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From the moment of production, artworks are constantly exposed to changing environmental factors potentially inducing degradation. Therefore, detailed knowledge of natural degradation phenomena is essential for proper damage assessment and preservation. With special focus on written cultural heritage, we present a study on the degradation of sheep parchment employing accelerated aging with light (295-3000 nm) for one month, 30/50/80% relative humidity (RH) and 50 ppm sulfur dioxide with 30/50/80%RH for one week. UV/VIS spectroscopy detected changes in the sample surface appearance, showing browning after light-aging and increased brightness after SO2-aging. Band deconvolution of ATR/FTIR and Raman spectra and factor analysis of mixed data (FAMD) revealed characteristic changes of the main parchment components. Spectral features for degradation-induced structural changes of collagen and lipids turned out to be different for the employed aging parameters. All aging conditions induced denaturation (of different degrees) indicated by changes in the secondary structure of collagen. Light treatment resulted in the most pronounced changes for collagen fibrils in addition to backbone cleavage and side chain oxidations. Additional increased disorder for lipids was observed. Despite shorter exposure times, SO2-aging led to a weakening of protein structures induced by transitions of stabilizing disulfide bonds and side chain oxidations.
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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.
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This study aims to investigate the chemical stability of some modern paint samples exposed to a new Light Emitting Diode (LED)-lighting system and a halogen lamp by using micro-attenuated total reflectance of Fourier transform infrared spectroscopy (µ-ATR-FTIR), µ-Raman, pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS), and thermally assisted hydrolysis and methylation of GC/MS (THM-GC/MS). Those investigations were performed before and after the exposure of the samples to lightings for 1250, 2400, 3300, and 5000 h. The results obtained with µ-Raman spectroscopy show the high stability of the selected inorganic pigments after the exposure to the lighting systems; while similar to the UV/Vis/NIR results reported in a previous study, µ-ATR-FTIR and THM-GC/MS results evidence greater chemical changes occurring principally on the linseed oil binder-based mock-ups among the acrylic and alkyd-based samples. Moreover, principal component analyses (PCA) and hierarchical cluster analyses (HCA) of THM-GC/MS results highlight that those changes were mostly dependent on the exposure time and on the type of pigment, while being independent of the lighting system used. Finally, semi-quantitative µ-ATR-FTIR results show slight pigment enrichment at the paint surface due to the auto and photo-oxidative degradation of the linseed oil binder.
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A multianalytical approach was used to characterize the materials in the "Vienna Moamin", an outstanding richly illustrated manuscript from the late thirteenth century, which was made in Italy and is now kept in the Kunsthistorisches Museum Wien. The investigations were carried out with a non-invasive approach by using complementary techniques, such as X-ray fluorescence (XRF), reflection Fourier transform infrared spectroscopy (rFTIR), Raman spectroscopy, and fiber optic reflectance spectroscopy (FORS). In addition, XRF scans were performed in two areas which yielded chemical maps showing the elemental distribution. The results revealed that typical materials from the medieval times were applied for the manuscript. Calcium carbonate on the parchment surface indicated a dehairing process with lime and/or whitening with chalk. Two different iron gall inks were detected in the main text and marginal notes, and vermilion was used for rubrication. The color palette included azurite, a green colorant composed of orpiment and indigo, yellow ochre, brown iron oxide pigments, minium, vermilion, brazilwood lake, and carbon black. Moreover, mosaic gold was detected in gold-beige hues. Lead white was identified for white areas and fine decoration lines, as well as in mixture with blue and red pigments for light color shades. No reliable information could be obtained concerning the binding media. Two differing application techniques for gold leaf were detected, which correspond with stylistic differences: either on gypsum or chalk preparation layers. Furthermore, calcium soap contents in certain colors were determined only on one folio with unique characteristics. The XRF scans of two historiated initials revealed that similar materials were applied in both cases and provided further valuable information about the painting technique. The results obtained enabled to gain insights into Italian thirteenth century manuscript production techniques and to characterize the used materials. The investigations showed the importance of scanning XRF for the elucidation of painting techniques, but also the demand of scanning devices utilizing compound specific analytical techniques such as rFTIR. SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1186/s40494-021-00553-w.
