Experimental alteration of volcanic tuff from Almeria, southeastern Spain, was performed in solutions with different Na/K ratios (0.01, 1, 10, and 100), different total salt concentrations (0.01, 0.1, 0.2, 0.33, and 1 M), and in deionized water, at 60, 80, 120, and 160°C, for periods of 60, 90, 180, and 360 d. Two particle size fractions of volcanic tuff were used: 10–200 and 20–60 μm. Alteration products were examined by X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), laser-particle size analysis, scanning electron microscopy equipped with an energy dispersive X-ray spectrometer (SEM-EDS), image computer analysis, and transmission electron microscopy with microanalysis (TEM-AEM). XRD detected neoformed phases only in the products from experiments of 180–360 d at high temperatures (120–160°C), and with Na/K ratios above unity and in deionized water. The synthesized phase is a random mixed-layer illite-smectite (I-S) with 75% smectite. The quantity of newly formed I-S, determined by FTIR, ranged between 3–30%. There was no apparent change in grain size and shape of the grains after the experiments as compared to before.

SEM-EDS and TEM-AEM revealed the following alteration sequence: 1) intense etching on glass-grain surfaces; 2) formation of hemispherical morphologies on grain surfaces; 3) precipitation of very thin, individual flakes of illite-smectite on glass-grain surfaces; 4) development of I-S at the edges of glass grains; and 5) development of I-S honeycomb structures either covering large areas of the glass grains or resulting from the complete alteration of glass grains. A direct transformation of glass to I-S seems to be the major reaction mechanism, although there also is evidence of glass dissolution and subsequent I-S precipitation.

The Bracarense ceramics are characterized by a fine, pale yellow paste covered with a brownish yellow slip. The name is derived from Bracara Augusta, the Roman town located in the north of Portugal, where this type of ceramic paste was first found and identified. Various forms with the same type of paste occur, such as imitations of sigillata, terra sigillata and thin walls from the Augustus-Tiberius period, and common ware. Later, similar ceramics were also found in other archeological sites, e.g. Aquis Querquennis (Galiza, Spain), which question the location of the production center of this type of ceramic paste.

Mineralogical and chemical analyses showed that the majority of the Bracarense shards studied differ from the common ware of the Braga region. Despite minor differences, the Bracarense shards collected in Aquis Querquennis have the same geochemical pattern as those found in Bracara Augusta, i.e. they appear to have been manufactured with the same clay type. The firing products found indicate a kaolin character of the source clay, and point to firing temperatures near 900°C. The Aquis Querquennis shards have greater Br contents, which can be explained by use-wear and/or post-depositional processes, as this site is located in a thermal-water region.

Este trabajo se propone avanzar en la comprensión de los procesos históricos de pintado del sitio arqueológico de Oyola (Sierra El Alto-Ancasti, Catamarca, Argentina). En particular, se evalúan similitudes y diferencias en la composición material de las mezclas pigmentarias para entrever la existencia de antiguas recetas pictóricas en la confección de las pinturas rupestres negras. Para ello se realizaron análisis microestratigráficos de 28 motivos mediante microscopía electrónica de barrido con análisis elemental por espectroscopía dispersiva en energía de rayos X (MEB-EDS), y microespectroscopía Raman (RS). Su estudio comparativo señaló el uso alternativo de dos pigmentos negros (carbón vegetal y óxidos de manganeso) combinados, en algunos casos, con un aditivo (sulfato de calcio). De esta forma, fue posible conocer ciertos aspectos de las recetas pictóricas que orientaron la preparación de las mezclas pigmentarias negras, aproximándonos a algunas de las tradiciones y saberes retomados. Para alcanzar una comprensión histórica de dichas recetas, se evaluó la distribución espacial, temporal y algunas características formales de los motivos rupestres realizados con ellas. Al no identificarse tendencias claras, se propone una definición menos normativa de receta pictórica que resalta los aspectos compartidos entre distintos episodios de pintado sin perder de vista las posibilidades creativas de cada evento.

