Micro-energy Dispersive X-ray Fluorescence Research Articles

Analysis of Cation Composition in Dolomites on the Intact Particles Sampled from Asteroid Ryugu.

Characterization of the elemental distribution of samples with rough surfaces has been strongly desired for the analysis of various natural and artificial materials. Particularly for pristine and rare analytes with micrometer sizes embedded on specimen surfaces, non-invasive and matrix effect-free analysis is required without surface polishing treatment. To satisfy these requirements, we proposed a new method employing the sequential combination of two imaging modalities, i.e., microenergy-dispersive X-ray fluorescence (micro-XRF) and Raman micro-spectroscopy. The applicability of the developed method is tested by the quantitative analysis of cation composition in micrometer-sized carbonate grains on the surfaces of intact particles sampled directly from the asteroid Ryugu. The first step of micro-XRF imaging enabled a quick search for the sparsely scattered and micrometer-sized carbonates by the codistributions of Ca2+ and Mn2+ on the Mg2+- and Fe2+-rich phyllosilicate matrix. The following step of Raman micro-spectroscopy probed the carbonate grains and analyzed their cation composition (Ca2+, Mg2+, and Fe2+ + Mn2+) in a matrix effect-free manner via the systematic Raman shifts of the lattice modes. The carbonates were basically assigned to ferroan dolomite bearing a considerable amount of Fe2+ + Mn2+ at around 10 atom %. These results are in good accordance with the assignments reported by scanning electron microscopy-energy-dispersive X-ray spectroscopy, where the thin-sectioned and surface-polished Ryugu particles were applicable. The proposed method requires neither sectioning nor surface polishing; hence, it can be applied to the remote sensing apparatus on spacecrafts and planetary rovers. Furthermore, the non-invasive and matrix effect-free characterization will provide a reliable analytical tool for quantitative analysis of the elemental distribution on the samples with surface roughness and chemical heterogeneity at a micrometer scale, such as art paintings, traditional crafts with decorated shapes, as well as sands and rocks with complex morphologies in nature.

Ionic liquids (ILs)-loaded hydrogels as a potential cleaning method of metallic stains for stone conservation

In the field of built heritage, the removal of reddish-brown and greenish stains presents a complex challenge frequently encountered by experts. Consequently, numerous studies strive to develop sustainable and respectful cleaning methods for conserving stone materials in their original esthetic state. In pursuit of this objective, agar hydrogels were here investigated as solid support, capitalizing on their slow-release capability and capacity to store chemical species. As chelating and biocidal loading, three different ionic liquids (ILs) (trihexyltetradecylphosphonium chloride (TP), bis(2-ethylhexyl) phosphate (BP), and Alicy (AL) and a mixture of Aliquat 336 and Cyanex 272 were tested for the controlled removal of iron and copper stains. The homogeneity and cleaning effectiveness of the different loaded agar hydrogels were assessed on artificial stains using a combination of micro-energy dispersive X-ray fluorescence (µ-ED-XRF) and Raman imaging analyses. The spectroscopic data were supported by inductively coupled plasma atomic emission spectroscopy (ICP-AES) and colorimetric measurements. Additionally, the inhibitory effect on microbial growth of the most effective treatments was tested prior to their in situ application on naturally stained stones. The results indicated that agar provides suitable solid support to apply ILs, specifically highlighting the strong affinity of AL and BP for sequestering iron and copper ions, respectively, from stained stone surfaces. Furthermore, the disk-diffusion results evidenced that the proposed treatments could play a bi-functional role if a biocidal action is required to remove biological colonization, reaching nwhalo average values in the range of 0.6 - 0.8 against Micrococcus Luteus. Thus, this study showcases the potential of agar hydrogels loaded with ILs as a sustainable and gentle cleaning method in built heritage conservation.

