic compound analysis by pulsed glow discharge time of flight mass spectrometry as a structural elucidation tool.

Pulsed glow discharge (PGD) coupled to time of flight mass spectrometry (TOFMS) has been investigated for volatile organic compound (VOC) identification and determination. Optimization of PGD operational conditions (chamber design, applied power, pressure and duty cycle) was performed using acetone and benzene as model compounds. During the different optimizations, molecular, fragment and elemental information were obtained when characteristic GD pulse regions were measured. An exploratory study for several VOCs (lineal hydrocarbons, oxygen-containing compounds and aromatic compounds) revealed the capability of the PGD to provide crucial information to elucidate structures (fragments), molecular ions or even proton affinity nature of the molecules; this last information is a consequence of the enriched proton environment generated along the afterglow region for the ionization chamber used. Analytical characteristics were evaluated with solid phase microextraction-gas chromatography coupled to PGD-TOFMS for special aromatic hydrocarbons (benzene, toluene, ethylbenzene, xylene: BTEX) in water, showing a good performance in terms of reproducibility and sensitivity. Copyright © 2017 John Wiley & Sons, Ltd.

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 800µm, using a stage displacement velocity of 4mm/s and a laser frequency of 5Hz was employed (e.g. an area of 130×165mm2 was measured in less than 3h). 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 446-463nm) 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.

Analytical potential of a laser ablation-glow discharge-optical emission spectrometry system for the analysis of conducting and insulating materials.

The analytical capabilities of a glow discharge (GD) as a secondary source for excitation/ionization of the material provided by laser ablation (LA) have been compared to conventional laser induced breakdown spectroscopy (LIBS). In LA-GD both sources can be independently adjusted to optimize the sampling process and then its subsequent excitation. This could involve a number of analytical performance advantages, such as reduced matrix dependence, greater precision and sensitivity than those encountered in LIBS. For such purpose, an ablation chamber design including two electrodes to generate the GD discharge has been built and assayed. A comparison between LIBS and LA-GD-OES has been carried out, both, under reduced argon and helium atmospheres. Different sets of samples (conducting reference materials, glass and fluorine pellets) have been used to evaluate the novel coupled technique. The LA-GD coupled system has shown to provide lower detection limits. In addition, best linear correlations between intensities and concentrations and lower matrix effects have also been found using the coupled system. Moreover, special advantages of the LA-GD-OES have also been demonstrated for the analysis of fluorine.

Characterization of a new mobility separation tool: HRIMS as differential mobility analyzer.

High resolution ion mobility spectrometer (HRIMS) is a new instrument that uses parallel plate Differential Mobility Analysis as principle of separation. Gas phase analysis of volatile organic compounds (VOCs) has been performed for the characterization of this new mobility system using an UV-lamp for ionization. Studies of the effect of temperature and the presence of a desiccant are detailed. Identification of the different peaks obtained with an electrometer was successfully carried out for a group of alcohols, aromatic compounds and ketones (ethanol, 1-propanol, isopropanol, 1-butanol, 1-pentanol, 1-heptanol, acetone, 2-butanone, 2-pentanone, 2-octanone, benzene, toluene, xylene and bromobenzene) following a modified Millikan equation. Moreover, the investigation of the discrimination capabilities within the different VOCs families as well as the mobility dependence with molecular mass was successfully achieved.

RF-pulsed glow discharge time-of-flight mass spectrometry for glass analysis: investigation of the ion source design.

