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Phthalates or phthalate esters (PAEs) have become a serious concern due to their toxicity and risks of migration from contact materials to food matrices and the environment. The aim of this study is to monitor the possible migration potential of PAEs in pelagic fish stored in vacuum packaging depending on the storage time and to determine the polyethylene polymers. In order to achieve this goal, sea bass (Dicentrarchus labrax) and anchovy fish (Engraulis encrasicolus) were randomly packaged in vacuum bags and then stored for 90 days. Phthalate content was determined by GC/MS technique in the muscle tissue of each fish species at certain periods (0, 30, and 90 days) of storage, and on the first day in the packaging material and fish meat. As a result of the analysis performed in µ-Raman spectroscopy, no microplastics were detected in both fish species' meats. FTIR spectroscopy results of the packaging material determined nylon in the chemical content of the packaging material before processing. It has been determined that the chemical composition of the packaging used in the vacuum packaging process is affected by the temperature, depending on the storage period, and different polymer types are formed in the processed package material. It was determined that the dominant PAE homologues were Di-n-pentyl phthalate (DPENP) in both fish meat and Di-(2-ethylhexyl)-phthalate (DEHP) in the package. However, during storage, Dibutylphthalate (DBP) became dominant in anchovies and DPENP became dominant in sea bass, differing according to fish species and storage time. [ABSTRACT FROM AUTHOR]

Wastewater networks are intrinsically attacked by the production of H2S, a highly reactive gas known for its extremely aggressive nature. This study employs a range of techniques, such as XRD, SEM–EDS, TGA, and Raman spectrometry, to investigate the interaction between low concentrations of H2S—averaging 1.3 ppm and various types of Portland cementitious materials (CEM I, CEM II, CEM III, and CEM V). The objective is to discern the chemical alterations contributing to structural deterioration and to provide a mineralogical characterization of the deterioration layers present on these binders. Through a comprehensive examination of the durability of these materials exposed to low concentrations of H2S in a Paris Region sewage system over nearly four years, the findings extend beyond surface-level observations. Despite the absence of visible signs of deterioration, high-precision analytical techniques reveal significant mineralogical transformations within the cementitious matrix. Expansive products such as gypsum, ettringite, and elemental sulfur are identified in mortar samples, underscoring the critical role of precise analysis in comprehending the deterioration process. [ABSTRACT FROM AUTHOR]

Abstract In recent years, the presence and migration of PAEs in packaging materials and consumer products has become a serious concern. Based on this concern, the aim of our study is to determine the possible migration potential and speed of PAEs in benthic fish stored in vacuum packaging, as well as to monitor the storage time and type as well as polyethylene (PE) polymer detection.As a result of the analysis performed by µ-Raman spectroscopy, 1 microplastic (MP) of 6 µm in size was determined on the 30th day of storage in whiting fish muscle and the polymer type was found to be Polyethylene (PE) (low density polyethylene: LDPE). Depending on the storage time of the packaging used in the vacuum packaging process, it has been determined that its chemical composition is affected by temperature and different types of polymers are formed. 10 types of PAEs were identified in the packaging material and stored flesh fish: DIBP, DBP, DPENP, DHEXP, BBP, DEHP, DCHP, DNOP, DINP and DDP. While the most dominant PAEs in the packaging material were determined as DEHP, the most dominant PAEs in fish meat were recorded as BBP and the lowest as DMP. The findings provide a motivating model for monitoring the presence and migration of PAEs in foods, while filling an important gap in maintaining a safe food chain.

In recent years, the presence and migration of PAEs in packaging materials and consumer products has become a serious concern. Based on this concern, the aim of our study is to determine the possible migration potential and speed of PAEs in benthic fish stored in vacuum packaging, as well as to monitor the storage time and type as well as polyethylene (PE) polymer detection.As a result of the analysis performed by µ-Raman spectroscopy, 1 microplastic (MP) of 6 µm in size was determined on the 30th day of storage in whiting fish muscle and the polymer type was found to be Polyethylene (PE) (low density polyethylene: LDPE). Depending on the storage time of the packaging used in the vacuum packaging process, it has been determined that its chemical composition is affected by temperature and different types of polymers are formed. 10 types of PAEs were identified in the packaging material and stored flesh fish: DIBP, DBP, DPENP, DHEXP, BBP, DEHP, DCHP, DNOP, DINP and DDP. While the most dominant PAEs in the packaging material were determined as DEHP, the most dominant PAEs in fish meat were recorded as BBP and the lowest as DMP. The findings provide a motivating model for monitoring the presence and migration of PAEs in foods, while filling an important gap in maintaining a safe food chain. [ABSTRACT FROM AUTHOR]

Concern about atmospheric microplastic (MP) contamination has increased in recent years. This study assessed the abundance of airborne anthropogenic particles, including MPs, deposited in rainfall in Bahia Blanca, southwest Buenos Aires, Argentina. Rainwater samples were collected monthly from March to December 2021 using an active wet-only collector consisting of a glass funnel and a PVC pipe that is only open during rain events. Results obtained show that all rain samples contained anthropogenic debris. The term “anthropogenic debris” is used to refer to the total number of particles as not all the particles found could be determined as plastic. Among all the samples, an average deposition of 77 ± 29 items (anthropogenic debris) m−2d−1 was found. The highest deposition was observed in November (148 items m−2d−1) while the lowest was found in March (46 items m−2d−1). Anthropogenic debris ranged in size from 0.1 mm to 3.87 mm with the most abundant particles being smaller than 1 mm (77.8%). The dominant form of particles found were fibers (95%), followed by fragments (3.1%). Blue color predominated (37.2%) in the total number of samples, followed by light blue (23.3%) and black (21.7%). Further, small particles (