Multi-Analytical Approach to Evaluate Elements and Chemical Alterations in Pteris vittata Plants Exposed to Arsenic

The aim of this study was the development of a new multi-analytical approach to evaluate chemical alterations and differences in the element content in relation to arsenic (As) in the As hyperaccumulator fern P. vittata. P. vittata plants were grown on two natural As-rich soils with either high or moderate As (750 and 58 mg/kg). Dried samples from plant tissues were then analysed by means of micro-energy dispersive X-ray fluorescence spectrometry (μ-XRF), attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) and hyperspectral imaging (HSI) with a multivariate approach. The As and micro- and macronutrients content was evaluated by μ-XRF and a significant correlation between As, potassium (K), iron (Fe), calcium (Ca) and manganese (Mn) contents were found at both moderate and high As levels. The same samples were then analysed by ATR-FTIR spectroscopy and HSI (SWIR range, 1000–2500 nm). Interestingly, by FTIR analysis it was found that the main differences between the control and the As-contaminated samples are due to the intensity of the absorption band related to polysaccharides (i.e., cellulose, hemicellulose and pectin), lignin, lipid and amide groups. The same chemical alterations were detected by an HSI analysis and all the FTIR and HSI data were validated by a PCA analysis. These results suggest a possible complexation of As ions with the amide group. Moreover, the proposed μ-XRF, HSI and ATR-FTIR combining approach could be a promising strategy to monitor in-field phytoremediation approaches by directly controlling the As content in plants.

Characterization of Chalcolithic Ceramics from the Lisbon Region, Portugal: An Archaeometric Study

The Chalcolithic period in the Lisbon region, Portugal, is usually divided into three phases chronologically: the Early Chalcolithic, characterized by cylindrical corrugated cups, Full Chalcolithic by so-called acacia-leaf decoration, and Late Chalcolithic by Bell Beaker pottery. The aim of this research is to determine if Chalcolithic ceramic raw materials and production techniques have remained the same over time and whether the pottery is locally produced. Regarding the Lisbon region, 149 ceramic samples from four Chalcolithic settlements (Vila Nova de São Pedro, Penedo do Lexim, Espargueira and Baútas) were evaluated concerning textural, chemical and mineralogical compositions. Textural analysis was performed using optical microscopy, chemical characterization was achieved using micro-energy dispersive X-ray fluorescence spectrometry and mineralogical characterization was undertaken using X-ray powder diffraction and petrographic microscopy as main techniques. Results suggest that production techniques may have remained similar throughout all the Chalcolithic period, with firing temperatures between 700 and 800 °C. Multivariate analysis of results from chemical and mineralogical analyses suggests that multiple sources of raw materials must have been used in the manufacture of the pottery collected at the four Chalcolithic settlements.

Biomineralization induced by chitosan and collagen-based materials with fluoride for dentin coverage: Chemical and morphological analysis.

The prevention and treatment of erosive tooth wear are becoming increasingly important due to its increasing prevalence. The use of natural solutions to modify dental surfaces has become an area of research. Organic materials such as chitosan and hydrolyzed collagen may be a promising option to treat dentin. This in vitro study aimed to evaluate the influence of chitosan or hydrolyzed collagen, alone or combined with acidulated phosphate fluoride (APF) gel, on the composition and morphology of dentin after erosion. Bovine dentin samples were prepared (n= 84) and treated with artificial saliva (AS, negative control); APF gel (F, positive control); chitosan solution (Chi); hydrolyzed collagen solution (Col); fluoride/chitosan composition (F_Chi); and fluoride/hydrolyzed collagen composition (F_Col). Erosive cycles (six cycles of immersion in orange juice for 1min, followed by immersion in AS for 1 hr) were performed. The materials were characterized by their morphology, composition, and particle size distribution. Micro-energy dispersive X-ray fluorescence spectroscopy and scanning electron were used to evaluate the dentin's inorganic chemical composition and morphology. The F_Col and F groups had a reduction in calcium loss by 17 and 26%, respectively (p<.001). Both of these groups still had a covering layer of agglomerates at the dentin surface after the erosive cycles. The fluoridated chitosan or collagen solutions improved the dentin resistance to erosion as a novel hybrid-fluoride-based material approach to provide surface protection from erosion.