Radiofrequency (RF) millisecond pulsed glow discharge (PGD) coupled to time-of-flight mass spectrometry (TOFMS) was investigated for direct elemental analysis of glass samples. Aiming at achieving highest elemental sensitivity, appropriate discrimination from polyatomics, and good crater shapes on glasses, a new Grimm-type GD chamber (termed from now "UNIOVI GD", designed and constructed in our laboratory) was coupled to TOFMS, and the results compared with those obtained with the former GD design (here denominated as "GD.1") of the initial RF-PGD-TOFMS prototype. The critical differences distinguishing the two GDs under scrutiny are the GD chamber thickness (15.5 mm for the GD.1 and 7 mm for the UNIOVI GD) and the "flow tube" which is inserted in the GD.1 and inexistent in UNIOVI GD. A pulse period of 4 ms and a duty cycle of 50% were selected for the PGD studies. In order to characterizing the UNIOVI GD, the effect of RF-PGD experimental conditions (pressure and power) on signal shapes along the pulse was first investigated. Then, the analytical performance achieved was compared with results obtained using the GD.1 chamber. Results show that the UNIOVI GD source induced less thermal stress on the glass specimens. Consequently higher GD power can be applied to the UNIOVI GD (up to at least 130 W), as compared to the GD.1 (maximum of 60 W), without glass sample breakdown. Also, better crater shapes on samples were obtained using the UNIOVI GD. Moreover, the detection limits attained with the UNIOVI GD (in the range of µg g(-1)) were in most cases about one order of magnitude better for the analytes investigated (B, Na, Al, Si, Mn, Ni, Co, Cu, Zn, As, Sr, Ag, In, Sn, Sb, Ba, Pb and Bi), than those observed using the GD.1.

Evaluation of pulsed radiofrequency glow discharge time-of-flight mass spectrometry for precious metal determination in lead fire assay buttons.

In this paper, an exploration of the capabilities and limitations of pulsed radiofrequency glow discharge time-of-flight mass spectrometry (GD-TOFMS) for the determination of the precious metals Ag, Au, Pd, Pt and Rh in lead buttons obtained by Pb fire assay is reported on. Since the matrix consists almost entirely of lead (>99%), the occurrence of doubly charged Pb (Pb(2+)) ions can hinder accurate determination of Rh. This problem was counteracted by relying on the time-resolved formation of different ion types over the pulse period of the glow discharge, which allows discrimination against the Pb(2+) ions. The formation of ArCu(+) ions as a result of the use of a copper anode was assessed to pose no threat to the accuracy of the results obtained for the set of samples analyzed as its contribution to the total signal at m/z=103 could be adequately corrected for. The method developed was evaluated in terms of accuracy and precision using a set of Pb button standards with analyte concentrations between 5 and 100 µg g(-1). For the purpose of validation, a 10 µg g(-1) standard was considered as a sample. Overall, an acceptable accuracy was obtained with a bias of <5% between the experimental results and the corresponding reference values, except for Au, for which a larger deviation occurred. Precision values (repeatability) of typically <5% relative standard deviation (RSD) (for N=3) were obtained and the limits of detection (LODs) vary from ~0.020 µg g(-1) for Ag to ~0.080 µg g(-1) for Pt.

Pulsed radiofrequency glow discharge time-of-flight mass spectrometry for molecular depth profiling of polymer-based films.

We demonstrate the potential of an innovative technique, pulsed radiofrequency glow discharge time-of-flight mass spectrometry, for the molecular depth profiling of polymer materials. The technique benefits from the presence, in the afterglow of the pulsed glow discharge, of fragment ions that can be related to the structures of the polymers under study. Thin films of different polymers (PMMA, PET, PAMS, PS) were successfully profiled with retention of molecular information along the profile. Multilayered structures of the above polymers were also profiled, and it was possible to discriminate among layers having similar elemental composition but different polymer structure.

Nitrogen effects in multi-matrix calibrations by radiofrequency glow discharge--optical emission spectrometry.

A study about the effect of nitrogen in the calibration curves of a series of analytical emission lines has been carried out in this work. Fifteen reference materials with different matrices (Fe, Al, Zn, Cu and Ni) were used (three of these reference materials contain nitrogen in their composition) and plots of intensity versus the product "sputtering rate times element concentration" were constructed for emission lines of the analytes considered in this work (Al, Fe, Cu, Cr, C, Mo, Zn, Si, Ti and Ni). Two different fits were performed in each plot, first considering only the points corresponding to samples without nitrogen in their composition and secondly including all the points. The results show almost negligible differences in the emission yields calculated. On the other hand, a mixture of Ar containing 0.5% N2 was employed to check if the nitrogen effect was present at higher concentrations than those expected in analysis when samples with high nitrogen concentrations are used. Differences between the slopes of the calibration curves with the Ar/N2 and pure Ar discharges were obtained (up to 30%). A study of the molecular bands recorded in the spectra when nitrogen is present in the discharge and determination of the resulting interferences on the analytes have been performed.

