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Ancient Chinese bronzes, particularly bronze mirrors, often develop a fatty, oily, or greasy film on their surface, known as patina. This film can appear silvery, green, or black. Bronze mirror samples from the Spring and Autumn Period (770–476/403 BCE) to the Ming Dynasty (1368–1644 CE) were analyzed using a systematic approach that included super depth of field three-dimensional microscopy, scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM–EDS), Raman spectroscopy, and THM-Py-GC/MS. The analysis indicates the presence of advanced organic acid lead in the matrix of ancient bronze mirrors. The ancient existence of the lost wax method combined with the mould method of bronze casting technology is verified through simulation experiments and ancient literature. Ancient bronze mirrors may have utilized this technique, with advanced organic acid lead remaining in the mirror mould that entered the bronze mirror matrix during pouring. The Lead organic acids in bronze mirrors readily precipitate on the surface and cover the mirror. The change in the greasy sheen on the surface of the bronze mirror may be related to the degree of corrosion. If the mirror's corrosion level is low, the organic acid lead film remains transparent. If the level of corrosion is significant, the organic acid lead film may darken in color due to oxidation, aging, hydrolysis, or microbial activity.

Weathering steel (WS) is widely used in bridge construction due to its high corrosion resistance, durability, and low maintenance requirements. This paper reviews the performance of WS bridges in Canadian climates, focusing on the formation of protective patina, influencing factors, and long-term maintenance strategies. The protective patina, composed of stable iron oxyhydroxides, develops over time under favorable wet–dry cycles but can be disrupted by environmental aggressors such as chlorides, sulfur dioxide, and prolonged moisture exposure. Key alloying elements like Cu, Cr, Ni, and Nb enhance corrosion resistance, while design considerations—such as drainage optimization and avoidance of crevices—are critical for performance. The study highlights the vulnerability of WS bridges to microenvironments, including de-icing salt exposure, coastal humidity, and debris accumulation. Regular inspections and maintenance, such as debris removal, drainage system upkeep, and targeted cleaning, are essential to mitigate corrosion risks. Climate change exacerbates challenges, with rising temperatures, altered precipitation patterns, and ocean acidification accelerating corrosion in coastal regions. Future research directions include optimizing WS compositions with advanced alloys (e.g., rare earth elements) and integrating climate-resilient design practices. This review highlights the need for a holistic approach combining material science, proactive maintenance, and adaptive design to ensure the longevity of WS bridges in evolving environmental conditions.

Bronze cultural heritage in urban areas is susceptible to decay due to the significant amount of pollutants present in the air. This causes the dissolution of bronze and the patina on its surface. The efficient protection of outdoor bronze cultural heritage is still an unresolved problem. The aim of this work is to investigate 16-phosphonohexadecanoic acid as an environmentally friendly and non-toxic corrosion inhibitor for patinated bronze. The corrosion protection of sulphide-patinated bronze by phosphonic acid alone and in combination with acrylic coating Paraloid B-72 is examined. In order to achieve efficient corrosion protection, various parameters of the phosphonic acid application were studied. The efficiency of protection is examined by electrochemical impedance spectroscopy (EIS) during the immersion in simulated acid rain solution and after exposure to a corrosion chamber. It was found that the studied phosphonic acid provides corrosion protection to patinated bronze and significantly improves the protective properties of Paraloid B72. This was also confirmed by scanning electron microscopy (SEM) examination of the coating surface after exposure to a corrosive environment.

Atmospheric pollutants in the air form acid rain which interacts with bronze surfaces exposed in urban outdoor environment. In this study, different types of patinas on bronze were investigated during and after 9 years of exposure to urban environment in moderately polluted continental city. Natural bronze patina and artificial brown sulphide, green chloride, and green–blue nitrate patinas were investigated. Visual assessment was carried out at defined periods. After 9 years of exposure, an electrochemical study was performed to investigate the electrochemical activity of the patinas in artificial urban rain. Additionally, the patinas were characterised using a variety of techniques, including metallographic examination, scanning electron microscopy/energy dispersive X-ray spectroscopy, Raman spectroscopy, X-ray diffraction analysis, X-ray-photoelectron spectroscopy, and time-of-flight secondary ion mass spectrometry to analyse the surface morphology, chemical composition, and stratigraphic features of the patinas. Evolution of the patinas was shown to be a result of both, the composition of the acid rain and the hydrophobicity of the patinated surfaces.

What might commend so drab a creature to your sight, when overhead the low clouds split and the upturned bowl of a silver moon pours milk out on the river?” But there is something about Helen that compels our attention, something that has driven her from an English home to isolation overseas. All these accounts have a pleasing patina of scholarship, again giving the book that sinister feeling of sliding between the real and unreal: there is an ersatz 18th-century letter and a pretended extract from a 20th-century woman's collected letters, but the predominant testimony about Melmoth is called “The Hoffman Document”, presented as a last confession by a dying man of how he became “a cog in the machine” of Nazi pogroms. Helen's circle consists of a couple, Karel and Thea, who appear to cultivate her out of stubbornness as much as love, and a monstrous landlady who serves as a part of Helen's self-inflicted punishment.