Mapping the distribution of mercury (II) chloride in zebrafish organs by benchtop micro-energy dispersive X-ray fluorescence: A proof of concept

BackgroundMercury (Hg) is a globally ubiquitous pollutant and one of the most dangerous metal contaminants, which presents a high risk of bioaccumulation in living organisms. In this study, we mapped the distribution of Hg and other trace elements in zebrafish (Danio rerio), which were exposed to mercury (II) chloride in order to assess its toxicity, bioaccumulation and distribution in fish organs. MethodsAdult zebrafish were exposed for 7 days to different concentrations of mercury (II) chloride and the elemental distribution was obtained through the micro-energy dispersive X-ray fluorescence technique (μ-EDXRF). ResultsThe results showed that Hg levels, measured in fish tissues, were indicative of bioaccumulation within some of its organs (e.g. visceral mass, gills), and that the physiological processes of accumulation were highly dose-dependent. In addition, the results showed higher concentrations of Hg in the gills. Moreover, other trace elements (e.g. Fe, Cu and Zn) levels were not altered after fish exposure to mercury(II) chloride. ConclusionThe μ-EDXRF results were assessed along with the determination of some oxidative stress biomarkers (e.g. antioxidant enzymes) to understand the effects behind the Hg bioaccumulation and toxicity. These results suggest that the metabolic changes in zebrafish due to the exposure to Hg are consistent with oxidative stress.

Non-Destructive Analytical Investigation of Decorative Wallpapers Samples of the Nineteenth Century before Their Restoration.

In this work, decorative wallpapers (19th century) from an historical palace located in Oiartzun (Basque Country, Spain) were analyzed before their restoration. Micro-energy dispersive X-ray fluorescence spectroscopy, Raman spectroscopy, and attenuated total reflectance infrared spectroscopy were used to investigate the elemental and molecular composition of pigments, the presence of binders, and the state of conservation of the paper support. The aim of the investigation was trying to understand the possible degradation pathways and identify the raw materials in order to choose the best restoration protocol according to the original aspect of wallpapers. As stated from both the elemental distribution and the identification of mineral phases by Raman spectroscopy, the most used pigment was lead chromate. It was mixed with other pigments such as ultramarine blue, zinc chromate, hematite, and atacamite among others to obtain different shades and they were applied mixed with an animal glue. Brass, identified thanks to elemental micro-EDXRF maps, was employed as a shiny decorative element. In addition, a partial degradation of cellulose was detected due to its natural ageing, the acidic nature of lignin, and to a phenomenon of humidity of the walls. Probably the deposition of black particulate matter was the cause of the darkening of the painting surfaces.

Phytoextraction efficiency of Pteris vittata grown on a naturally As-rich soil and characterization of As-resistant rhizosphere bacteria

This study evaluated the phytoextraction capacity of the fern Pteris vittata grown on a natural arsenic-rich soil of volcanic-origin from the Viterbo area in central Italy. This calcareous soil is characterized by an average arsenic concentration of 750 mg kg−1, of which 28% is bioavailable. By means of micro-energy dispersive X-ray fluorescence spectrometry (μ-XRF) we detected As in P. vittata fronds after just 10 days of growth, while a high As concentrations in fronds (5,000 mg kg−1), determined by Inductively coupled plasma-optical emission spectrometry (ICP-OES), was reached after 5.5 months. Sixteen arsenate-tolerant bacterial strains were isolated from the P. vittata rhizosphere, a majority of which belong to the Bacillus genus, and of this majority only two have been previously associated with As. Six bacterial isolates were highly As-resistant (> 100 mM) two of which, homologous to Paenarthrobacter ureafaciens and Beijerinckia fluminensis, produced a high amount of IAA and siderophores and have never been isolated from P. vittata roots. Furthermore, five isolates contained the arsenate reductase gene (arsC). We conclude that P. vittata can efficiently phytoextract As when grown on this natural As-rich soil and a consortium of bacteria, largely different from that usually found in As-polluted soils, has been found in P. vittata rhizosphere.

