Search Results (494)

This article presents a comprehensive analysis of the polychrome paintings on the Flower Peking Opera Theatre in Bozhou, Anhui Province, China. A multi-technique approach was employed, including polarized light microscopy (PLM), X-ray fluorescence (XRF), micro-Raman spectroscopy, X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy with energy-dispersive spectrometry (SEM-EDS), and Herzberg staining to determine the composition and methodologies involved in the formation of the pigment layer, the white primer, and the ground layer. The analysis identified cinnabar (red), both artificial ultramarine and Prussian blue (blue), a mixture of barite and gypsum (white), a mixture of chromite and Prussian blue (green), and carbon black (black) in the pigment layer. The ground layer was found to consist of clay and plant fibers (cotton and hemp), while the white prime layer was primarily composed of barite and gypsum. This research provides insights for future conservation and restoration efforts. Full article

This study investigates the Lower Cretaceous Madongshan Formation in the Liupanshan Basin, a classic saline lacustrine succession, to elucidate the key mechanisms for high-quality source rock development. An integrated approach combining organic geochemistry (Rock-Eval, Gas Chromatography–Mass Spectrometry [GC-MS], δ¹³C) and inorganic elemental geochemistry (X-ray Fluorescence [XRF]) was applied to a well-characterized outcrop section. The results reveal that the Madongshan Formation contains mature, oil-prone source rocks dominated by Type II₁ and II₂ kerogen. Geochemical proxies consistently indicate deposition within an arid to semi-arid climate, which drove the formation of a stratified, saline-to-hypersaline water column with persistent bottom-water anoxia (Pristane/Phytane [Pr/Ph] < 0.5). Isotopic and biomarker data confirm a mixed source input, with an average contribution of approximately 55% from aquatic organisms supplemented by a significant terrestrial influx. Based on these findings, we propose a “Salinity-Driven Preservation” model. This model posits that climate-induced salinity played a critical role in establishing a persistent halocline, leading to an intensely anoxic “preservation factory” at the lake bottom. Current evidence suggests that this exceptional preservation efficiency was a pivotal factor compensating for moderate productivity to control organic matter enrichment. This study provides a robust framework for predicting source rock quality in the Liupanshan Basin and serves as a valuable analogue for other saline lacustrine systems. Full article

Documenting baseline elemental distribution patterns in crops under non-contaminated conditions provides a physiological reference for understanding constitutive metal homeostasis. This study compared the internal allocation of elements in sunflower (Helianthus annuus), wheat (Triticum aestivum), and maize (Zea mays) grown in soil with a specific geochemical profile. Soil was characterized using X-ray Fluorescence Spectroscopy (XRF) and Inductively Coupled Plasma Mass Spectrometry (ICP-MS). Plants were grown under controlled conditions, and elemental concentrations in roots and shoots were quantified to calculate Bioaccumulation (BCF) and Translocation (TF) Factors. Soil analysis confirmed nickel (42.6 mg kg⁻¹) and copper (32.8 mg kg⁻¹) concentrations within typical global ranges for uncontaminated soils. Species exhibited different distribution tendencies: sunflower showed balanced root–shoot allocation for nickel (TF = 1.00); wheat demonstrated pronounced root retention of nickel and copper (TF < 0.5); and maize exhibited preferential translocation of copper (TF = 0.76) alongside root retention of nickel. Concentrations of lead, selenium, and silver were minimal across all species. The study delineates different species-specific tendencies in internal elemental allocation under given growth conditions. These patterns represent baseline physiological behaviors rather than responses to contamination, providing a comparative dataset that contributes to the understanding of crop ionomics and informs the interpretation of tissue metal concentrations in relation to soil conditions. Full article

Ancient bronzes are invaluable for studying the cultures and history of ancient societies around the world. However, corrosion can diminish their research and aesthetic value, as well as affect their longevity. Therefore, it is crucial to study the corrosion behavior and mechanisms of these artifacts using advanced characterization techniques. This article provides a systematic review of the corrosion behavior of bronze artifacts and the advanced characterization techniques employed in their study. It summarizes the corrosion mechanisms of bronze artifacts and the factors affecting corrosion, including composition, structure, and the external environment. It also describes advanced analytical techniques for characterizing corrosion products and mechanisms, such as X-ray fluorescence (XRF), laser ablation coupled to quadrupole mass spectrometry (LAMQS), X-ray tomography (CT), and neutron diffraction. Bronze corrosion studies can be enhanced by the integration of artificial intelligence (AI) and machine learning (ML). Finally, it discusses potential future research directions in the field of bronze artifact corrosion and conservation. Full article