In this work an extensive characterization over XeCl multishot laser irradiation was performed at different energy densities and with different thicknesses of graphitic coating superimposed on P and Al implanted 4H–SiC epitaxial layers. It was noted that at 0.6 J/cm2 the 180 nm coating provides a smooth surface unlike lower thicknesses or uncoated treatments. The μ-Raman investigation showed the crystalline quality as a function of the energy density. Through Medium Angle Annular Dark Field-Scanning Transmission Electron Microscopy (MAADF-STEM) and High Angle Annular Dark Field (HAADF)-STEM investigations, the absence of extended defects and the presence of regions with higher density of carbon interstitials (C i) was revealed. Circular Transfer Length Method (CTLM) measurements demonstrated how irradiation at 0.9 J/cm2 succeeded to reach values of (7.28 ± 1.15) × 102 Ω/sq, lower than the findings achieved with furnace treatment at 1650 °C. However, electrical characterization carried out through μ-Raman investigation over the Folded Transverse Acoustic (FTA) modes showed consistent activation of the order of 7 × 1019 cm−3 at 0.6 J/cm2 while exhibited CTLM extracted sheet resistance of (3.17 ± 0.06) × 104 Ω/sq. Therefore, this work highlights the contrast between fast processes as the accommodation and ionization of dopant atoms in substitutional positions and slow processes such as the recovery of ion implantation damage. By offering faster processing rates, lower thermal budgets, and high spatial control over the annealing process, laser annealing on 4H–SiC as a post-implantation thermal treatment approach presents several advantages over conventional annealing methods. This study marks a significant progress in comprehending and improving the effectiveness of laser annealing on 4H–SiC. [Display omitted] [ABSTRACT FROM AUTHOR]

Natural Fe-bearing ochres ranging in color from yellow to deep red and brown abound on earth’s crust. Quite often, ochres can be used for pigmenting purposes upon little or no processing, and, hence, the pertinent materials have been widely employed for decorative and artistic purposes since the dawn of prehistory; ochres have also found medicinal applications. This paper offers an overview regarding the range and composition of the available natural ochre pigments, their origin, properties, and potential processing. In addition, the production and processing of artificial ochres is presented. The prevailing analytical techniques currently employed in ochres’ identification and provenancing are also discussed, and guidelines for good practice are provided. Finally, authors offer some insight on ochres’ potential applications and their limitations, while a discussion pertaining to ochres in the Greco-Roman world is also included. [ABSTRACT FROM AUTHOR]

Abstract In this study, in order to analyze the materials and techniques used for the production of the inscribed plaques, multi-analytical scientific approach, including optical microscopy (OM), scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM–EDS), X-ray diffraction (XRD), micro-attenuated total reflection Fourier transform infrared spectroscopy (μ-ATR-FTIR), and micro-Raman spectroscopy (μ-Raman), were used to explore the materials and techniques utilized to create the “Chun Rong Xuan Mao” birthday inscribed plaque of the Qing Dynasty. The results showed that the plaque was made of cypress wood and decorative parts consisting of the surface lacquer layers, plaster lacquer layers and primer lacquer layers. Chinese lacquer was the principal material used in the surface lacquer layers; gypsum and Chinese lacquer were the materials used in the plaster lacquer layers; and the primer lacquer layers was composed of Chinese lacquer, calcite, and mixed pigments by cinnabar and minium. The surface lacquer layers of the inscribed plaque were lacquered black. Gypsum lacquer plaster has been commonly used in the ground layer of lacquerware in modern history. This study confirmed the existence of technology to make lacquerware using gypsum lacquer plaster in the Bashu area during the late Qing Dynasty. Moreover, this study not only provides new findings regarding the traditional production of inscribed plaques and offers technical support for the protection and restoration of such plaques but also has great significance to exploring the history of ancient techniques of lacquering and decorating lacquerware.

Green contemporary art conservation cleaning methods are explored as sustainable museum practices, ensuring the conservator's health and reducing the environmental impact. The performance of selected biodegradable cleaning agents, namely deionised (DI) water, a chelate based on trisodium salt of methylglycinediacetic acid (MGDA), Trilon® M, a non-ionic surfactant based on alkoxylated fatty alcohols (Plurafac® LF900), and two solvents, limonene and ethyl lactate, was evaluated for the surface cleaning of polymethyl methacrylate (PMMA), polylactic acid (PLA), polypropylene (PP), and plasticized polyvinyl chloride (pPVC). Plastic mockups were used untreated or artificially soiled, simulating particulate matter or sebum stains produced by handling. Furthermore, the efficacy of ink removal from the plastic's surface was evaluated. Surface examination was carried out using optical microscopy (OM), scanning electron microscopy (SEM), and atomic force microscopy (AFM), while µ-Raman and gloss measurements complemented the cleaning assessment methodology. The cleaning agents' potency depends on the type of plastic, precluding a general cleaning protocol. However, their cleaning efficacy is very promising, enriching the available choices for the cleaning of plastics, using sustainable materials and practices. This study offers valuable information to the conservation field regarding the effects of the selected biodegradable cleaning agents on each type of plastic, their application method, and their cleaning efficacy for the removal of different types of soil and ink. [ABSTRACT FROM AUTHOR]

Red and yellow pigments on more than 50 panel paintings were investigated. The studied artefacts dated from the mid‐15th to the mid‐19th centuries and came from regions in modern‐day Greece. Cinnabar and yellow ochres predominated. Ιn the case of the region of north‐west Greece there was a persistent use of orpiment and the employment of a peculiar ochre‐type pigment, while the rare lead‐antimony‐tin yellow was identified in an early 18th‐century Greek icon. Trends in pigments use during the post‐Byzantine period are revealed and compared with contemporary Western European ones. Recipes and terms of the Hermeneia manual are revisited in light of the analytical data, and pertinent misconceptions are restored. [ABSTRACT FROM AUTHOR]

This work aims to characterise the chemical composition of Roman opaque red glass sectilia dated to the 2nd century A.D and to shed light on Roman glassmaking production of different shades of red, from red to reddish-brown. Due to the lack of technical historical sources for this period many questions about technological aspects still remain. In this project a multi-disciplinary approach is in progress to investigate the red glass sectilia with several red hues from the Imperial Villa of Lucius Verus (161−169 A.D.) in Rome. First, colorimetric measurements were taken to identify the various red hues. The second step was chemical characterization of the samples and the identification of crystalline colouring phases. Particle Induced X-Ray Emission (PIXE) analysis was used to investigate the chemical composition of these glass samples, while the crystalline phases were identified by Raman Spectroscopy and Scanning Electrons Microscope with Energy Dispersive X-ray Spectrometry (SEM-EDS). Using SEM-EDS nanoparticles were detected as a colouring agent, the chemical composition and the morphology of which has been studied in depth. This information has been compared with the colorimetric analysis to establish any correlation with the different colour hues.