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This research focuses on the investigation of the effect of a new light emitting diode (LED)-lighting system which reproduces indoor museum conditions, on some self-made art paint colours (acrylic-, alkyd-, and linseed oil-based paints) often used in modern-contemporary art. A halogen lamp representing a traditional light source for museum lighting was also considered. Lighting-set-up and lighting optimization parameters were considered while Ultraviolet/Visible/Near Infrared (UV/Vis/NIR) spectrophotometry was used for investigating the colour change of the paint samples. Univariate analyses allowed determining the highest effect of the lighting systems on the linseed oil binder and ultramarine blue PB29 mixture upon ageing, according to the highest total colour change ΔE*ab. In a more specific and detailed way, variance analyses not only demonstrated the strong correlation between the type of binder and pigment used for the paint samples with the colour variation, but also showed that the short-wavelength blue LEDs influenced the change along the yellow-blue b* axis of the yellow and blue samples, whereas the halogen lamp mostly had an impact towards the red-green a* axis of mostly the green specimens.
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From their first employment in the 1950s, acrylic emulsions have remained widely used as art material today. Although under certain deteriorating conditions they are very stable, if exposed to high humidity and atmospheric pollutant gases, their structural and chemical conformation is strongly affected. Dealing with the resulting surfactant migration, various cleaning treatments were considered over the years. However, their choice remains difficult as they easily alter the acrylic component, especially if in contact with aqueous solutions. The present study focuses on investigating the stability of acrylic emulsion films exposed to accelerated aging by various pollutant gases. Firstly, a comparative analytical study was carried out in order to morphologically (by 3D optical and Atomic Force Microscopy) and chemically (by Raman and Infrared spectroscopy) characterize the reactions and degradation products. Subsequently, two water-based cleaning treatments were tested, and a preliminary evaluation of their cleaning effectiveness was performed. The results show that the reaction of atmospheric gas pollutants with water molecules in moisture leads to acidic reaction products that attack the acrylic matrix and favor the migration of the surfactant to the surface. The effectiveness of cleaning treatments depends on the aging conditions applied, which further lead to different surface morphological changes.
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The ageing behavior of phenol formaldehyde (PF) foam, a material increasingly used in modern-contemporary art, was investigated by a multi-analytical approach. PF foams with open- and closed-cell structures were selected and analyzed in their unaged and naturally indoor-aged state by employing optical microscopy (OM) and fiber optical reflectance spectroscopy (FORS) for assessing their morphology and color alteration. Micro-Fourier transform infrared spectroscopy (µ-FTIR) was used for determining chemical changes and oxidation processes, and the acidity was monitored by pH measurements. The results clearly showed the extreme sensitivity of both open- and closed-cell PF foams to conditions typically found in indoor museums. OM indicated that the cells of the foams are prone to disrupt, and a tendency towards a red color shift was observed with FORS. µ-FTIR revealed the formation of quinone groups resulting from oxidation reactions. Finally, a slight decrease in the acidity was found by pH measurements.
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Polymers are used in a variety of different areas, including applications in food packaging, automotive and the semiconductor industry. Information about degradation of these materials during application, but also uptake of pollutants from the surrounding environment is therefore of great interest. Conventional techniques used for polymer characterization such as FT-IR or Raman spectroscopy, but also thermo-analytical techniques offer insights into degradation processes but lack the possibility to detect uptake of inorganic species. Moreover, these techniques do not allow the measurement of depth profiles, thus information about degradation or pollutant uptake with sample depth is not accessible. In this work, we propose LA-ICP-MS and LIBS as powerful analytical tools for polymer characterization, overcoming the limitations of conventional analytical techniques used for polymer analysis. Applicability of the developed procedures is demonstrated by the analysis of artificially weathered polyimides and modern art materials, indicating that the degradation of the polymer but also the uptake of corrosive gases is not limited to the sample surface. Finally, a tandem LA-ICP-MS/LIBS approach is employed, which combines the advantages of both laser-based procedures, enabling the simultaneous analysis of polymer degradation and cadmium uptake of polystyrene after exposure to UV radiation and treatment with artificial sea water.
