Search Results (66)

This study investigates Hispano-Muslim plasterworks, exemplified by the Cuarto Real de Santo Domingo, the Madraza, and the Alhambra in Granada, focusing on cleaning methods to remove oil-based repaintings without damaging the original polychromies. To this end, samples replicating traditional materials (gypsum coating, pigments, and binders) and techniques (tempera painting) were prepared and subjected to an artificial ageing protocol (AAP). Subsequently, cleaning tests aimed at removing the oil repaintings were performed to recover the original polychromies. Analytical techniques, including Fourier Transform Infrared Spectroscopy (FTIR), Gas Chromatography–Mass Spectrometry (GC–MS), and colorimetry, were employed to evaluate ageing effects and cleaning efficacy. Results revealed significant chromatic alterations in vermilion and azurite bound with animal glue, while ochre remained comparatively stable. Chemical analyses indicated marked binder deterioration, including protein denaturation in animal glue and oxidation/polymerization in linseed oil. Cleaning tests demonstrated that both a heptane–acetone gel and a novel polyamidoamine–glycine (PAAGLY) treatment effectively removed oil-based repaintings while preserving the original layers. These findings highlight the critical role of pigment–binder interactions in conservation strategies and advocate for selective, minimally invasive restoration methods. Full article

The colour degradation of murals presents a significant challenge in the conservation of architectural heritage. Previous research has often concentrated on localized pigment changes while paying insufficient attention to the interaction between colour variation and indoor environmental conditions. Although non-destructive analytical techniques are widely used in heritage studies, their integrated application in combination with colourimetry has been limited, particularly in the context of Tibetan Buddhist murals in highland continental climates. This study investigates the murals of Liuli Hall in Meidai Lamasery, Inner Mongolia, as a representative case. We employed a comprehensive methodology that combines non-destructive analytical tools, gas chromatography–mass spectrometry, and quantitative colour analysis to examine pigment composition, binding material, and surface deterioration. Through joint analysis using the CIE Lab and CIE LCh colour space systems, we quantified mural colour changes and explored their correlation with material degradation and environmental exposure. The pigments identified include cinnabar, atacamite, azurite, and chalk, with animal glue and drying oils as binding materials. Colourimetric results revealed pronounced yellowing on the east and west walls, primarily caused by the ageing of organic binders. In contrast, a notable reduction in brightness on the south wall was attributed to dust accumulation. These findings support tailored conservation measures such as regular surface cleaning for the south wall and antioxidant stabilization treatments for the east and west walls. Initial cleaning efforts proved effective. The integrated approach adopted in this study provides a replicable model for mural diagnostics and conservation under complex environmental conditions. Full article

The Aït Abdellah copper deposit in the Bou Azzer-El Graara inlier of the Moroccan Anti-Atlas provides key insights into structurally and lithologically controlled mineralization in Precambrian terranes. The deposit is hosted in feldspathic sandstones of the Tiddiline Group, which unconformably overlie the Bou Azzer ophiolite, and is spatially associated with a NE–SW-trending shear zone. This zone is characterized by mylonitic fabrics, calcite veining, and an extensive network of fractures, reflecting a two-stage deformation history involving early ductile shearing followed by brittle faulting and brecciation. These structural features enhanced rock permeability, enabling fluid flow and metal precipitation. Copper mineralization includes primary sulfides such as chalcopyrite, bornite, pyrite, chalcocite, digenite, and covellite, as well as supergene minerals like malachite, azurite, and chrysocolla. Sulfur isotope values (δ³⁴S = +5.9% to +22.8%) indicate a mixed sulfur source, likely derived from both ophiolitic rocks and volcano-sedimentary sequences. Carbon and oxygen isotope data suggest fluid interaction with marine carbonates and meteoric waters, potentially linked to post-Snowball Earth deglaciation processes. Fluid inclusion studies reveal homogenization temperatures ranging from 195 °C to 310 °C and salinities between 5.7 and 23.2 wt.% NaCl equivalent, supporting a model of fluid mixing between magmatic-hydrothermal and volcano-sedimentary sources. The paragenetic evolution of the deposit comprises three stages: (1) early hydrothermal precipitation of quartz, dolomite, sericite, pyrite, and early chalcopyrite and bornite; (2) a main mineralizing stage characterized by fracturing and deposition of bornite, chalcopyrite, and Ag-bearing sulfosalts; and (3) a late supergene phase with oxidation and secondary enrichment. The Aït Abdellah deposit is best classified as a shear zone-hosted copper system with a complex, multistage mineralization history. The integrated analysis of structural features, mineral assemblages, isotopic signatures, and fluid inclusion data reveals a dynamic interplay between deformation processes, hydrothermal alteration, and evolving fluid sources. Full article