This work presents strategic multi-analytical investigations performed on “Orange Car Crash” by Andy Warhol in order to make a well-informed conservation decision. For determining the type of binding medium used in the artwork, Pyrolysis–Gas Chromatography/Mass Spectrometry (Py–GC/MS) and Thermally Assisted Hydrolysis and Methylation of GC/MS (THM–GC/MS) were employed. The presence of a coating was investigated by Py–GC/MS. Moreover, the comprehension and elucidation of the paint stratigraphy were studied by examining cross-sections of samples taken from both canvases with Optical Microscopy (OM) under reflected visible (Vis) and ultraviolet light (UV) and by Scanning Electron Microscopy with Energy Dispersive X-ray spectroscopy (SEM–EDX). The investigation of possible synthetic organic pigments (SOPs) and extenders was performed by µ-Raman spectroscopy, while micro-Attenuated Total Reflection of Fourier-Transform Attenuated Total Reflection (µ-ATR–FTIR) allowed us to assign each component detected by Py–GC/MS or THM–GC/MS to a specific layer. The data collected from “Orange Car Crash” show mostly the application of acrylic-based paint as well as alkyd with rosin acids-based ink, thus providing fundamental information about the paint stratigraphy and chemical composition of each layer. In addition to the goal of informing an appropriate conservation–restoration strategy, this work represents a rare scientific study of a work by Andy Warhol.

A set of decorative contemporary tile panels, created by the Portuguese artist Maria Keil (1914–2012) for the Lisbon metro stations, was studied under a noninvasive analytical methodology. This methodology combines X‐ray fluorescence spectrometry (μ‐XRF) and Raman spectroscopy in microscopic (μ‐Raman) mode for an elemental and structural composition characterisation of the glaze (glass matrix and network modifiers such as fluxes, opacifiers and colouring agents). μ‐XRF quantitative evaluation of the glassy matrix shows that all glazes have a lead silicate glass base. Results obtained by the combined use of μ‐XRF and μ‐Raman show that a zirconium‐based opacifier was used. Naples yellow (Pb2Sb2O7), lead–tin yellow type II (Pb(Sn,Si)O3), Pb–Sn–Sb triple oxide, cobalt blue (CoAl2O4), chromium oxide (Cr2O3) and malayite sphene (CaO·SnO2·SiO2) have been identified by μ‐Raman as some of the colouring agents, either used by themselves or in mixtures for obtaining the desirable colours intended by the artist. [ABSTRACT FROM AUTHOR]

In this study, in order to analyze the materials and techniques used for the production of the inscribed plaques, multi-analytical scientific approach, including optical microscopy (OM), scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM–EDS), X-ray diffraction (XRD), micro-attenuated total reflection Fourier transform infrared spectroscopy (μ-ATR-FTIR), and micro-Raman spectroscopy (μ-Raman), were used to explore the materials and techniques utilized to create the "Chun Rong Xuan Mao" birthday inscribed plaque of the Qing Dynasty. The results showed that the plaque was made of cypress wood and decorative parts consisting of the surface lacquer layers, plaster lacquer layers and primer lacquer layers. Chinese lacquer was the principal material used in the surface lacquer layers; gypsum and Chinese lacquer were the materials used in the plaster lacquer layers; and the primer lacquer layers was composed of Chinese lacquer, calcite, and mixed pigments by cinnabar and minium. The surface lacquer layers of the inscribed plaque were lacquered black. Gypsum lacquer plaster has been commonly used in the ground layer of lacquerware in modern history. This study confirmed the existence of technology to make lacquerware using gypsum lacquer plaster in the Bashu area during the late Qing Dynasty. Moreover, this study not only provides new findings regarding the traditional production of inscribed plaques and offers technical support for the protection and restoration of such plaques but also has great significance to exploring the history of ancient techniques of lacquering and decorating lacquerware. [ABSTRACT FROM AUTHOR]

This paper is a preliminary study on the origin of the precious red pigment cinnabar by μ‐Raman analysis. The importance of this pigment is partly due to its low availability. When the mineral was used in the Roman Age, the district of Almadén, Spain, was probably the most exploited region. However, it is still not well defined if further ores were chosen for supply. A scientific methodology has to be assessed. In the present study, samples with known provenance (Spain, Slovenia, Italy, Russia, China, and minor European deposits) were collected from Italian Mineralogical and Earth Science Museums. μ‐Raman analysis was chosen to acquire structural data, which were finally treated by statistical analysis. Most of the samples from China were characterized by the presence of selenium. This was proved by the additional band at ~200 cm−1. The statistical analysis of Raman data suggests that the position of the most intense band at ~252 cm−1 also influences the discrimination of the Chinese samples. This work also demonstrates that a higher purity may be revealed by μ‐Raman analysis, eventually leading to the discrimination of natural sources from synthetic cinnabar. It also proves that the most common exploitation sites, Almadén and Idrija, may be statistically distinguished. Despite its exploratory nature, this study is intended as a successful preliminary step to gain information of provenance from a single, potentially non‐destructive technique, such as μ‐Raman spectroscopy. [ABSTRACT FROM AUTHOR]