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This study provides an example in the emerging field of biocodicology showing how metagenomics can help answer relevant questions that may contribute to a better understanding of the history of ancient manuscripts. To this end, two Slavonic codices dating from the 11th century were investigated through shotgun metagenomics. Endogenous DNA enabled to infer the animal origin of the skins used in the manufacture of the two codices, while nucleic sequences recovered from viruses were investigated for the first time in this material, opening up new possibilities in the field of biocodicology. In addition, the microbiomes colonizing the surface of the parchments served to determine their conservation status and their latent risk of deterioration. The saline environment provided by the parchments selected halophilic and halotolerant microorganisms, which are known to be responsible for the biodegradation of parchment. Species of Nocardiopsis, Gracilibacillus and Saccharopolyspora, but also members of the Aspergillaceae family were detected in this study, all possessing enzymatic capabilities for the biodeterioration of this material. Finally, a relative abundance of microorganisms originating from the human skin microbiome were identified, most probably related to the intensive manipulation of the manuscripts throughout the centuries, which should be taken with caution as they can be potential pathogens.
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DNA Antigo , Manuscritos como Assunto/história , Microbiota , Animais , Biodegradação Ambiental , Conservação dos Recursos Naturais , DNA Antigo/isolamento & purificação , Europa Oriental , História Antiga , Humanos , Saccharopolyspora , Pele/microbiologiaRESUMO
The ever-increasing speed of exchange of ideas, information, and culture allows contemporary art to be in constant growth, especially concerning the choice of artistic materials. Their characterization is not only crucial for the study of artistic techniques but also for research into the stability of the material and, consequently, the best preservation practices. For this aim, an analytical method should have the advantages of not requiring sample preparation, performing superficial micro-analysis, and obtaining detailed spectral information. For this study, laser-induced breakdown spectroscopy (LIBS) was employed. It was used for the identification of modern paints composed of inorganic pigments and organic binders, such as acrylics, alkyds, and styrene-acrylics. Principal component analysis (PCA) was used to classify the different pure materials, above all, the polymeric binders. To distinguish the paint mixtures, whose LIBS spectral results were more complex due to the pigment/binder interaction, a statistical method recently employed in the cultural heritage field was chosen, namely, random decision forest (RDF). This methodology allows a reduction of the variance of the data, testing of different training data sets by cross-validation, an increase of the predictive power. Furthermore, for the first time, the distribution of different inorganic pigments and organic binder materials in an unknown sample was mapped and correctly classified using the developed RDF. This study represents the first approach for the classification of modern and contemporary materials using LIBS combined with two different multivariate analyses. Subsequent optimization of measurement parameters and data processing will be considered in order to extend its employment to other artistic materials and conservation treatments.
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This work presents a comprehensive, multi-analytical scientific approach for determining the type of lacquer and artistic materials used by Jean Dunand on his work "The Return of the Hunters" (1935). For this purpose, thermally assisted hydrolysis and methylation - gas chromatography/mass spectrometry (THM-GC/MS), optical microscopy (OM) in visible (Vis) and ultraviolet light (UV), and scanning electron microscopy - energy-dispersive X-ray spectroscopy (SEM-EDX) were selected. Furthermore, a novel application of micro attenuated total reflection Fourier transform infrared (µATR-FTIR) spectroscopic mapping by univariate and multivariate analysis was applied for studying the complex lacquer paint stratigraphy. The results show that Vietnamese lacquer was used as a binder, mixed together with linseed oil and pine resins as additives in combination with inorganic pigments, and that shellac was included on the top of the paint; they document an important step in the story of the transfer of Vietnamese lacquer painting techniques to Europe.
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In illuminated manuscripts, a reliable identification of oxyanion pigments such as azurite by rFTIR is simple, as several combination and overtone bands are strongly enhanced compared to transmission mode. However, the characterization of the used binding media is rather difficult, as the analysis of four medieval manuscripts from the late thirteenth to the fifteenth century (e.g. Cod. slav. 8 in the collection of the Austrian National Library), as well as the earliest known map of Vienna (Albertinischer Plan from 1421, Wien Museum) showed. According to the literature, mainly glair (egg white) and plant gums were applied as binding media for azurite. Moreover, both were used in many cases also as "varnishes" in order to improve optical and mechanical properties of the paint layer. In order to assess the possibilities and to distinguish between proteinaceous and carbohydrate binders, mock-ups with azurite were prepared on parchment support with various quantities of binders. Additionally, some of the specimen were varnished using the binders mentioned above. Furthermore, mock-ups on aluminium foil were prepared to evaluate the influence of the support on the reflection spectra. The results showed that the binding medium content in the mock-ups usually was too low for a reliable determination by rFTIR (except the ones with the highest contents), whereas it was possible to characterize the varnish materials. Only an insignificant influence of the support on the spectra from the mock-ups was observed. However, the spectra obtained from three manuscripts suggested a certain influence of the parchment support, which indicates thinner paint layers.