Portuguese ceramic tile (azulejo) production has evolved significantly since its beginnings in the 16th century. While historic tiles reflect well-established traditional techniques and styles, modern and contemporary works began to explore new aesthetic and material possibilities, introducing textures, surface effects, and experimental approaches that challenge conventional conservation methods. This study examines a contemporary Portuguese tile panel dated from 1987, featuring decorative effect glazes with crater and crazing textures, which were characterized and reproduced. Analytical techniques, including optical microscopy, micro-X-ray fluorescence spectrometry, and Raman spectroscopy in microscopic mode, were employed to characterize material composition and formation mechanisms. Results showed that the crater-effect glazes were achieved with a silica-rich glaze recipe with MnO₂ and ZrO₂. The crazing effect developed in regions where unmelted crystalline silica induced internal stresses within a lead-silicate glaze, contributing to localized degradation. Experimental reproductions of the glazes, guided by analytical data, were conducted to better understand their formation and inform conservation strategies. The results provide essential insights for the technical assessment, documentation, and preservation of contemporary ceramic artworks featuring decorative effect glazes and contribute to the broader field of cultural heritage conservation. Full article

The growing demand for critical elements vital to the energy transition highlights the need for sustainable secondary sources. Sedimentary phosphate mining generates waste rock known as spoil piles (SPs). These SPs retain valuable phosphate and other critical elements such as rare earth elements (REEs). This study examines the potential of recovering these elements from SPs. A comprehensive sampling strategy was implemented, and a 3D topographic model was generated using drone imagery data. The model revealed that these SPs cover an area estimated at 48,633,000 m², with a total volume of approximately 419,612,367 m³. Chemical analyses using X-ray fluorescence and inductively coupled plasma mass spectrometry techniques indicated valuable phosphate content, with an overall concentration of 12.6% P₂O₅ and up to 20.7% P₂O₅ in the fine fraction (<1 mm). The concentrations of critical and strategic elements in the SPs were as follows: magnesium [1%–8%], REEs [67–267 ppm], uranium [48–173.5 ppm], strontium [312–1090 ppm], and vanadium [80–150 ppm]. Enrichment factors showed that these elements are highly concentrated in fine fractions, with values exceeding 60 for Y, 40 for Sr, and 780 for U in the +125/−160 µm fraction. A positive correlation was observed between these elements and phosphorus, except for magnesium. Automated mineralogy confirmed that the fine fraction (<1 mm) contains more than 50% carbonate-fluorapatite (CFA), alongside major gangue minerals such as carbonates and silicates. These findings demonstrate the potential for sustainable recovery of phosphate, magnesium, REEs, strontium, vanadium, and uranium from phosphate mining waste rock. Full article

Quality control of herbal medicinal products (HMPs) is challenging due to their multicomponent composition. For most HMPs, chemical reference standards (CRSs) required for traditional chromatographic and spectral analyses are unavailable. According to USP and Ph. Eur., an exception is valerian tincture, for which highly specific CRSs have been developed. The aim of this study was to use principal component analysis (PCA) and the novel two-dimensional diffuse laser scattering (2D-DLS) method to identify HMPs and their aqueous-ethanolic extracts according to their botanical genera without relying on specific marker compounds. Spectral data were compiled into an extensive library covering a wide wavelength range—from 0.02 nm to 15,000 nm. PCA of the spectral data (UV spectrophotometry, fluorimetry, FTIR spectroscopy, and X-ray diffraction) enabled clustering of samples by individual botanical genera. The most significant information for sample differentiation was provided by wavenumbers of 1400, 1180, and 931 cm⁻¹ in the IR spectra and wavelengths of 450 nm and 672 nm in the UV and fluorescence spectra, respectively. During model cross-validation, all “blind samples” were correctly classified by botanical genus, achieving a non-error rate (NER) of 100%. Furthermore, the unique 2D-DLS method was used to rapidly identify tinctures without opening the glass bottles. Full article