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Highlights • Microplastics were found in coastal waters and in fish gastrointestinal tract from the Tyrrhenian Sea. • Microplastics appeared in fragments or in filamentous shapes, in water and in fish respectively. • Microplastics have been characterized by FT-IR and Raman spectroscopies. Abstract In this work it is reported for the first time the characterization of microplastics from sea water samples and in two congener species of seabreams: Pagellus erythrinus and P. bogaraveo, Mediterranean fish species of great commercial importance. An experimental survey was conducted on May–June 2017 in the southernmost part of the Tyrrhenian Sea. Microplastics found in the sea water and in the grastrointestinal tract of two teleosts were characterized by Raman and IR spectroscopies. Microplastics found in sea water samples appeared in the form of fragments made of plastics of low and high density (PVC and LPDE). All the microplastics found in fish belonged to Nylon 66, typical fibers used in industry and in fisheries. Our findings highlighted the importance of further studies along the food web chain for a better understanding of the diffusion and possible consequences of this terrible threat. [ABSTRACT FROM AUTHOR]

Abstract Saint Demetrius of Stomion is a historical monastery placed in the geographical area of Larissa town, Greece, with a remarkable presence from its founding until nowadays. The monastery's present catholicon (main church) has been dated in the 16th century and its surviving wall paintings were constructed in 1758. In addition to the characterization of the materials applied, the purpose of this study is to determine the existence of a sole pictorial phase, that of the mid-18th century, or the occurrence of overpaintings. Additionally, the present study aims to begin the establishment of the documentation of materials and techniques of the late post-Byzantine iconographic guilds, which acted in Central and Northern Greece. The collected samples were analyzed by means of microscopic, spectroscopic and thermogravimetric methods. The use of fresco technique is implied by the major participation of calcium carbonate in all of the painting layers, its main contribution in the plaster layers and the microstratigraphic analysis of the samples' cross-sections, while the scarce and local presence of a proteinaceous material implies the limited use of egg-tempera technique for the highlights. The pigment analysis shows that mostly traditional pigments were used, including cinnabar, ferrous pigments (ochre, sienna, umber), minium, Naples yellow, massicot/litharge, green earth (celadonite), malachite, carbon and bone black, calcite, kaolinite and lead white. The absence of modern pigments, the consistency of all samples regarding microstratigraphy and applied materials, and the lack of the extensive use of an organic medium, strongly suggest the lack of overpaintings. [ABSTRACT FROM AUTHOR]

Abstract The aim of this research was to characterize ten Provisini , one of the most common silver coins in the Middle Age, dating back to the 13th century A.D. These coins are composed by Ag-Cu alloy and were coined in the Roman mint. A non-destructive, micro-destructive and multi-analytical approach was used, aiming to preserve the surfaces of the coins. The results of XRD and micro-Raman spectroscopy allow defining the alloy composition and the mineralogical nature of the alteration products (e.g. cuprite, tenorite, chlorargyrite, stromeyerite). X-ray maps provided information on major elements distribution on the surface. Finally, Electrochemical Impedance Spectroscopy (EIS) and Voltammetry of Immobilized Micro-Particles (VIMP) permitted to reconstruct the possible scheme of the multi-layering of the patina on the coins. Then, the conservation status was monitored. Highlights • Provisini are Ag-Cu coins most diffused in Middle Ages. • Two different layers occur and appear inhomogeneous. • The crack pattern is caused by metallurgical processing. • The superficial treatments of tosatura and imbiancatura were applied. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • The two K-Ca-Si glass compositions show different alteration behaviour. • Glass structure plays a dominant role in early stages under similar ageing conditions. • The Pb2+ and Ca2+ content may relate with more reactive structural arrangements. • Preservation state of extant pieces agrees with the replica's early stages. Abstract Several K-Ca-Si glass compositions typical of Central-European glassworks are susceptible to damage beyond recall, even in mild museum conservative conditions. In order to provide a comprehensive picture of the deterioration process, replica samples were produced and exposed to four different museum-like environments. The corrosion experiment was followed by the use of ToF-SIMS, μ -Raman and μ -FTIR, performing a systematic compositional and structural study for the early stages (one year) of surface alteration. This work demonstrates the dominant role of Pb2+ and Ca2+ content for the inferable existence of connected conduction pathways, with strong implications on the surface's hydration, alkali-diffusion and hydrolysis. [ABSTRACT FROM AUTHOR]

Microplastics (MPs) have been found in marine systems more frequently. We aim to analyze the MPs abundances, distribution, and characteristics in the intertidal sediments along the Oman Sea. Samples were collected from 7 locations with three replicates. Density separation was used to extract MPs, which were then visually counted and categorized based on their size, shape, and color. MPs abundance ranged between 219.6 ± 38.3 particles.kg−1dw and 617.3 ± 99.9 particles.kg−1dw with a mean abundance of 315.4 ± 24.4 particles.kg−1 dw. Fragments and fibers were the dominant shapes. Red and blue colors were observed in 61.6 % of the collected MPs. In addition, 100–500 μm size range of MPs were more abundant. Micro-Raman spectroscopy analysis revealed polypropylene was the major polymer constituent. The present study revealed the widespread occurrence of MPs as anthropogenic pollutants throughout the Oman Sea and highlighted the urgent need for regulations and policies to reduce the entry of this material into marine environments. [Display omitted] • Baseline information of MP abundance in the intertidal sediments along the Oman Sea was documented for the first time. • Microplastics were ubiquitous in the surface intertidal sediments along the Oman Sea. • Fragments and fibers were the most abundance shapes of microplastics. • Polypropylene was the major polymer constituent in the samples. [ABSTRACT FROM AUTHOR]