The existence of historical pigments databases is important to speed up cultural heritage research. Knowledge of their chemical composition and their manufacture contributes to the study of art history and helps develop accurate conservation-restoration strategies. In this study, a total of nineteen pigments, among which we find silicates (Egyptian blue, natural and synthetic blue ultramarine, green earth and chrysocolla), oxides (natural and synthetic hematite, red and yellow natural ochres, and chromium green), carbonates (natural and synthetic azurite, natural and synthetic malachite, and white lead), sulphides (natural and synthetic cinnabar, and orpiment) and acetates, (verdigris) have been characterized by Fourier Transform Infrared-Spectroscopy in Attenuated Total Reflection (ATR-FTIR) and Diffuse Reflectance (DRIFT) modalities. Considering the latter, there is still a great deal of uncertainty in the interpretation of the different IR vibrational bands. Therefore, a comparative study between these two techniques has been carried out to highlight the potential of DRIFT spectroscopy as a portable and non-destructive technique that allows the differentiation and characterization of historical pigments in the field of cultural heritage. Before performing FTIR analysis, pigments were analysed using X-ray diffraction (XRD) to detect impurities and/or additives in the pigments. Differentiation between natural and synthetic pigments was possible due to the identification of impurities in natural pigments, and manufacture-related compounds or additives in synthetic pigments. Results obtained in this study have proven DRIFT to be a very useful analytical technique for in situ characterization of heritage materials. This study serves as an initial step in clarifying the challenges and uncertainties associated with interpreting spectra obtained through the DRIFT modality. However, the use of other complementary analytical techniques is required. Full article

The main objective of the present study was to develop a real-time mineral classification system designed for multiple detection, which integrates classical computer vision techniques with advanced deep learning algorithms. The system employs three CNN architectures—VGG-16, Xception, and MobileNet V2—designed to identify multiple minerals within a single frame and output probabilities for various mineral types, including Pyrite, Aragonite, Quartz, Obsidian, Gypsum, Azurite, and Hematite. Among these, MobileNet V2 demonstrated exceptional performance, achieving the highest accuracy (98.98%) and the lowest loss (0.0202), while Xception and VGG-16 also performed competitively, excelling in feature extraction and detailed analyses, respectively. Gradient-weighted Class Activation Mapping visualizations illustrated the models’ ability to capture distinctive mineral features, enhancing interpretability. Furthermore, a stacking ensemble approach achieved an impressive accuracy of 99.71%, effectively leveraging the complementary strengths of individual models. Despite its robust performance, the ensemble method poses computational challenges, particularly for real-time applications on resource-constrained devices. The application of this methodology in Mineral Quest, an educational Python-based game, underscores its practical potential in geology education, mining, and geological surveys, offering an engaging and accurate tool for real-time mineral classification. Full article

Traditional mining activities in Zaruma-Portovelo (SE Ecuador) have led to high concentrations of pollutants in the Puyango River due to acid mine drainage (AMD) from abandoned waste. Dispersed alkaline substrate (DAS) passive treatment systems have shown efficacy in neutralizing acidity and retaining metals and sulfates in acidic waters, achieving near a 100% retention for Fe, Al, and Cu, over 70% for trace elements, and 25% for SO₄²⁻. However, significant solid residues are generated, requiring proper geochemical and mineralogical understanding for management. This study investigates the fractionation of elements in AMD precipitates. Results indicate that Fe³⁺ and Al³⁺ predominantly precipitate as low-crystallinity oxyhydroxysulfate minerals such as schwertmannite [Fe³⁺₁₆(OHSO₄)_12–13O₁₆·10–12H₂O] and jarosite [KFe³⁺₃(SO₄)₂(OH)₆], which retain elements like As, Cr, Cu, Pb, and Zn through adsorption and co-precipitation processes. Sulfate removal occurs via salts like coquimbite [AlFe₃(SO₄)₆(H₂O)₁₂·6H₂O] and gypsum [CaSO₄·2H₂O]. Divalent metals are primarily removed through carbonate and bicarbonate phases, with minerals such as azurite [Cu(OH)₂·2CuCO₃], malachite [Cu₂(CO₃)(OH)₂], rhodochrosite [MnCO₃], and calcite [CaCO₃]. Despite the effectiveness of DAS, leachates from the precipitates exceed regulatory thresholds for aquatic life protection, classifying them as hazardous and posing environmental risks. However, these residues offer opportunities for the recovery of valuable metals. Full article