Compositional and microstructural outlook of grave goods from Anta do Malhão and Soalheironas (Portugal): The diachronic use of arsenical copper in southwestern Iberian Peninsula

Although in recent years the prehistoric metallurgy of southwestern Iberian Peninsula has become increasingly well understood, the southernmost region still requires additional research. This work presents the technological study of artefacts from burial contexts located in this area, namely the necropolises of Anta do Malhão and Soalheironas (Algarve region). Typologies of metalwork and pottery ascribe the single inhumation at Anta do Malhão to a late phase of the “Ferradeira Horizon” (last quarter of the 3rd millennium BC), while assigning the necropolis of cists at Soalheironas to an earlier phase of the Middle Bronze Age (1st half of the 2nd millennium BC). The elemental and microstructural composition of artefacts was established by micro-energy dispersive X-ray fluorescence spectrometry, optical microscopy and scanning electron microscopy with X-ray microanalysis. Results show artefacts made of arsenical copper alloys (2.01–3.40% As) with very low iron content (<0.05% Fe). The microstructures display deformed equiaxed grains with annealing twins and slip bands, evidencing cycles of hammering and annealing, followed by a finishing hammering operation. The integration of results in the prehistoric metallurgy of southwestern Iberian Peninsula suggests a shared technological tradition, while a more comprehensive discussion discloses important developments involving the increased production of strain-hardened tools and weapons, together with a rising substitution of the copper metal by arsenical copper alloys from the 3rd to the 2nd millennium BC.

Physicochemical composition, phytochemical analysis and biological activity of ciricote (Cordia dodecandra A. D.C.) fruit from Yucatán

The physicochemical properties, proximate composition, minerals, total polyphenols, carotenoids, phenolic compounds, antioxidant, and antibacterial activities of ciricote (Cordia dodecandra A. DC.) tropical fruit were investigated. Minerals were quantified by using micro-Energy Dispersive X-Ray Fluorescence. Lutein and β-carotene were identified in ciricote fruit by using UPLC-PDA analysis. The highest values of the total polyphenols content and antioxidant activity were presented in ethanolic crude extracts obtaining by the ultrasonic-assisted method with freeze-dried fruit. The phenolic acids profile was identified and quantified by UPLC-PDA-ESI-MS. The main phenolic acids were caffeoyl hexoside, rufescenolide, quercetin 3-O-rutinoside, and rosmarinic acid. The ciricote extracts presented antibacterial activity against Staphylococus aureus (Gram+) and Salmonella typhymurium (Gram−). In conclusion, the ciricote (Cordia dodecandra A. DC.) tropical fruits could be very useful source of biological macromolecules, micro-elements, and phytochemical compounds for the food and pharmaceutical industry.

Effects of violet radiation and nonthermal atmospheric plasma on the mineral contents of enamel during in-office dental bleaching.

This in vitro study assessed the effects of in-office bleaching with gels (35% hydrogen peroxide [HP] or 37% cabamide peroxide [CP]) and two activation sources (violet radiation [LED] or nonthermal atmospheric plasma [NTAP]) on the mineral content of bovine enamel. Dental blocks (n = 90) were assessed for initial microhardness before random distribution into nine groups: LED, LED + HP, LED + CP, NTAP, NTAP + HP, NTAP + CP, HP, CP and control (without treatment). Specimens were subjected to bleaching (2 clinical sessions, 7 days apart) using LED [20x/session, 1-min/each, 30 s apart] or NTAP [1x/session, 10 min]. μRaman determined contents of phosphate (PO43) and carbonate (CO32). Micro-energy dispersive X-ray fluorescence (μEDXRF) and spectrophotometry of enamel microbiopsy evaluated the calcium to phosphorous ratios (Ca/P). Two-way ANOVA and Tukey tests analyzed μRAMAN and μEDXRF results. Spectrophotometry results were analyzed using Kruskal-Wallis and Dunn tests. Pearson correlation tested μEDXRF and spectrophotometry results (α = 5%). NTAP and NTAP + HP exhibited greater PO43- content than LED, LED + HP and control (p < 0.05). No statistical differences were detected between CO32- among groups. While μEDXRF evaluation demonstrated that NTAP and LED did not alter Ca/P ratio of enamel (p > 0.05), spectrophotometry showed that Ca/P reduced for LED + HP (p < 0.05). No correlation was found between μEDXRF and enamel microbiopsy spectrophotometry (p > 0.05). Activation sources did not adversely impact enamel's phosphate and carbonate concentrations after specimens' exposure to bleaching gels (either HP or CP). Visible light radiation emitted by a LED source was shown to adversely impact specimens' Ca/P ratios when treated with HP-containing bleaching gels.