We investigate the evolution of the surface of a highly alloyed stainless steel (Sanicro 28) upon immersion in aqueous phosphoric acid solutions. For this purpose, both short- (few hours) and long-term immersion (several days) were carried out. A detailed analysis of XPS spectra allowed a distinction to be made between oxygen originating from the organic adlayer (adventitious contamination), the passive oxide layer, and adsorbed phosphate species. By estimating the fraction of oxygen due to phosphate species ( O ph ), it was shown that the O ph / P molar concentration ratio was ranging from about 2 to 3. This suggests the presence of a polyphosphate layer at the stainless steel surface, as also supported by Raman analysis, which influence the electrochemical behavior of SS in the acidic media. [ABSTRACT FROM AUTHOR]

Cobalt blue is a famous pigment in human history. In the past decade it is widely reported that the cobalt aluminate has been detected in ancient ceramics as blue colorant in glaze, yet the acquired Raman spectra are incredibly different from that of synthesised references, necessitating a reassessment of such contradictory scenario with more accurate analytic strategies. In this study, micro-Raman spectroscopy (MRS) and scanning electron microscopy (SEM) in association with energy dispersive spectrometry (EDS) were performed on under-glaze cobalt pigments from one submerged blue and white porcelain shard dated from Wanli reign (1573–1620 CE) of Ming dynasty (1365–1644 CE) excavated at Nan'ao I shipwreck off the southern coast of China. The micro-structural inspection reveals that the pigment particles have characteristics of small account, tiny size, heterogeneously distribution, and more importantly, been completely enwrapped by well-developed anorthite crystals in the glaze, indicating that the signals recorded in previous publications are probably not from cobalt pigments themselves but from outside thickset anorthite shell. The further spectromicroscopic analyses confirm this presumption when the accurate spectra of cobalt aluminate pigment and surrounding anorthite were obtained separately with precise optical positioning. Accordingly, we reassess and clarify the previous Raman studies dedicated to cobalt blue pigment in ancient ceramics, e.g. cobalt blue in celadon glaze, and in turn demonstrate the superiority and necessity of coupling spectroscopic analysis with corresponding structure observation, especially in the characterization of pigments from complicated physico-chemical environment like antiquities. Thus, this study promotes a better understanding of Raman spectroscopy study of cobalt blue pigments in art and archaeology field. [ABSTRACT FROM AUTHOR]

This work focuses on the study of the 19th century yellow chromate pigments based on barium (BaCrO), zinc (4ZnCrO·KO·3HO) and strontium (SrCrO). These pigments, which are reported to shift in hue and darken, have been found in 19th century artworks. A better understanding of their historic manufacture will contribute to the visual/chemical interpretation of change in these colours. Research was carried out on the Winsor & Newton (W&N) 19th century archive database providing a unique insight into their manufacturing processes. One hundred and three production records were found, 69% for barium, 25% for zinc and 6% for strontium chromates, mainly under the names Lemon, Citron and Strontian Yellow, respectively. Analysis of the records shows that each pigment is characterised by only one synthetic pathway. The low number of records found for the production of strontium chromate suggests W&N was not selling this pigment formulation on a large scale. Furthermore, contrary to what the authors have discovered for W&N chrome yellow pigments, extenders were not added to these pigment formulations, most probably due to their lower tinting strength (TS). The latter was calculated in comparison to pure chrome yellow (PbCrO, 100% TS) resulting in 92% for barium, 65% for zinc potassium and 78% for strontium chromate pigments. This indicates that W&N was probably using extenders primarily to adjust pigment properties and not necessarily as a means to reduce their costs. Pigment reconstructions following the main methods of synthesis were characterised by complementary analytical techniques: Fibre optic reflectance spectroscopy, X-ray diffraction, micro-Raman and micro-Fourier transform infrared spectroscopies. These pigments can be clearly distinguished on the basis of their infrared CrO asymmetric stretching fingerprint profile (between 1000 and 700 cm) and of their Raman CrO stretching bands (850-950 cm). This enabled their identification in historic paint samples: a tube of late 19th century W&N Lemon Yellow oil paint and micro-samples from paintings by three Portuguese painters, António Silva Porto (1850-1893), João Marques de Oliveira (1853-1927) and Amadeo de Souza-Cardoso (1887-1918). The good correlation found between the reconstructions and historic samples validates their use as reference materials for future photochemical studies. [ABSTRACT FROM AUTHOR]

New catalytic systems are still in development to meet the challenge of regulations concerning the emission of volatile organic compounds (VOCs). This is because such compounds have a significant impact on air quality and some of them are toxic to the environment and human beings. The catalytic combustion process of VOCs over non-noble metal catalysts is of great interest to researchers. The high conversion parameters and cost effective preparation makes them a valuable alternative to monoliths and noble metal catalysts. In this study, the cobalt catalyst was prepared by non-equilibrium plasma deposition of organic precursor on calcined kanthal steel. Thus prepared, cobalt oxide based microstructural short-channel reactors were tested for n -nonane combustion and the catalyst surfaces were examined by in situ μ-Raman spectroscopy and in situ infrared spectroscopy. The spectra collected at various temperatures were used in generalised two-dimensional correlation analysis to establish the sequential order of spectral intensity changes and correlate the simultaneous changes in bands selectively coupled by different interaction mechanisms. The 2D synchronous and asynchronous contour maps were proved to be a valuable extension to the standard analysis of the temperature dependent 1D spectra. [ABSTRACT FROM AUTHOR]