Azurite, a natural mineral pigment consisting of basic copper carbonate (2CuCO₃·Cu(OH)₂), is one of the Middle Ages’ most common blue pigments. Why paintings originally coated with azurite appear blackened today remains debated. Using a non-invasive multi-analytical approach, the study analysed several unexpectedly black-appearing details (objects such as books or clothing such as veils, robes, or mantles) in Antoine de Lonhy’s works. The aim was to investigate if the black colour was due to intentional iconographic reasons, incautious restoration work, or painting deterioration. The analytical results displayed the presence of the blue pigment azurite, therefore, the expected original colour of various areas should be blue. To shed light on the discussion regarding the blackening, several other Renaissance paintings with similar black details were analysed, all from the same period and geographic area as de Lonhy’s works and conserved under identical conditions. The reasons why the blackening takes place are still unclear. However, the combined use of X-ray fluorescence spectrometry (XRF), UV-visible diffuse reflectance spectrophotometry with optical fibres (FORS), portable X-ray diffraction (XRD), and the elemental mapping based on the XRF data revealed that these blackened areas were originally painted with azurite, suggesting they were once blue. This finding significantly changes the overall appreciation of these artworks. Full article

This study examines the effects of drying oils—Tung and linseed—on the properties of traditional polychrome coatings applied to wood. Samples prepared with cinnabar, malachite green, yellow ochre, and azurite pigments were analyzed using colorimetric, gloss measurements, surface roughness testing, adhesion strength, and SEM imaging. The results show that Tung oil generally enhances gloss by over 20% and provides superior adhesion, consistently achieving an adhesion grade of 0 (no peeling) across all pigments. Linseed oil, although effective at higher concentrations, displayed more variable adhesion, particularly with blue and yellow pigments. Surface roughness measurements revealed that higher oil content (6:4 ratio) reduced roughness, achieving smoother finishes with Ra values as low as 2.36 μm for Tung oil. SEM analysis confirmed that Tung oil yields a smoother and more even pigment distribution compared to the rougher, clustered morphology in linseed oil samples. These findings underscore the importance of oil type and concentration in achieving desired esthetic and durability outcomes in restoration work. Full article

Choirbooks are historical heritage manuscripts used for the performance of vocal music in religious ceremonies in colonial times. This study aimed to understand the characteristics of choirbook manuscripts produced in the Real Audiencia de Quito during the 17th century. The methodology combined non-invasive techniques, such as infrared false-color imaging (IRFC) and X-ray fluorescence (XRF), together with spot analysis by scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDX) and Fourier transform infrared spectroscopy with attenuated total reflection (FTIR-ATR). The analytical results revealed the use of pumice, chalk and lime carbonate as support materials in the manufacturing process and surface treatment of the parchment. In the illuminations, three pictorial techniques based on protein, polysaccharide and lipid binders were recognized, establishing that the pigments used with greater regularity in the illuminations were vermilion, minium, verdigris, orpiment, azurite, and indigo, preferably in a pure state. Materials used less regularly were also identified, such as yellow ochre, saffron, smalt, red ochre, and bone black, among others. Regarding the vulnerability of the pictorial materials, it was determined that, although most of the pigments exhibit chemical stability, they present some vulnerabilities associated with their intrinsic composition and the medium that contains them. Full article

To search for a conceptual picture describing the magnetization plateau phenomenon, we surveyed the crystal structures and the spin lattices of those magnets exhibiting plateaus in their magnetization vs. magnetic field curves by probing the three questions: (a) why only certain magnets exhibit magnetization plateaus, (b) why there occur several different types of magnetization plateaus, and (c) what controls the widths of magnetization plateaus. We show that the answers to these questions lie in how the magnets under field absorb Zeeman energy, hence changing their magnetic structures. The magnetic structure of a magnet insulator is commonly described in terms of its spin lattice, which requires the determination of the spin exchanges’ nonnegligible strengths between the magnetic ions. Our work strongly suggests that a magnet under the magnetic field partitions its spin lattice into antiferromagnetic (AFM) or ferrimagnetic fragments by breaking its weak magnetic bonds. Our supposition of the field-induced partitioning of spin lattices into magnetic fragments is supported by the anisotropic magnetization plateaus of Ising magnets and by the highly anisotropic width of the 1/3-magnetization plateau in azurite. The answers to the three questions (a)–(c) emerge naturally by analyzing how these fragments are formed under the magnetic field. Full article