Raman imaging to quantify the thermal transformation degree of Pompeian yellow ochre caused by the 79 AD Mount Vesuvius eruption.

Most of the wall paintings from Pompeii are decorated with red and yellow colors but the thermal impact of 79 AD Mount Vesuvius eruption promoted the partial transformation of some yellow-painted areas into red. The aim of this research is to develop a quantitative Raman imaging methodology to relate the transformation percentage of yellow ochre (goethite, α-FeOOH) into red color (hematite, α-Fe2O3) depending on the temperature, in order to apply it and estimate the temperature at which the pyroclastic flow impacted the walls of Pompeii. To model the thermal impact that took place in the year 79 AD, nine wall painting fragments recovered in the archeological site of Pompeii and which include yellow ochre pigment were subjected to thermal ageing experiments (exposition to temperatures from 200 to 400 °C every 25 °C). Before the experiments, elemental information of the fragments was obtained by micro-energy dispersive X-ray fluorescence (μ-ED-XRF). The fragments were characterized before and after the exposition using Raman microscopy to monitor the transformation degree from yellow to red. The quantitative Raman imaging methodology was developed and validated using synthetic pellets of goethite and hematite standards. The results showed almost no transformation (0.5% ± 0.4) at 200 °C. However, at 225 °C, some color transformation (26.9% ± 2.8) was observed. The most remarkable color change was detected at temperatures between 250 °C (transformation of 46.7% ± 1.7) and 275 °C (transformation of 101.1% ± 1.2). At this last temperature, the transformation is totally completed since from 275 to 400 °C the transformation percentage remained constant.

Multi-analytical study of 14th to 19th century illuminated Moroccan manuscripts

Moroccan manuscripts heritage preserves valuable information regarding different fields of Arabian history and culture. Despite this fact, analytical studies carried out in Moroccan manuscripts are scarce. In this work, we made use of a multi-analytical methodology to study, for the first time, four illuminated manuscripts from the Royal library of Rabat covering the span 14th to 19th centuries. The chemical structure of inks and paper support was identified. Elemental distribution obtained by micro-energy dispersive X-ray fluorescence (μ-EDXRF) showed the use of iron, copper and vermillion in black, blue and red inks, respectively. Arsenic and lead were identified as orange inks in the 17th and 19th century manuscripts, respectively. Quantitative characterization of the paper supports obtained by triaxial geometry EDXRF spectrometry showed high levels of sulphur, chlorine and potassium. Regarding the study of the manuscripts support, cellulose $I_{\beta}$ was determined by X-ray diffraction (XRD) in all the analyzed samples. Cellulose fibers observations by scanning electron microscopy showed that the manuscripts are in general, in a good condition. Calcite is the main filler determined by XRD.

Elemental characterization of surface and bulk of copper-based coins from the Byzantine-period by means of spectroscopic techniques

Thirty-three Byzantine copper-based coins (so-called anonymous follis) from 970 to 1085 CE were investigated in order to determine the elemental composition both of the bulk and of the surface. The ancient coins analysed - belonging to the Thomas Bertelè Collection, now located in the Bottacin Museum of Padova (Italy) - were studied by way of physical, chemical and chemometric testing techniques. This study aims to obtain information on socio-economic aspects of the Byzantine Empire using chemical and physical data of currency as indirect indicators. First, the weight, diameter and thickness of each piece were measured, then a micro-Energy Dispersive X-ray Fluorescence (μ-EDXRF) technique was applied on a cleaned and polished area of the surface of the coin to evaluate the presence of minor elements in a non-destructive fashion. A micro-destructive sampling method for both surface and bulk samples, based on mechanically drilling the edge, was finally employed, and Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES) was used for the quantitative determination of Cu (the major alloying element), Pb, As, Fe, Zn, Ag, Ni, Sn and Mn (minor elements) in the powder which resulted from drilling each coin, previously dissolved via aqua regia dissolution technique overnight at room temperature.The average copper concentration of the folles was 95.9 ± 3.1% for the bulk and 91.7 ± 3.5% for the surface. The Pb-Cu ratio appears to be an index which can be used to discriminate between different coins, in particular for Class B (from 1030 to 1042 CE), as confirmed by exploratory chemometric data analysis. According to our results, all the anonymous Byzantine folles under examination were minted in much the same way and using the same mineral raw materials. Using the chemical data measured on the bulk, we can grasp that the monetary choice of the period under study excluded silver, gold and bronze (concentrations of Pb is low, while Sn resulted undetectable or unquantifiable) to turn, substantially, to a copper-only coinage (deducted the impurities given by the gangue of the starting minerals). Moreover, along the observed period of 120 years, the mass of the coins was significantly reduced (with an overall loss of material of approximately 60%).