Apatite is a key indicator mineral whose chemical signature can reveal the genesis and evolution of ore-forming systems. However, correctly interpreting these signatures requires a robust discrimination between apatite types formed by different geological processes, such as metamorphism and hydrothermal activity. This study aims to chemically characterize and genetically classify apatite samples from the Slyudyanka deposit (Siberia, Russia) to establish discriminative geochemical fingerprints for metamorphic and hydrothermal apatite types. We analyzed 80 samples of apatite using total reflection X-ray fluorescence (TXRF) and inductively coupled plasma mass spectrometry (ICP-MS). The geochemical data were processed using principal component analysis (PCA) and k-means cluster analysis to objectively discriminate the apatite types. Our analysis reveals three distinct geochemical groups. Metamorphic veinlet apatite is defined by high U and Pb, low REE, Sr, and Th, and suprachondritic Y/Ho ratios. Massive metamorphic apatite from silicate–carbonate rocks shows extreme REE enrichment and chondritic Y/Ho ratios. Hydrothermal–metasomatic apatite features high Sr, Th, and As, with intermediate REE concentrations and chondritic Y/Ho ratios. Furthermore, we validated the critical and anomalous Y concentrations in the metamorphic veinlet apatite by cross-referencing TXRF and ICP-MS data, confirming the reliability of our measurements for this monoisotopic element. We successfully established diagnostic geochemical fingerprints that distinguish apatite formed in different geological environments at Slyudyanka. The anomalous Y/Ho ratio in metamorphic veinlet apatite serves as a key discriminant and provides insight into specific fractionation processes that occurred during the formation of phosphorites in oceanic environments, which later transformed to apatites during high-grade metamorphism without a change in the Y/Ho ratio. This work underscores the importance of multi-method analytical validation for accurate geochemical classification. Full article

Two folding screens by futurist artist Giacomo Balla (1871–1958) in the collection of the Kröller-Müller Museum (the Netherlands) were investigated: Paravento con linea di velocità (1916–1917) and Paravento (1916/1917–1958). The screens are painted on both sides, the first on four canvases, stretched onto two wooden strainers and framed with painted wooden strips, and the second on wooden panels set into four painted stiles. In the past, damages on Paravento con linea di velocità were restored by conservators, while Paravento was probably first reworked by the artist himself and later restored by conservators. Yellowed varnish and discolored retouches on both screens led to a wish for treatment. The aim of this research was to gain insight into the painting techniques, layer buildup, pigments, binders, and varnishes of the two artworks. This information supported the decision making for treatment, and it broadens the knowledge on the materials used by Balla. Up to now, only a few published studies deal with the technical examination of paintings by this artist. Both folding screens were subjected to technical photography (UV, IR photography, and X-ray) and were examined with portable point X-ray fluorescence (pXRF) and Raman spectroscopy. Moreover, samples were taken. Cross-sections were studied with optical microscopy, scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDX), attenuated total reflection Fourier-transform infrared (ATR-FTIR) imaging, and micro-Raman spectroscopy. Loose samples were examined with SEM-EDX, FTIR and micro-Raman spectroscopy, and pyrolysis gas chromatography mass spectrometry (Py-GC/MS). For Paravento con linea di velocità, all pigments and fillers of the painted canvases are compatible with the dating of the screen (1916–1917), but they differ from those on the frame. Here, rutile, in combination with various pigments, among which are blue copper phthalocyanine (PB15) and other synthetic organic pigments, was found. This indicates that the frame has been painted later, likely after the Second World War. The composition of the binders differs as well. Drying oil and pine resin have been used on the canvases, explaining the smooth and glossy appearance and solvent-sensitivity of the paint. On the frame, oil with some alkyd resin was identified. The provenance of the screen before 1972 is not clear, nor when the frame was made and painted and by whom. The results for Paravento indicate that the palettes of the two sides—painted in different styles—are comparable. Mainly inorganic pigments were found, except for the dark red areas, where toluidine red (PR3) is present. pXRF showed high amounts of zinc; cross-sections revealed that zinc white is present in the lower layers. These pigments are compatible with the dating of the screen (1916–1917). In many of the upper paint layers though, except for some green, dark red, and black areas, rutile has been identified. This indicates that these layers were applied later, likely after the Second World War. Since this folding screen was used by the artist and his family until his death in 1958, it seems likely that Balla himself reworked the screen. Full article

Coated fabrics featuring plasticised poly(vinyl chloride) (p-PVC) and thermoplastic polyurethane (TPU) coatings are widespread in fashion collections. These materials pose significant conservation challenges due to their production and chemical variability, coupled with issues of rapid deterioration. Despite their prevalence and instability, systematic research on their composition and ageing behaviour remains limited, as most studies rely mainly on infrared spectroscopy and cover a small number of cases, which cannot fully capture their chemical complexity. This knowledge gap represents a pressing issue, as it hampers the development of well-informed conservation strategies. This research addresses this gap by investigating a representative set of twenty-five historical and contemporary fabrics from the 1990s onwards, coated with aromatic and aliphatic polyester-based TPUs, as well as phthalate- and terephthalate-plasticised PVCs. Samples were characterised using a multi-analytical approach combining optical microscopy, infrared spectroscopy, pyrolysis–gas chromatography/mass spectrometry, and X-ray fluorescence spectroscopy. This integrated strategy provided unprecedented detail on the chemical variability of p-PVC and TPU-coated fabrics, enabling the identification of primary components, additives, degradation products, and mixed compositions. This study underscores the value of multi-technique analysis to capture the complexity of such coated fabrics, providing essential knowledge for further research and development of effective conservation strategies for fashion collections. Full article