Against the backdrop of the increasing copper demand in a low-carbon economy, this work statistically forecasted the distribution of China’s copper tailings for the first time, and then characterized them as finely crushed and low-grade mining solid wastes containing copper mainly in the form of chalcopyrite, bornite, covelline, enargite and chalcocite based on available research data. China is the globally leading refined copper producer and consumer, where the typical commercial-scale bioleaching of copper tailings is conducted in the Dexing, Zijinshan and Jinchuan mining regions. And these leaching processes were compared in this study. Widely used chemolithoautotrophic and mesophilic bacteria are Acidithiobacillus, Leptospirillum, Acidiphilium, Alicyclobacillus and Thiobacillus with varied metal resistance. They can be used to treat copper sulfide tailings such as pyrite, chalcopyrite, enargite, chalcocite, bornite and covellite under sufficient dissolved oxygen from 1.5 to 4.1 mg/L and pH values ranging from 0.5 to 7.2. Moderate thermophiles (Acidithiobacillus caldus, Acidimicrobium, Acidiplasma, Ferroplasma and Sulfobacillus) and extreme thermophilic archaea (Acidianus, Metallosphaera, Sulfurococcus and Sulfolobus) are dominant in leaching systems with operating temperatures higher than 40 °C. However, these species are vulnerable to high pulp density and heavy metals. Heterotrophic Acidiphilium multivorum, Ferrimicrobium, Thermoplasma and fungi use organic carbon as energy to treat copper oxides (malachite, chrysocolla and azurite) and weathered sulfides (bornite, chalcocite, digenite and covellite) under a wide pH range and high pulp density. We also compared autotrophs in a planktonic state or biofilm to treat different metal sulfides using various sulfur-cycling enzymes involved in the polysulfide or thiosulfate pathways against fungi that produce various organic acids to chelate copper from oxides. Finally, we recommended a bioinformatic analysis of functional genes involved in Fe/S oxidization and C/N metabolism, as well as advanced representation that can create new possibilities for the development of high-efficiency leaching microorganisms and insight into the mechanisms of bioleaching desired metals from complex and low-grade copper tailings. Full article

During the restoration and digitalization intervention of the Manoscritto Parmense (Ms. Parm.) 3285 codex, a 14th-century illuminated volume that contains the three books of Dante Alighieri’s Divina Commedia belonging to the Biblioteca Palatina of Parma, the deposits present in the center of some bifoliums were removed using soft bristle brushes and collected. A preliminary observation of these deposits with a stereomicroscope allowed the detection of some pigment grains of different colors, likely detached from the full-page illuminations at the beginning of each book. These grains of the pigments were then analyzed in the Bologna ENEA Research Centre through Scanning Electron Microscopy (SEM), EDX microanalysis, and micro-Raman spectroscopy, allowing the identification of the minerals or the compounds used as pigments. Consequently, some pigments that were commonly used in the Middle Ages such as gold leaf, typically employed in illuminations and the decoration of heading initials, cinnabar red, and different types of blue pigments, including traces of lapis lazuli and azurite, were identified. Full article

This study measured the infrared spectra of secondary minerals in the oxidation zones of three types of copper ores: dioptase, malachite, and azurite, and assigned the peak positions of OH stretching vibrations and the origins of OH combination vibrations. Dioptase contains three types of water molecules with different orientations within its ring channels, which exhibit six kinds of OH stretching vibrations in the 3000–3600 cm⁻¹ range; the bond length range is 2.652 to 2.887 Å. Among them, the 3443 cm⁻¹ band shows strong near-infrared activity and combines with Si–O vibrations or OH bending vibrations in the structure, resulting in five combination vibration peaks in the 4000–5000 cm⁻¹ range. Malachite contains two inequivalent hydroxyls in its structure, leading to two OH stretching vibrations in the high-frequency region located at 3314 and 3402 cm⁻¹, respectively. Azurite contains only one type of hydroxyl, and thus only one characteristic OH stretching vibration is present at 3424 cm⁻¹. The OH stretching vibrations of malachite and azurite mainly combine with [CO₃]²⁻ vibrations or OH bending vibrations, leading to six and five combination peaks in the OH combination vibration region, respectively. By analyzing the combination of peak positions at 4341 cm⁻¹ in the near-infrared spectrum, the merged OH bending vibration at 921 cm⁻¹ in azurite was discovered. Spectroscopic research on secondary minerals can better provide a basis for ore exploration and geological remote sensing. Full article