The use of micro-energy dispersive X-ray fluorescence spectrometry combined with a multivariate approach to determine element variation and distribution in tobacco seedlings exposed to arsenate

Here, we present a new scheme of analysis combining micro-energy dispersive X-ray fluorescence spectrometry (μ-XRF) with a multivariate approach that allows to establish the inter-correlation of multiple elements and their elemental map in plants. The main advantage of this procedure is that XRF spectral profiles can be analysed directly, by means of principal component analysis (PCA), allowing a quick interpretation of the results. Furthermore, this analysis requires small amounts of plant material and can be performed in whole individual seedlings in the hydrated state without chemical extraction. With this technology, we determined the distribution of arsenic (As) and the variation and spatial distribution of multiple elements in whole tobacco seedlings grown in the presence of different arsenate concentrations. We observed that As is detectable mainly in roots, primarily in the basal part, but also in the root apex in seedlings grown in the highest arsenate concentration. The low rate of As translocation from roots to shoots and the significant increase in S are consistent with previous evidence showing that As is retained in roots by forming complexes with thiol peptides. We also found a significant non-linear increase in P, as arsenate is taken up by phosphate transporters and induces the expression of genes encoding them. A decrease in Mn, Fe and Zn proportional to the accumulation of As and in the same tissues, suggests a competition of these elements with As for cellular transporters.

Trentepohlia algae biofilms as bioindicator of atmospheric metal pollution

In this work, a reddish biocolonization composed mainly by Trentepohlia algae affecting a synthetic building material from a modern building from the 90s located in the Bizkaia Science and Technology Park (Zamudio, North of Spain) was characterized and its ability to accumulate metals coming from the surrounding atmosphere was evaluated. To asses if these biofilms can act as bioindicators of the surrounding metal pollution, a fast non-invasive in situ methodology based on the use of hand-held energy dispersive X-ray fluorescence (HH-ED-XRF) was used. In order to corroborate the in situ obtained conclusions, some fragments from the affected material were taken to analyze the metal distribution by means of micro-energy dispersive X-ray fluorescence spectroscopy (μ-ED-XRF) and to confirm the presence of metal particles deposited on it using Scanning Electron Microscopy coupled to an Energy Dispersive Spectrometer (SEM-EDS). In order to confirm if Trentepohlia algae biofilms growing on the surface of building materials could be a fast way to in situ provide information about the surrounding metal pollution, a second Trentepohlia algae biofilm growing on a different kind of material (sandstone) was analyzed from an older historical building, La Galea Fortress (Getxo, North of Spain).

Micro-EDXRF, SEM-EDS and OM characterisation of tin soldering found in handle attachments of Roman situlae from Conimbriga (Portugal)

Tin (Sn) or a Sn-rich solder applied to copper-based artefacts has been frequently used at least, since the Ancient Greece, although scarce studies have been published concerning the technology of this metallurgical joining technique.Several filler remnants were reported to be found in a Roman collection of handle attachments of situlae or cauldrons (2nd century BCE–5th century CE) from the archaeological site of Conimbriga, a Roman city from the Lusitania Province (Portugal). All these artefacts were cast in high leaded coppers and bronzes.The present study aims to contribute to the knowledge of Sn-rich soldering, an ancient metallurgical joining technique, by the characterisation of the fusible metallic alloy present in 10 Roman artefacts by means of micro-energy dispersive X-ray fluorescence spectrometry (micro-EDXRF), scanning electron microscopy with energy dispersive X-ray (SEM-EDS) microanalysis and optical microscope (OM) observations.Results of studied solders show the presence of Cu-Sn alloys, with Sn contents ranging from δ to η phase composition (30–60wt% Sn). As the attachments were made in leaded copper alloys, it was also observed, in some cases, the melting of the interdendritic Pb-rich chains with long-range diffusion of the solder alloy into the substrate.The fillers compositions suggest that the handle attachments have been joined to a situla body by the soldering metallurgical process with Sn or a Sn-rich alloy. The studied leaded Cu-Sn attachments, probably formulated by local craftsman, were joined into the body of a situla or cauldron with a soft solder (soldering), a common metallurgical joint from Antiquity, although no relation was found between composition or typology and the Sn or Sn-rich solder.