Gadolinium implanted cerium oxide (Gd-CeO 2 ) nanocomposites is an important candidate which have unique hexagonal structure and high K- dielectric constant. Gd-CeO 2 nanoparticles were synthesized using hydrothermal method. X-ray diffraction (XRD) results showed that the peaks are consistent with pure phase cubic structure the XRD pattern also confirmed crystallinity and phase purity of the sample. Nanocrystals sizes were found to be up to 25 nm as revealed by XRD and SEM. It is suggested that Gd gives an affirmative effect on the ion influence behavior of Gd-CeO 2 . XRD patterns showed formation of new phases and SEM micrographs revealed hexagonal structure. Photoluminescence measurement (PL) reveals the systematic shift of the emission band towards lower wavelength thereby ascertaining the quantum confinement effect (QCE). The PL spectrum has wider broad peak ranging from 390 nm to 770 nm and a sharp one centered on at 451.30 nm which is in tune with Gd ions. In the Raman spectra showed intense band observed between 460 cm −1 and 470 cm −1 which is attributed to oxygen ions into CeO 2 . Room temperature ferromagnetism was observed in un-doped and Gd implanted and annealed CeO 2 nanocrystals. In the recent studies, ceria based materials have been considered as one of the most promising electrolytes for reduced temperature SOFC (solid oxide fuel cell) system due to their high ionic conductivities allowing its use in stainless steel supported fuel cells. CeO 2 having an optical bandgap 3.3 eV and n-type carrier density which make it a promising candidate for various technological application such as buffer layer on silicon on insulator devices. [ABSTRACT FROM AUTHOR]

The gelatin-silver halide black and white prints represent an enormous photography heritage with a great value. Unaesthetic phenomena, the foxing stains that are caused by microbial growth on surface, have been described in stamps, drawings, books, and tissues but, until now, scarcely for photographic materials. In this study, a combination of various techniques, including culture-dependent and culture-independent approaches (RNA and DNA analysis), scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) and μ-Raman spectroscopy supported by X-ray fluorescence analysis (XRF), permitted to describe the microbial contamination dynamics of foxing stains present on the surface of two gelatin-silver halide photographs. The investigation provided also information on the effects of microbial activity on the materials' chemistry of the two prints. The action of microbial community resulted locally in either (a) formation of mixed aluminum-iron-potassium phosphate compounds that could be attributed to the hydrolytic activity of bacteria, (b) leaching of barite, (c) precipitation of a mixture of oxides, and (d) a change in the barium sulfate chemical structures. [ABSTRACT FROM AUTHOR]

Concern about atmospheric microplastic (MP) contamination has increased in recent years. This study assessed the abundance of airborne anthropogenic particles, including MPs, deposited in rainfall in Bahia Blanca, southwest Buenos Aires, Argentina. Rainwater samples were collected monthly from March to December 2021 using an active wet-only collector consisting of a glass funnel and a PVC pipe that is only open during rain events. Results obtained show that all rain samples contained anthropogenic debris. The term "anthropogenic debris" is used to refer to the total number of particles as not all the particles found could be determined as plastic. Among all the samples, an average deposition of 77 ± 29 items (anthropogenic debris) m -2 d -1 was found. The highest deposition was observed in November (148 items m -2 d -1 ) while the lowest was found in March (46 items m -2 d -1 ). Anthropogenic debris ranged in size from 0.1 mm to 3.87 mm with the most abundant particles being smaller than 1 mm (77.8%). The dominant form of particles found were fibers (95%), followed by fragments (3.1%). Blue color predominated (37.2%) in the total number of samples, followed by light blue (23.3%) and black (21.7%). Further, small particles (<2 mm), apparently composed of mineral material and plastic fibers, were recognized. The chemical composition of suspected MPs was examined by Raman microscopy. The analysis of μ-Raman spectra confirmed the presence of polystyrene, polyethylene terephthalate, and polyethylene vinyl acetate fibers and provided evidence of fibers containing industrial additives such as indigo dye. This is the first assessment of MP pollution in rain in Argentina., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2023 The Authors. Published by Elsevier Ltd.)

The finishes applied on stuccoworks deserves in-depth analytical investigations. A complete chemical and morphological survey is very useful in reconstructing the artist's technique, the history of the artworks through the sequence of the applied layers, and is needed as a basis for any conservation approach. Microscopic observations, both optical and electronic (SEM), and spectroscopic analyses (μRaman, μFTIR and EDS) of gilded and polychrome finishes on plaster relieves, were carried out on 17 samples from a celebrated neoclassical hall in the Royal Palace of Milan ( Hall of Caryatids ). The original decorative pattern had been damaged during a bomb-induced fire in the Second World War. Most of the surfaces have been fatally compromised and blackened by the effects of the fire. The survey presented here analysed the materials constituting the stucco surfaces and the damage induced by the fire. Green pigments were individuated and mapped, although no green surfaces were visible to the naked eye. It was therefore possible to reconstruct a decorative pattern painted in green, gold and white, similar to traditions of decoration in Austria and southern Germany. [ABSTRACT FROM AUTHOR]

Abstract SiGe islands have been proposed for applications in the fields of microelectronics, optoelectronics and thermoelectrics. Although most of the works in literature are based on MBE, one of the possible advantages of low-energy plasma-enhanced chemical vapor deposition (LEPECVD) is a wider range of deposition rates, which in turn results in the possibility of growing islands with a high Ge concentration. We will show that LEPECVD can be effectively used for the controlled growth of ordered arrays of SiGe islands. In order to control the nucleation of the islands, patterned Si (001) substrates were obtained by e-beam lithography (EBL) and dry etching. We realized periodic circular pits with diameters ranging from 80 to 300 nm and depths from 65 to 75 nm. Subsequently, thin films (0.8–3.2 nm) of pure Ge were deposited by LEPECVD, resulting in regular and uniform arrays of Ge-rich islands. LEPECVD allowed the use of a wide range of growth rates (0.01–0.1 nm s−1) and substrates temperatures (600–750°C), so that the Ge content of the islands could be varied. Island morphology was characterized by AFM, while μ-Raman was used to analyze the Ge content inside the islands and the composition differences between islands on patterned and unpatterned areas of the substrate.