Searching for residue in the glaze of porcelain or stoneware is a difficult task because these glazes are high-fired, well vitrified, and nonporous. This paper analyzes the chemical composition of residue observed in glaze cracks of porcelain via SEM-EDS to determine how the crackle effect was produced, in particular, if it was intentionally created during production or the result of post-depositional processes. This study offers insights to a specific type of ancient Chinese porcelain called “Ge-type ware”, which has two different types of cracks, and whose origin has been debated for nearly 60 years because it has never been found at any kiln site. This paper analyzes the chemical composition of the two crack types, first using elemental mapping to ascertain the different mechanisms that produced these two crack types of the Heirloom Ge ware, and second using residue analysis and chemical fingerprinting to determine the provenance of this puzzling type of porcelain. In doing so, this paper demonstrates how the residue in the glaze of porcelain can be observed and analyzed via microchemical approaches and hopes to inspire more research using this technique in future.

The morphology and composition of the corrosion products of archaeological arsenical copper alloys buried in a specific environment for a long time were investigated using optical microscopy (OM), scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDS), micro X-ray fluorescence (μ-XRF), and X-ray diffraction (XRD). The analyses demonstrated that the alloy composition of the artifacts was copper-arsenic (Cu-AS) with significant amounts of lead in some samples. Cuprite, malachite, and copper (II) hydroxychlorides were observed on a completely mineralized matrix. The surface of the objects was covered by two main corrosion layers formed on the internal cuprous oxide. However, several successive layers of corrosion products were recognized on the artifacts in some cases. Furthermore, phosphatic corrosion products including, mimetite [Pb5(AsO4)3Cl], and pyromorphite [Pb5(PO4)3Cl] were identified. Conichalcite [CaCu(AsO4)](OH), which grew in the form of Liesegang rings, was also identified as a corrosion product of one of the objects. As and Pb exhibited some enrichment in the corrosion crusts of the artifacts. Environmental changes in burial conditions, particularly due to seasonal streams and consequent changes in soil corrosivity, vicinity of objects to bone material, along with the migration of alloy elements, especially lead and arsenic, can explain the morphological features of these archaeological objects.

The members of the Bacteroidetes phylum move on surfaces by gliding motility in the absence of external motility appendages, leading to the formation of spreading colonies. Here, the structural features of the spreading colony were assessed in a uranium-tolerant Bacteroidetes bacterium, Chryseobacterium sp. strain PMSZPI, by using correlative light and scanning electron microscopy (CLSEM). We developed a simple and convenient workflow for CLSEM using a shuttle and find software module and a correlative sample holding slide designed to transport samples between the light/fluorescence microscope (LM/FM) and the scanning electron microscope (SEM) to image spreading colony edges. The datasets from the CLSEM studies allowed convenient examination of the colonial organization by LM/FM followed by ultrastructural analysis by SEM. The regions of interest (ROIs) of the spreading colony edges that were observed in LM/FM in the absence and presence of uranium could be re-identified in the SEM quickly without prolonged searching. Perfect correlation between LM and SEM could be achieved with minimum preparation steps. Subsequently, imaging of the correlated regions was done at higher resolution in SEM to obtain more comprehensive information. We further showed the association of uranium with the gliding PMSZPI cells by energy-dispersive X-ray spectroscopy (EDS) attached to SEM.

In this work, the technique and the pictorial materials employed by Claude Monet in Pink Water Lilies, presently housed at the National Gallery of Modern and Contemporary Art in Rome, were investigated. The painting underwent noninvasive investigations such as energy-dispersive X-ray fluorescence and visible reflectance spectroscopies. The combined use of these techniques allowed us to identify most of the inorganic pigments such as cobalt blue and violet, zinc oxide, cadmium yellow, vermilion, and mixtures. Particularly, the spectrophotometric curves allow for the detection of the anhydrous and hydrated chromium greens. Two micro-fragments of the painting were also examined with micro-Fourier transform infrared spectroscopy and the cross-sections obtained were analyzed with the optical microscope and with scanning electron microscopy (SEM) and energy-dispersive X-ray spectrometry (EDS). Fourier Transform Infrared spectroscopy analyses allowed us to recognize the animal glue used for priming the canvas, which was covered with a ground layer consisting of calcite and lead white mixed with an oil binder. A lipidic binder was also detected in the color layer. Optical microscopy and SEM-EDS were useful to retrieve information about the stratigraphy, the distribution of pigments, and a more complete palette identification of phosphate, arsenate, and magnesium arsenate cobalt violets, and the red lake was possible.