The presence of shaped stone balls at early Paleolithic sites has attracted scholarly attention since the pioneering work of the Leakeys in Olduvai, Tanzania. Despite the persistent presence of these items in the archaeological record over a period of two million years, their function is still debated. We present new results from Middle Pleistocene Qesem Cave on the use of these implements as percussion tools. Use-wear and abundant bone and fat residues found on ten shaped stone balls indicate crushing of fresh bones by thrusting percussion and provide direct evidence for the use of these items to access bone marrow of animal prey at this site. Two experiments conducted to investigate and verify functional aspects proved Qesem Cave shaped stone balls are efficient for bone processing and provide a comfortable grip and useful active areas for repeated use. Notably, the patina observed on the analyzed items precedes their use at the cave, indicating that they were collected by Qesem inhabitants, most probably from older Lower Paleolithic Acheulian sites. Thus, our results refer only to the final phases of the life of the items, and we cannot attest to their original function. As bone marrow played a central role in human nutrition in the Lower Paleolithic, and our experimental results show that the morphology and characteristics of shaped stone ball replicas are well-suited for the extraction of bone marrow, we suggest that these features might have been the reason for their collection and use at Qesem Cave. These results shed light on the function of shaped stone balls and are consistent with the significance of animal fat in the caloric intake of Middle Pleistocene humans as shown by the archeozoological evidence at Qesem Cave and possibly beyond.

This article discloses a rare and outstanding type of Mn-rich black-blue patina found on mural painting and granite ashlars located in the church of Sta. Marinha, north of Portugal, and conjectures the phenomenon associated to the appearance of such patinas in different surface materials. This Mn-patina reported on mural painting and their origin is probably assigned to manganese leaching from building materials (i.e., granite and phyllites). Stained mural painting and granite examined by XPS and SEM have showed patinas enriched with manganese (IV) oxide, potentially catalysed by a microbiota, like fungi, observed in SEM micrographs. The pigments used to depict mural painting and groundwater were also analysed by micro-Raman and ICP-MS, respectively, indicating that they are unlikely manganese sources. Unstained building materials, such as granite ashlars, historic joints, mortars and phyllite rocks, were also analysed by ICP-MS showing that historic joints and mortars present significant concentrations of manganese, possibly associated to their absorbing feature. The main materials with potential to impart manganese to Mn-rich patinas are granite ashlars and phyllites. The aim of this investigation is to reveal and ascertain the hypothetical sources and the phenomenon responsible for the Mn-rich black-blue patina appearance, both on mural painting and granite ashlars.

Archaeological coins are considered essential sources of historical documentation. Over time, they are subjected to corrosion processes that gradually alter their appearance, shape, and composition. This study aims to evaluate the effects of the patina and/or protective coating on the corrosion process. Protection of the original coin surface was crucial following the completion of the cleaning protocol. Various finishes of coin fragments (uncoated, aged, and freshly coated) were investigated to determine their chemical composition, nature of the patina, and corrosion products on their surface using stereo microscopy(SM), X-ray diffraction (XRD), and scanning electron microscopy (SEM) equipped with energy dispersive X-ray spectroscopy (EDX). The analysis revealed that the coins were composed of a Cu–Sn- and Pb bronze alloy. Furthermore, the efficiency of the patina and/or protective coatings on the coin fragments was evaluated using potentiodynamic polarization (PDP), electrochemical impedance spectroscopy (EIS), and cyclic voltammetry (CV) techniques. The highest protection was achieved for patinated-freshly protective coated fragments, while the most corrosive fragments were those affected by bronze diseases.

Samples of orange patinas found on a limestone window tracery and an ornament of the Batalha Monastery have been investigated by X-ray micro-diffractometry (μ-XRD) and low-vacuum scanning electron microscopy coupled with energy dispersive spectrometry (LV-SEM + EDS). The aim of the study was to determine the composition of the layered patinas, assess whether they have been intentionally applied or naturally formed, and study their degradation patterns. Preliminary results revealed that the orange patinas on the window tracery and the ornament showed different compositions and appearance, suggesting distinct formation pathways. Orange patinas on the ornament, which are now showing decay and delamination patterns, mainly consisted of gypsum with hematite as a minor component, implying the possibility of an intentional application of a mixture of ochre and lime as tint plaster. Orange patinas on the window tracery show, instead, the presence of Ca-oxalates, abundant weddellite, and minor whewellite, with minor hematite suggesting the yellowish/orange color as being due to Ca-oxalate patinas imbedding soil dust airborne particles. Such patina was possibly formed naturally either by the chemical attack due to atmospheric air pollutants from traffic exhausts emissions or by bacterial activity. No delamination was observed on the window tracery sample with granular decohesion as the major decay phenomenon. A comparison was made between this patina and the so-called scialbatura, a surface yellowish coating often found by conservators on limestone and marble in ancient monuments in the Mediterranean region.

The requirements for the formation of a protective patina on conventional weathering steels (WS) are well known in the scientific literature related to civil structures. However, these criteria are not always given due consideration when WS is used in cultural heritage, as in the case of sculptural work. An artificial patina was produced simulating artists’ working procedures using a direct patination technique, applying a solution of 10% H2SO4 on WS specimens. These were exposed for two years in the urban atmosphere of Madrid along with weathering steel specimens without artificial patina, called natural patina. The patinas generated have been analyzed using colorimetry, micro-Raman spectroscopy, scanning electron microscopy (SEM), X-ray diffraction (XRD) and thickness measurements.The artificial patina color formed hardly differs from the color that the natural patina acquires from practically the beginning of its formation in the atmosphere of Madrid. After two years, the atmospheric corrosion rate of patinated WS is lower than 6 µm/year. The sulfuric acid treatment accelerates the protective ability of the patina with respect to the natural patina according to the ratio goethite to lepidocrocite (α/γ). Chromium-rich goethite is located in the inner part of the artificial patina as well as chromium-rich ferrihydrite. Ferrihydrite may act as a precursor of nanophasic goethite.