The glazed tiles that paved the apse of the Monastery of St. Mary of Alcobaça were a rare decorative element in the most important part of this Cistercian construction. These medieval tiles, all monochromatic, are believed to be a thirteenth-century production and represent some of the first examples of tin-opacified glazed tiles in Christian Portugal. Although lead glazes have been extensively used in medieval pavements in North-Western Europe, opaque tin-glazes are far scarcer. The technology used in this case is a testimony of mixing cultures, combining Cistercian Order traditions of building materials and techniques with the Islamic tin-glazing technology brought to the Iberian Peninsula in the tenth century. These glazes were applied on tiles of several geometric shapes to achieve the final decorative effect. For the first time, these tiles were analytically characterized to determine the chemical composition of the different colours of glaze and these differences were assessed to explain the variety of colours and shades observed. The analytical techniques used were µ-PIXE (micro-particle-induced X-ray emission), µ-Raman spectroscopy and optical microscopy. Samples selected for this study comprise all colours observed in Alcobaça tiles: white, turquoise, brown and several shades of green. Results show that the variety of colours and shades are consistent with different proportions of CuO, Fe2O3and SnO2in a lead-glazed matrix, together with a K-feldspar-rich white inner layer, most likely to be a slip. [ABSTRACT FROM AUTHOR]

The purpose of this in vitro study was to assess whether the mineralization degree and elemental content in tooth enamel are altered when bleaching the teeth with two different over-the-counter bleaching gels, exceeding the recommendations of the manufacturer. In order to perform this evaluation, 12 healthy teeth were used, six samples were treated with Teeth Whitening Home Kit, and the other six samples were treated with WHITE! (Bingo-UK) bought in online shopping sites, for the period of 39 days. The pH of each product and the elemental content of each sample, before and after, were obtained by energy dispersive X-ray spectrometry and phosphate (PO43-) profile was evaluated with Raman spectroscopy. Data was analyzed accordingly to a pre-established plan with a mixed-model ANOVA for repeated measures, significance was set at 5%. Both products were markedly acidic and below enamel critical level of 5.5. Moreover, seven days after treatment, demineralization was significant, wherein at the end of the study the degree of demineralization seems to be permanent. Copyright © 2015 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

This case study illustrates the analytical characterization of 12 academic nude paintings by Veloso Salgado, made between 1883 and 1893. The study was done with in situ methods (infrared reflectography and EDXRF) and benchtop equipment (Raman and FTIR microscopes and SEM-EDS). Infrared reflectography revealed underdrawings, painting style, execution method and retouched/restored areas. Analytical techniques allowed the identification of gypsum, lead white, barium white, zinc white, yellow ochre, chrome yellow, zinc yellow, vermilion, synthetic ultramarine blue, cerulean blue, Prussian blue, viridian, green earth, Paris green, red ochre, raw umber and lamp black. These results provide valuable information on Salgado’s palette and his artistic production technique and allow the distinction between palettes used in Lisbon and Paris and consequently, technical interchanges between both Academies. Finally, this study intends to start a systematic analytical study of the Faculty of Fine Arts’ collection, allowing the characterization of many other authors and their influences for the development of painting methodology in this Academy. [ABSTRACT FROM AUTHOR]

This study outlines the chemical characterisation of a large number of commercial spray paints as used in street art, graffiti vandalism and for decoration purposes. The analyses were focused on the identification of the synthetic binding media, pigments and additives such as plasticisers and fillers, providing a database as well as a methodology which could remarkably help investigations in a broad panorama of case studies, ranging from forensic science to cultural heritage. A protocol has been developed based on a multi-technique approach. In particular, Fourier Transform Infrared (FTIR) spectroscopy, Pyrolysis/Gas Chromatography–Mass Spectrometry (Py/GC–MS) and μ-Raman spectroscopy were applied and their strength and weakness points as to the identification of all spray paints components are outlined. Each sample was first examined with FTIR spectroscopy as a preliminary screening step to obtain indications on the main binder, which could then be confirmed and detailed using Py/GC–MS. Some pigments and extenders could be efficiently identified by examination of the FTIR spectra and pyrolysis products. However, for most samples μ-Raman spectroscopy investigation was required in addition to the mentioned techniques in order to achieve the complete chemical characterisation of organic and inorganic pigments, extenders and fillers. Differences and common features among brands/colours are highlighted and discussed. [ABSTRACT FROM AUTHOR]

ZnO nano/micro rod arrays (N/MRAs) thin films were grown on ZnO nuclei layer using chemical bath deposition technique via mixed degree of supersaturation. In the present work, the interface energy barrier introduced by Mn doping confine the nucleation site is decisively investigated. Hexagonal wurtzite crystal structure of pure and Mn doped ZnO N/MRAs is clearly confirmed by structural and optical characterization techniques (X-ray diffraction and µ-Raman). From XRD spectra, it is shown that the preferentially oriented (002) diffraction peak changed to (100) by Mn doping that indicates the stacked crystallographic planes are produced under nucleation sites barrier. Scanning electron microscopic (SEM) images of ZnO N/MRAs clearly shows the ZnO microrods (MRs) are aligned on ZnO nanorods (NRs). By Mn doping, the ZnO N/MRAs converted into microcrystalline structures including rods and spherulitic under changing mixed degree of supersaturation. The Mn ions in ZnO N/MRAs is confirmed by energy dispersive X-ray spectroscopic analysis (EDX).The band gap energy value and atomic level defect states of pure and Mn doped ZnO N/MRAs are calculated and analyzed using UV–vis absorption and photoluminescence spectra respectively. [ABSTRACT FROM AUTHOR]

This paper presents the results of our investigations on a playing card preserved at The Mūzih-i Ā ynih va Rushanāī in Yazd, Iran. Conducting micro X-ray fluorescence spectrometry (μ-XRF), micro-Raman spectroscopy (μ-Raman), infrared reflectography (IRR), ultraviolet fluorescence photography, radiography, and optical microscopy, various paints applied on the playing card were identified. According to our analytical studies, red, green, blue, black, and gold-like metallic paints were identified to be a red monoazo pigment (β-naphthol PR 53:1), chrome green, artificial ultramarine blue, carbon black, and brass powder (Dutch metal powder), respectively, dating the playing card to 1895 onward based on the manufacturing date of the red monoazo pigment. Barite was also shown to be mixed with the pigments as an extender. On the other hand, the portrait's face of the playing card was peculiarly blackened. Our analytical approach toward characterizing the blackened face showed that the black paint was achieved by carbon black and, in other words, the face was not blackened due to the darkening of Pb-bearing pigments. Moreover, it was shown that there was no underdrawing under the black face and the black paint was most probably executed in the same time with the other paints. Considering the possible use of the playing card, it was suggested not to remove the blackened face in the cleaning process since the black paint was a part of the integrity of the playing card. [ABSTRACT FROM AUTHOR]