The interaction of NCC-A (no cement content, with tabular corundum) refractory castable with corrosive refining steel slag CaO–Al2O3–SiO2–MgO–(FeO, MnO) was studied with static crucible corrosion tests. The corrosion process was evaluated using chemical and phase analyses, and the macro- and microstructures on the corrosion boundary of slag–refractory materials were investigated. We describe the corrosion progress and explain the NCC-A corrosion mechanism by oxide metallurgical slags. The alumina refractory material surface was wetted with molten oxide slag (contact angle θ1390°C from 10° to 20°). The slag penetrated through dissolution of the matrix (fine alumina cement), and the Ca–Si–Al slag, enriched with alumina, attacked the corundum grog. Marked changes in the chemical composition of the slag had an impact on the primary crystallization temperature. As the concentration of Al–O complexes increased in the slag, the binding parameters in Si–O complexes changed and complex tetrahedral units (Al–O–Si) and (Al–O–Mg) were created. Analyses of the corrosion interface grog show that calcium ions diffuse through structural defects in the corundum but Mg2+ diffusion was not observed. A sharp interface is observed between the slag and the corroded corundum layer. Differences in the chemical composition of the slag in the corrosion zone affected the convention stream, and formed the concave corrosion profile of the crucible.

The south-eastern Black Sea area is a key region for understanding the history of iron metallurgy. While Classical texts mention the people living in this area as producers, and perhaps even inventors, of iron, material evidence has been lacking. Recent archaeological survey and scientific analyses now make it possible to investigate iron technologies in the region during the mid to late first millennium BC and the medieval period, providing new insights into the metallurgical tradition that inspired such admiration in the Graeco-Roman world. These results have implications for the smelting of iron in liquid state, although it remains unclear where and when this technology first appeared in Western Eurasia.

The gold technology in Iberia underwent an important development during the Early Iron Age (EIA) following the arrival of new technological skills from the Mediterranean region, including the use of filigree, granulation, and brazing. This work presents the microanalytical study of EIA gold jewels (22 spherical beads and four tongue pendants) recovered from three graves in southern Portugal. The set of jewelry, showing an extraordinary stylistic resemblance, was characterized by optical microscopy, micro energy-dispersive X-ray spectrometry and scanning electron microscopy with X-ray microanalysis to establish the alloy composition and production techniques. The pieces show a close technological relation, making use of artificial gold alloys with different amounts of silver (c. 40 and 25%). The decorative styles include different types of filigree (solid wires and hollow wires), while the joining techniques comprise brazing with Au-Ag-Cu solders and, probably, sintering. In spite of those technological and stylistic features, clearly pointing to a Mediterranean influence, the absence of granulation suggests an indigenous workshop where exogenous technologies/decorations were not yet fully integrated in the manufacture of such luxury items.

Highly porous alumina-based oxides, γ-Al2O3, SiO2–Al2O3, and TiO2–Al2O3 were synthesized by a modified sol–gel method. Polivinylpyrrolidone was used as the pore expanding agent, whereas cetyltrimethylammonium bromide was used as the template in the presence of alkoxide inorganic precursors. Both as-synthesized and calcined solids were used as catalysts for esterification of glycerol with acetic acid (EG). The XRD and SEM-EDS measurements demonstrated that the Si-containing solids are amorphous while those containing Ti are semicrystalline with the latter composed of TiO2 rutile, TiO2 anatase, and γ-Al2O3 phases. All solids possessed ordered porous structures comprising of micro- and mesoporosity, with interconnectivity between these pores of different length scales. The high acidity of γ-Al2O3 and TiO2–Al2O3 materials resulted in good catalytic performances in the EG. Porosity of the solids plays a secondary role in determining the catalytic activity. Under the same conditions, the as-synthesized solids exhibited slightly lower catalytic performances compared to that of the calcined ones.