Quantification of bromine in flame-retardant coatings by radiofrequency glow discharge-optical emission spectrometry.

There is an increasing concern regarding the toxicity and environmental distribution and impact of brominated organic compounds employed as flame retardants. Thus, present interest in searching for new analytical techniques and methods allowing a rapid, simple and reliable detection of those compounds in materials and wastes potentially containing such flame retardants is not surprising. The feasibility of using radiofrequency glow discharge plasma spectrometry coupled with optical emission spectrometry (rf-GD-OES) as a rapid and simple tool to directly analyse bromine-containing flame-retardant polymeric layers is investigated here. Polymeric layers for calibration were made by mixing appropriate amounts of tetrabromobisphenol A, bisphenol A, phloroglucinol and diphenylmethane-4,4'-diisocyanate in tetrahydrofuran. The corresponding blanks (polymers without tetrabromobisphenol A) were also prepared. Detection of bromine was investigated both in the visible (at 470.48 nm) and in the near-infrared (at 827.24 nm) regions, using a charge-coupled device for detection. Discharge parameters affecting the emission intensity of bromine were first optimized (in argon and helium as possible plasma gases) and the analytical performance characteristics were then evaluated. The best detection limit (0.044% Br) was achieved measuring Br I 827.24 nm in a He discharge, using a forward power of 70 W and a pressure of 45 Torr. The linearity range extended up to 27% Br. Finally, the applicability of the rf-GD-OES method proposed to the quantitative analysis of bromine in solid materials coated with flame-retardant commercial paints was successfully demonstrated.

In-depth profile analysis of thin films deposited on non-conducting glasses by radiofrequency glow-discharge-optical emission spectrometry.

The potential of radiofrequency glow-discharge-optical emission spectrometry (rf-GD-OES) for quantification of thin films on non-conducting materials has been investigated. A commercial rf-GD chamber from Jobin Yvon operated at 13.56 MHz with Ar as discharge gas was used. The signal integration time was 0.1 s. The effect on emission yields of thin conducting layers on glasses of different thickness was studied in detail, using the rf-GD in the common operating mode "constant pressure-constant forward power". Calibration curves were obtained for two types of material-conducting reference materials and a set of non-conductors comprising homogeneous glass of known composition and three different thicknesses coated (or not) with thin layers of gold. Qualitative and quantitative in-depth profile analyses of different coated non-conducting samples were investigated. A variety of samples, including different thick glass substrates (from 1.8 to 5.8 mm), different thin films deposited on homogeneous glasses (from 6 nm to 35 nm), and different kinds of coating (conductors such as Fe, Ni, Cr, Al, and Nb and non-conductors such as Si3N4) were studied at 450 Pa pressure and 20 W forward power. The quantitative in-depth profiles proved satisfactory and results for depths and concentrations were similar to nominal values.

Depth profiling with modified dc-Grimm and rf-Grimm-type glow discharges operated with high gas flow rates and coupled to a high-resolution mass spectrometer.

The improved analytical capability of direct-current (dc) and radiofrequency (rf) "fast flow" glow discharges coupled to a sector field mass spectrometer (GD-SFMS) are presented. In particular, the effect of GD chamber design has been studied to obtain suitable crater shapes for depth-profile analysis of solid samples while maintaining the high sensitivity and stability of this source. In this study it was observed that the distance between the sample surface and the end of the flow tube is critical and so careful optimisation is needed. Under optimum conditions plane crater profiles, with high ion-signal sensitivity and sufficient stability, were obtained. The capability to determine qualitative and semi-quantitative depth profiles is presented here using, as model, a coated sample of certified thickness. Finally, the depth resolution achieved for qualitative depth profiles obtained by rf-GD-(SF)MS is compared with that for the well-established rf-GD optical emission spectroscopy (OES) technique.