Comprehensive studies of Famille rose porcelains, particularly ruby-back pieces, are rare and have generally not addressed the vibrational signatures arising from gold nanoparticles. Due to the high cultural and material value of these artifacts, a strictly non-invasive approach combining X-ray fluorescence (XRF) and Raman (micro-)spectrometry must be employed. If the conservation of porcelain does not pose any difficulties, fakes exist and they must be identified. Preliminary studies show that the presence of metal nanoparticles generates plasmon-related fluorescence. Our results confirm that plasmon fluorescence is more effective than pXRF for detecting colloidal gold, whereas pXRF efficiently identifies associated elements such as arsenic, tin, and, newly observed, antimony; the presence of iron is difficult to demonstrate due to its ubiquitous occurrence. Yellow and green hues, distinct from those produced by Cu²⁺ ions alone, are mainly due to simple tin yellow (PbSnO₃), while the cobalt used originates from a mixture of European smalt (rich in arsenic and potassium) and Asian ores (rich in manganese). Minimal variability was observed among egg-shell porcelains with similar decorations and dimensions, suggesting a common workshop or standardized raw materials and procedures. Two other egg-shell plates employ a different gold preparation technique (addition of Sn and Sb rather than As), which is visually evident in the ruby color. Full article

In this work, we developed and characterized a hydroxyapatite (HA) ceramic coating derived from Ucides cordatus crab-shell waste and applied it onto Ti–Al–V titanium substrates for biomedical use. Substrate analysis confirmed an α + β two-phase microstructure and Rockwell C hardness of ~35 HRC; optical emission spectrometry indicated a non-conforming Ti–6Al–4V composition (Al slightly above and V slightly below ASTM F136-18 limits), with expected α-phase predominance. Aqueous synthesis of biogenic HA used CaO (from 800 °C calcined shells) reacted with β-tricalcium phosphate (β-Ca₃(PO₄)₂), followed by deposition onto Ti–Al–V surfaces prepared with or without a thermochemical treatment that homogenized roughness (Ra ≈ 0.587 µm). The coatings were continuous, ~95–98 µm thick, and showed good qualitative adhesion. Scanning Electron Microscopy (SEM) revealed porous, nanocrystalline, acicular morphologies typical of biogenic apatite’s. Energy-Dispersive X-ray Spectroscopy (EDS) yielded Ca/P ≈ 1.85–1.88, while X-ray Fluorescence (XRF) indicated Ca-enrichment relative to stoichiometric HA. X-ray Diffraction (XRD) confirmed a predominantly hexagonal HA phase with high crystallinity. These results demonstrate a technically and environmentally feasible route to bioactive coatings using marine biowaste, aligning low-cost, local waste valorization with functional performance on titanium implants. Full article

Land desertification in the Agropastoral ecotone of arid and semi-arid regions poses significant threats to ecological security. Elucidating the geochemical characteristics and provenance of surface sediments is crucial for understanding desertification mechanisms and developing effective sand-control strategies. This study focuses on Kangbao County in the Bashang region of Hebei Province. We systematically collected 57 surface sediment samples from four geomorphic units: low mountains-hills, gently sloping hills, gully depressions, and undulating plains. Major and trace element concentrations were determined using X-ray fluorescence spectroscopy (XRF) and inductively coupled plasma mass spectrometry (ICP-MS). Elemental ratios, principal component analysis (PCA), and Non-metric Multidimensional Scaling (nMDS) were employed to decipher sediment geochemical signatures and provenance, emphasizing geomorphologically controlled source differentiation mechanisms. Key findings are as follows: (1) Geochemical characteristics reveal that sediment elemental enrichment or depletion patterns exhibit fundamental differences depending on the specific bedrock reference. When normalized against felsic versus mafic end-members, elements including Fe₂O₃, MgO, TiO₂, CaO, Cr, Ni, Co, V, Rb, and Ba demonstrate contrasting geochemical behaviors. (2) The sediments originate from a homogenized mixture derived from the weathering of regional bedrock, clearly distinct from the high-maturity aeolian sands of the Hunshandake Sandy Land. (3) The spatial geochemical differentiation of surface sediments follows a two-stage process: the initial formation of a homogenized sediment source from bedrock weathering products, followed by subtle modification through landform-specific geomorphic processes, resulting in weak but systematic geochemical variations across the landscape. Based on these findings, a zonal management strategy is proposed to disrupt the localized sediment cycle by intercepting sources in hilly areas, restoring gully depressions, and blocking aeolian pathways on the plains. This study provides a scientific basis for precise desertification control in Kangbao and supports ecological barrier enhancement for the Beijing–Tianjin–Hebei region. Full article