This work explores the combination of µ-Raman spectroscopy and scanning electron microscopy with X-ray energy dispersive spectrometry (SEM-EDS) for the study of the glazes in 15th–16th century Hispano-Moresque architectural tiles. These are high lead glazes that can be tin-opacified or transparent, and present five colors: tin-white, cobalt-blue, copper-green, iron-amber, and manganese-brown. They are generally homogenous and mineral inclusions are mostly concentrated in the glaze-ceramic interface. Through SEM-EDS, these inclusions were observed and chemically analyzed, whereas µ-Raman allowed their identification on a molecular level. K-feldspars, wollastonite and diopside were the most common compounds, as well as cassiterite agglomerates that render the glaze opaque. Malayaite was identified in green glazes, and andradite and magnesioferrite in amber glazes. Co–Ni–ferrites were identified in blue glazes, as well as Ni–Fe–olivines. Manganese-brown is the color where most compounds were identified: bustamite, jacobsite, hausmannite, braunite, and kentrolite. Through the µ-Raman analysis of different areas in large inclusions previously observed by SEM, it was possible to identify intermediate phases that illustrate the reaction process that occurs between the color-conferring compounds and the surrounding lead glaze. Furthermore, the obtained results allowed inference of the raw materials and firing temperatures used on the manufacture of these tiles.

The history and iconography of Swiss stained glass dating between the 16th and 18th centuries are well studied. However, the chemical and morphological characteristics of the glass and glass paints, particularly the nature of the raw materials, the provenance of the glass, and the technology used to produce it are less well understood. In this paper, we studied two sets of samples from stained-glass panels attributed to Switzerland, which date from the 16th to 17th centuries: the first set comes from Pena National Palace collection, the second from Vitrocentre Romont. The aims were to identify the materials used in the production of the glass, to find out more about their production origin and to characterize the glass paints. Both glass and the glass paints were analysed by particle-induced X-ray emission; the paints were additionally analysed by scanning electron microscopy–electron-dispersive X-ray spectroscopy (SEM-EDS). The results show that the glass from both sets was probably produced in the same region and that wood ash was used as a fluxing agent. Different recipes have been used to make the blue enamels. However, the cobalt ore used as a coloring agent in all of the blue enamels came from the mining district in Schneeberg, Germany.

In this work, weddellite and sylvite crystals are identified for the first time on the involucral bracts and petals of Xeranthemum annuum and Xeranthemum cylindraceum using scanning electron microscopy coupled with energy dispersive spectrometric (SEM-EDS) analysis. Well-developed crystals of weddellite (CaC2O4·2H2O) occur in the form of a tetragonal bipyramid (hhl), rarely in combination of a bipyramid and tetragonal prism (h00). Indumentum of involucral bracts of X. cylindraceum consists of nonglandular and glandular trichomes. Sylvite (KCl) crystals are observed only on the petal surface of X. cylindraceum. The crystals of sylvite occur in the form of perfect cubes (hexahedrons), but some crystals are deformed, i.e., partially elongated. Taxonomic significance of investigated microcharacters as well as the use of SEM-EDS analysis in taxonomic studies of plants are discussed.

Secondary fluorescence, the final term in the familiar matrix correction triumvirate Z·A·F, is the most challenging for Monte Carlo models to simulate. In fact, only two implementations of Monte Carlo models commonly used to simulate electron probe X-ray spectra can calculate secondary fluorescence—PENEPMA and NIST DTSA-IIa (DTSA-II is discussed herein). These two models share many physical models but there are some important differences in the way each implements X-ray emission including secondary fluorescence. PENEPMA is based on PENELOPE, a general purpose software package for simulation of both relativistic and subrelativistic electron/positron interactions with matter. On the other hand, NIST DTSA-II was designed exclusively for simulation of X-ray spectra generated by subrelativistic electrons. NIST DTSA-II uses variance reduction techniques unsuited to general purpose code. These optimizations help NIST DTSA-II to be orders of magnitude more computationally efficient while retaining detector position sensitivity. Simulations execute in minutes rather than hours and can model differences that result from detector position. Both PENEPMA and NIST DTSA-II are capable of handling complex sample geometries and we will demonstrate that both are of similar accuracy when modeling experimental secondary fluorescence data from the literature.