The Imourkhssen porphyry Cu±Mo±Au±Ag deposit is located at the Ouzellagh-Siroua Salient (OSS) straddling the boundary between the central Anti-Atlas and the central High Atlas. It is characterized by a typical porphyry-style mineralization. The volcanic rocks are intruded by numerous magmatic rocks of the Ouarzazate Group (580–539 Ma), referred to as the Late Ediacaran magmatic suites (LEMS). Of these, the Askaoun, Imourkhssen, and Imourgane granites are the most significant as they are related to the porphyry mineralization. The entire set is intruded by the Zaghar mafic dyke swarms. Zircon U-Pb dating of the Imourkhssen granite and the ore-bearing granite porphyry shows that these intrusive rocks were emplaced at 558 ± 1 and 550 ± 2 Ma, respectively. Moreover, the whole-rock major and trace element geochemistry reveal a high-K calc-alkaline I-type composition, consistent with an emplacement in a post-collisional setting under a trans-tensional tectonic regime. Ore bodies are hosted by the Askaoun granodiorite as well as the Imourgane granite. The mineralization occurs as fine-grained dissemination and infills of hydrothermally altered NNE–SSW to N–S trending veins and veinlets. Ore-related hydrothermal alteration consists of potassic, chlorite-sericite, serecitic, and propylitic mineral assemblages along with pervasive silicification and pyritization, providing a porphyry-style alteration pattern. The ore periods comprise supergene and magmatic-hydrothermal periods. The latter includes primary dissemination and secondary NNE–SSW to N–S ore-bearing system stages. The occurrence of molybdenite is either restricted to the potassic and chlorite-sericite alteration zones of the ore-bearing granite as fine disseminations or alternatively as veinlet infills within the propylitic halos. The molybdenite occurrences along with pyrite, chalcopyrite, galena, and tennantite dissemination are assigned to the primary ore stage, while the NNE–SSW to N–S ore-bearing system is related to the secondary ore stage. It consists of pyrite, chalcopyrite, bornite, covellite, diagenite, sphalerite, hematite, galena, gold, and chenguodaite. The predominance of cockade and crack-and-seal textures suggest multiple episodes of ore-forming fluid circulations under epithermal conditions. The supergene stage is achieved by subordinate malachite, azurite, barite, hematite, epsomite, and chrysocolla. From the descriptions above, we argue that the Imourkhssen Cu±Mo±Au±Ag mineralization shares many mineralogical and paragenetic attributes of porphyry-copper deposits. Full article

Yuzhen Palace in Wudang Mountain, established in the 10th year of the Yongle reign of the Ming dynasty (1412 AD), is a significant heritage site within the ancient architectural complex of Wudang Mountain, recognized as a UNESCO World Heritage Site. Despite being entirely relocated, the original paintings on the wooden beams of the Dragon and Tiger Hall exhibit clear characteristics of early Ming dynasty style, potentially being the only surviving wooden painted structures from the Ming dynasty in Wudang Mountain. To protect these valuable cultural relics and provide accurate information regarding the construction period of the paintings, this study sampled the paintings from the central and western sections of the front eaves in the Dragon and Tiger Hall. Using optical microscopy, scanning electron microscopy (SEM), Raman spectroscopy, and infrared spectroscopy, the study analyzed the stylistic features, material composition, and craftsmanship of the paintings. The results indicate that the paintings are typical official Xuanzi paintings from the early Ming dynasty, consistent with the style of the Golden Roof in Taihe Palace, Wudang Mountain. The pigments used are all natural minerals: azurite (2CuCO₃·Cu(OH)₂) for blue, malachite (CuCO₃·Cu(OH)₂) for green, and vermilion (HgS) and hematite (Fe₂O₃) for red, reflecting typical early Ming dynasty characteristics. The craftsmanship shows that the paintings were applied directly onto the wooden components without a ground layer, using ink lines to outline the images, and a thin ground layer made of tung oil mixed with lime was applied under the oil coating. This study provides scientific material analysis and data support for the subsequent protection and restoration of the Yuzhen Palace architectural complex, ensuring the preservation of these historically and artistically significant relics for future generations. Full article