The Lower Cambrian Niutitang Formation was deposited precisely during the Cambrian Explosion period, a short-lived interval marked by drastic shifts in oceanic chemistry and climate. This stratigraphic sequence preserves a comprehensive record of early-ocean evolution and constitutes a world-class reservoir for rare and precious metals, widely termed the “poly-metallic enrichment layer”. Despite its metallogenic prominence, the genetic model for metal enrichment in the Niutitang Formation remains contentious. In this study, we employed inductively coupled plasma mass spectrometry (ICP-MS), carbon and sulfur analyzer, and X-ray fluorescence spectrometry (XRF) to quantify trace-metal abundances, redox-sensitive element distribution patterns, rare-earth element signatures, and total organic carbon contents. Results reveal that metal enrichment in the Niutitang Formation was governed by temporally distinct mechanisms. Member I records extreme enrichment in As, Ag, V, Re, Ba, Cr, Cs, Ga, Ge, Se and In. This anomaly was driven by the Great Oxidation Event and intensified upwelling that oxidized surface waters, elevated primary productivity and delivered abundant organic matter. Subsequent microbial sulfate reduction generated high H₂S concentrations, converting the water column to euxinic conditions. Basin restriction imposed persistent anoxia in bottom waters, establishing a pronounced redox stratification. Concurrent vigorous hydrothermal activity injected large metal fluxes, leading to efficient scavenging of the above metals at the sulfidic–anoxic interface. In Members II and III, basin restriction waned, permitting enhanced water-mass exchange and a concomitant shift from euxinic to anoxic–suboxic conditions. Hydrothermal metal fluxes declined, yet elevated organic-matter fluxes continued to sequester Ag, Mo, Ni, Sb, Re, Th, Ga, and Tl via carboxyl- and thiol-complexation. Thus, “organic ligand shuttling” superseded “sulfide precipitation” as the dominant enrichment mechanism. Collectively, the polymetallic enrichment in the Niutitang Formation reflects a hybrid model controlled by seawater redox gradients, episodic hydrothermal metal supply, and organic-complexation processes. Consequently, metal enrichment in Member I was primarily governed by the interplay between vigorous hydrothermal flux and a persistently sulfidic water column, whereas enrichment in Members II and III was dominated by organic-ligand complexation and fluctuations in the marine redox interface. This study clarifies the stage-dependent metal enrichment model of the Niutitang Formation and provides a theoretical basis for accurate prediction and efficient exploration of polymetallic resources in the region. Full article

The great city of Mayapan has experienced a technological change in pottery making, and our results confirm a shift in the raw materials and possibly the potters’ knowledge about them. The dynamics of change during the Postclassic period in the Maya area are reflected in the material changes used to make pottery. A comprehensive analysis was conducted on a collection of 248 pottery items from the archaeological site of Mayapán in Yucatán, Mexico, dating from the Middle Preclassic to Postclassic periods (700 BC–1500 CE). Non-invasive methods were used for the entire pottery set, including X-ray fluorescence (XRF) and fiber-optic reflectance spectroscopy (FORS). Additionally, for a representative subset, minimally invasive techniques such as inductively coupled plasma optical emission spectrometry (ICP-OES) and laser-induced breakdown spectroscopy (LIBS) were employed. The resulting data enabled the identification of materials used in the pottery’s manufacture. The elemental composition of the objects was determined, revealing correlations between elements such as Si with Al that yield a $R^2$ factor of 0.94. The results indicate the presence of smectite clays, carbonates, and iron oxides. The results show that a higher proportion of carbonates was found in the pieces from the Postclassic period compared to those from the Preclassic period, which may be associated with a change in the manufacturing process. Likewise, the Postclassic pieces are distinguished by a greater contribution of the Mg-OH signal, unlike the Preclassic and Classic, which show a greater contribution of the Al-OH group. The implications for the technological knowledge of the potters suggest the use of different technologies across various periods and material changes driven by shifts in political and economic relations in the city and the northern plains. Full article