Characterization of 18th century Portuguese glass from Real Fábrica de Vidros de Coina

This work reports the first systematic chemical characterization of Portuguese 18th century glassware. 28 selected glass fragments, recovered from an archaeological excavation carried out in the site where King D. João V of Portugal established an important glass manufacture, Real Fábrica de Vidros de Coina (Coina Royal Glass Factory), were studied. This factory operated from 1719 until 1747, the year in which the factory was transferred to Marinha Grande. The fragments were analysed by micro-energy dispersive X-ray fluorescence (micro-EDXRF), using a portable spectrometer ArtTAX, and scanning electron microscopy (SEM-EDX). The analytical data showed that a large variety of glass types was manufactured in that factory, namely soda-lime glass, mixed-alkali glass, high lime-low alkali glass, potash glass and lead glass. In general, the composition of the glass varies according to the function of the objects. It was demonstrated that micro-EDXRF can be an important tool to characterize museum glass objects when only in situ non-invasive analytical methods are allowed.

Evaluation of metals distribution in Solanum lycopersicum plants located in a coastal environment using micro-energy dispersive X-ray fluorescence imaging

The metal accumulation in edible parts of the plants is an important issue to provide a healthy food for the population. Some plants have the ability to take up certain trace elements from metal-polluted soils. Depending on the characteristics of the area and the environment where these plants have been grown, a different metal distribution can be observed on them. The aims of this work were to determine which are the general trends of metals distribution (e.g. K, Ca, Mn, Fe, Zn, Cu, Sr, etc.) in the different parts (roots, stems, leaves and fruits) of Solanum lycopersicum plants located in a seaside village (Barrika, Basque Country, North of Spain) and to asses if there is any potential dangerous accumulation in the edible part, the tomato fruit. Moreover, it was also evaluated if halogen elements (e.g. Cl, Br) emitted by the marine aerosol to the atmosphere are also highly distributed on these parts of Solanum lycopersicum plants. To perform this study a portable micro energy dispersive X-ray fluorescence spectrometer (μ-EDXRF) was used, which allows performing a mapping of each section of the plant in order to obtain the distribution of each element. The results obtained showed that a portable μ-EDXRF is a good analytical technique in order to know the distributions of these elements. Most of the elements identified in the roots, stem and leaves were not detectable in the fruit using this elemental technique. Moreover, it was detected the possible influence of the marine aerosol taking in to account the high distribution in all the parts of the plants of Cl and Br, except in the fruits.

Roman situlae from Conimbriga (Portugal): Compositional and microstructural characterization of anthropomorphic handle attachments

ABSTRACTA collection of 33 anthropomorphic handle attachments of Roman situlae recovered from the archeological site of Conimbriga (Central Portugal, 2nd century BC–5th century AD) was studied by micro-Energy Dispersive X-Ray Fluorescence Spectrometry (micro-EDXRF), Scanning Electron Microscopy - Energy Dispersive Spectroscopy (SEM-EDS) and metallographic techniques. Regarding the characterization of Roman artifacts of regional production, the relation among typology, composition and microstructure was evaluated in order to infer the Roman influence on the copper metallurgy in Western Iberia. The collection was found to be heterogeneous, mainly constituted by leaded copper and leaded bronzes, with a wide range of lead contents. The artifacts were all produced by mold casting, and most of them show some post-casting processing. Important casting faults and broken artifacts were associated with higher lead contents, and were mainly leaded copper. The leaded bronzes were more carefully produced. The overall results suggest a local metallurgical tradition, with the usage of copper and copper alloy scraps, with high additions of lead. The aim was to produce colored (and cheaper) artifacts, without any major concerns about the finishing details.