The present study characterizes the main deterioration mechanisms affecting the early 17th frescoes of Casa de Fresco, the only known example in Portugal of a semi-underground leisure room richly decorated with a balcony over a water well. Frescoes from the vault are at risk due to salt weathering and biodeterioration. The aim of the research was identification of the deterioration materials, determination of their origin, and their effect on the frescoes before future intervention. Scanning electron microscopy with an energy-dispersive X-ray detector (SEM-EDS) was used to determine salt morphology and microanalysis. The mineralogical characterization was performed by X-ray powder diffraction, complemented with µ-Raman and µ-Fourier transform infrared spectroscopy. Biological assessment was evaluated with optical microscopy and SEM-EDS. Bacterial and fungal isolation and identification were performed using standard culture media and methods according to Bergey’s Manual of Systematic Bacteriology and from the Compendium of Soil Fungi. The results show that Ca and Ca-Mg carbonates from the paint renderings are the predominant salt species affecting the site. Bacterial strains from the genera Bacillus and Pseudomonas and fungal strains from the Cladosporium spp. and Penicillium spp. were isolated in the salt formations, within and between the mortar layers. Azurite, malachite, and smalt paint layers are the most affected by the weathering conditions.

This work comprises the use of a multi-analytical approach combined with microbiological studies to characterize six paper samples, containing foxing stains, from the 20th century, regarding their cellulose matrix, fillers, and sizing materials, and to evaluate possible paper degradation that might have occurred during the foxing stains. Photography under different illuminations and optical microscopy were used for morphological characterization of the paper samples and foxing stains. Scanning electron microscopy coupled energy dispersive spectroscopy (SEM-EDS) was of particular importance for defining the presence of fiber disorder and disruption on the surface of some of the stains, and localized accumulations of mineral-like particles on the surface of others. SEM-EDS, attenuated total reflection Fourier transform infrared spectroscopy (ATR-FT-IR), and energy dispersive X-ray fluorescence (EDXRF) were used for the identification of mineral fillers, whereas sizing agents were analyzed using ATR-FT-IR. EDXRF results showed that no differences, within the standard deviation, were found in iron and copper contents between the foxed and unfoxed areas. Fungi belonging to the genus Penicillium spp. were found in all the paper samples. Unfoxed areas presented lower contamination than the foxed areas.

The objects of this study are various local charters (cartas de foral, in Portuguese) granted by Dom Manuel I, King of Portugal (1495–1521), which substituted for medieval ones and were intended to achieve an administrative unification. These are luxuriously illuminated manuscripts, and our study aims at obtaining a better understanding of the gilding and silvering techniques applied to the parchments, in which the forais were written, between 1500 and 1520. The combined use of microscopy and X-ray spectroscopy analyses allowed us to identify the vestigial materials used for making the parchments, including products such as salt (NaCl), lime (CaO), pumice stone (SiO2+Al2O3), and chalk (CaCO3). Chalk was employed as a whitening agent to give the parchment its final color and opacity. Shell-gold and shell-silver mixed in with animal glue or gum binding media were directly applied on type 1 and 3 forais, while very thin gold leaves (<1 µm) were applied over lead-based tempera grounds (50–180 µm thick) in type 2 forais. Silver was always employed in its finest form without a further protective layer (thus its recursive state of corrosion), while gold was used in various alloy grades.

The analysis of a Portuguese “papier-mâché” sculpture depicting Saint Anthony is presented in this case study. Several questions were addressed such as the characteristics of the support, pigments used, and artistic technique in order to establish a possible timeline for its production. Qualitative analyses of the cross-sections and of the paper support were performed by optical microscopy using reflected light. Two polychrome layers from different periods and a rag pulped support were identified on the sculpture. The use of micro X-ray fluorescence and Raman microscopy techniques enabled the differentiation of coloring materials used in both polychromies. Semi-quantitative analyses of the gilded samples were also performed by scanning electron microscopy in combination with energy-dispersive spectroscopy allowing the determination of a common Au–Ag–Cu alloy with differences in the purity of the gold. The identified coloring materials lead us to believe that the sculpture was produced in the 19th century, being overpainted in the first half of the 20th century.

The artwork “Smoke Rings: Two Concentric Tunnels, Non-Communicating” by Bruce Nauman represents a case study of corrosion of a black patina-coated Al-alloy contemporary artwork. The main concern over this artwork was the widespread presence of white spots on its surface. Alloy substrate, patina, and white spots were characterized by means of energy-dispersive X-ray fluorescence and scanning electron microscopy with energy-dispersive spectroscopy. Alloy substrate was identified as an aluminum alloy 6,000 series Al–Si–Mg. Patina’s identified composition confirmed the documentation provided by the atelier. Concerning the white spots, zircon particles were found on patina surface as external elements.