Corrosion layers in some copper and bronze archaeological objects from Haft Tappeh archaeological site, southwest Iran, were studied. For this purpose, optical microscopy, scanning electron microscopy with energy dispersive X-ray microanalysis, micro- Raman spectroscopy and X-ray diffraction methods were applied to observe corrosion stratigraphy and their characteristics as well as identification of chemical composition and phase determination of different corrosion layers. Based on optical and electron microscopy, three different corrosion strata were identified in cross section of different metallic objects including various red, green, white-grey powdery and dark internal compact layers. Scanning electron microscopy with energy dispersive X-ray microanalysis on different corrosion layers revealed that Cu, Sn and Cl are the main elements in the chemical composition of different layers. Tin-rich phases were detected in white-grey and dark layers that may be formed because of the internal oxidation of tin as well as the decuprification (selective dissolution of copper) phenomena occurring during long-termburial period in the soil. Also, the XRD and micro-Raman spectroscopy results proved that the main corrosion products are nantokite (CuCl), copper trihydroxychlorides and copper oxides. The combination of these analytical methods allows us to explore the surface and internal corrosion layers of the archaeological copper and bronze samples, and major interest is on studying their chemistry, microstructural properties and corrosion stratigraphy. [ABSTRACT FROM AUTHOR]

Sherds representative of the three Portuguese faience production centers of the 17th century – Lisbon, Coimbra and Vila Nova were studied with the use of mostly non-invasive spectroscopies, namely: ground state diffuse reflectance absorption (GSDR), micro-Raman, Fourier-transform infrared (FT-IR) and proton induced X-ray (PIXE) or X-ray fluorescence emission (XRF). X-ray diffraction (XRD) experiments were also performed. The obtained results evidence a clear similarity in the pastes of the pottery produced Vila Nova and some of the ceramic pastes from Lisbon, in accordance with documental sources that described the use of Lisbon clays by Vila Nova potters, at least since mid 17th century. Quartz and Gehlenite are the main components of the Lisbon’s pastes, but differences between the ceramic pastes were detected pointing out to the use of several clay sources. The spectroscopic trend exhibited Coimbra’s pottery is remarkably different, Quartz and Diopside being the major components of these pastes, enabling one to well define a pattern for these ceramic bodies. The blue pigment from the Lisbon samples is a cobalt oxide that exists in the silicate glassy matrix, which enables the formation of detectable cobalt silicate microcrystals in most productions of the second half of the 17th century. No micro-Raman cobalt blue signature could be detected in the Vila Nova and Coimbra blue glazes. This is in accordance with the lower kiln temperatures in these two production centers and with Co 2+ ions dispersed in the silicate matrix. In all cases the white glaze is obtained with the use of tin oxide. Hausmannite was detected as the manganese oxide mineral used to produce the purple glaze (wine color “vinoso”) in Lisbon. [ABSTRACT FROM AUTHOR]

Based on micro-Raman spectroscopy (μ-Raman), micro X-ray fluorescence spectrometry (μ-XRF), X-ray diffractometry (XRD) and optical microscopy, this paper presents the results of our analytical studies on the early Islamic pigments used in the Masjid-i Jame of Fahraj, central Iran. Our investigations showed that ultramarine blue and haematite were used as blue and red pigments, respectively. Moreover, huntite was identified as white pigment with which whewellite was associated as a degradation product. Interestingly, the black paint was identified to be mainly composed of black plattnerite mixed with mimetite, hydromorphite and galena. Our geological survey at the Darreh Zanjir mine, located 35 km west of Fahraj, suggested this mine to be a possible source for supplying the black plattnerite. Accordingly, black plattnerite is suggested to be most probably used as a pigment and not to have formed as a degradation product of lead-based pigments. [ABSTRACT FROM AUTHOR]

The first archaeological evidence reported for tile production in Portugal was discovered in Santo António da Charneca (SAC), late 15th or early 16th centuries' pottery kiln, south riverside of Tagus River. Samples from this kiln were studied with the use of non-invasive spectroscopies, namely, μ-Raman, ground-state diffuse reflectance absorption, Fourier transform infrared and particle-induced X-ray or X-ray fluorescence emission. These results were compared with the ones obtained for coeval tiles produced in Seville, Spain, originated from Portuguese archaeological sites, because it is well know that the Portuguese King Manuel the First imported in 1498 significant quantities of those tiles to decorate several palaces. The obtained results provided new spectroscopic insights, used to establish similarities but also clear differences regarding the SAC and the coeval Seville tiles found in Portugal. White glaze from both tiles gave evidence about the use of tin oxide as whitening agent and lead oxide as glassy agent. Cobalt oxides were also used as blue pigments in the two production centres. The brown and amber pigments in the samples from SAC derive from the manganese oxides dispersed in the lead-tin glaze, and kentrolite crystals were identified by μ-Raman in these tiles. In the arista and cuerda-seca tiles from Seville, diopside was detected. Divalent copper also exists in the green glaze matrix but in small amounts, which did not allow the Raman detection of the copper compound's microcrystals. However, diffuse reflectance measurements point to malachite green as responsible of green coloration. The Seville pastes contain calcium carbonate, although the SAC pastes do not evidence significant amounts of that compound in its composition. All the SAC pastes evidenced a high silica level, and quartz and anatase were clearly detected in the paste and possibly kaolinite. The Raman signals of orthoclase and calcium carbonate were detected in the Seville tiles. Copyright © 2014 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]