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Knowledge of the techniques employed by artists, such as the composition of the paints, colour palette, and painting style, is of crucial importance not only to attribute works of art to the workshop or artist but also to develop strategies and measures for the conservation and restoration of the art. While much research has been devoted to investigating the composition of an artist's materials from a qualitative point of view, little effort has been made in terms of quantitative analyses. This study aims to quantify the relative concentrations of binders (acrylic and alkyd) and inorganic pigments in different paint samples by IR and Raman spectroscopies. To perform this quantitative evaluation, reference samples of known concentrations were prepared to obtain calibration plots. In a further step, the quantification method was verified by additional test samples and commercially available paint tubes. The results obtained confirm that the quantitative method developed for IR and Raman spectroscopy is able to efficiently determine different pigment and binder concentrations of paint samples with high accuracy.
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This study presents the replication of a color-causing nanostructure based on the upper laminae of numerous cover scales of Morpho peleides butterfly wings and obtained solely by imprinting their upper-wing surfaces. Our results indicate that a simple casting technique using a novel integrated release agent can obtain a large positive replica using negative imprints via Polyvinylsiloxane. The developed method is low-tech and high-yield and is thus substantially easier and less expensive than previous methods. The microstructures were investigated with light microscopy, the nanostructures with both scanning and transmission electron microscopy, and the reflections with UV visible spectrometry. The influence of the release agent and the quality of the master stamp were determined by comparing measurements of the cover-scale sizes and their chromaticity values obtained by their images and with their positive imprints. The master stamp provided multiple positive replicas up to 3 cm(2) in just 1 h with structural coloration effects visible to the naked eye. Thus, the developed method proves the accuracy of the replicated nanostructure and its potential industrial application as a color-producing nanostamp.
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Borboletas/ultraestrutura , Cor , Impressão Molecular/métodos , Nanopartículas/química , Polivinil/química , Siloxanas/química , Asas de Animais/ultraestrutura , Animais , Colorimetria/métodos , Refratometria/métodos , Propriedades de SuperfícieRESUMO
Twenty one mock-up samples containing inorganic pigments primarily used at the turn of the 19th and 20th century were selected for comparative study and measured by micro-Raman and portable Raman spectrometers. They included pure grounds (chalk-based, earth-based and lithopone-based), grounds covered by resin-based varnish, and different paint layers containing mixtures of white, yellow, orange, red, green, blue and black pigments, usually in combination with white pigments (titanium, zinc and barium whites or chalk). In addition, ten micro-samples obtained from seven paintings of two world-famous modern painters Edvard Munch and Frantisek Kupka have been investigated. Infrared reflection spectroscopy (FTIR), portable X-ray fluorescence (XRF) and scanning electron microscopy with energy dispersive spectroscopy (SEM-EDS) were used as supplementary methods. The measurements showed that blue pigments (ultramarine, Prussian blue and azurite), vermilion and ivory black in mixture with whites provided characteristic Raman spectra, while Co-, Cd- and Cr- pigments' bands were suppressed by fluorescence. The best success rate of micro-Raman spectroscopy has been achieved using the 780 nm excitation, however, the sensitivity of this excitation laser in a portable Raman instrument significantly decreased. The analyses of micro-samples of paintings by E. Munch and F. Kupka showed that micro-Raman spectroscopy identified pigments which would remain unidentified if analyzed only by SEM-EDS (zinc yellow, Prussian blue). On the other hand, chromium oxide green and ultramarine were not detected together in a sample due to overlap of their main bands. In those cases, it is always necessary to complement Raman analysis with other analytical methods.
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Copper phthalocyanine (CuPc) blues (PB15) are largely used in art and industry as pigments. In these fields mainly three different polymorphic modifications of PB15 are employed: alpha, beta and epsilon. Differentiating among these CuPc forms can give important information for developing conservation strategy and can help in relative dating, since each form was introduced in the market in different time periods. This study focuses on the classification of Raman spectra measured using 532 nm excitation wavelength on: (i) dry pigment powders, (ii) unaged mock-ups of self-made paints, (iii) unaged commercial paints, and (iv) paints subjected to accelerated UV ageing. The ratios among integrated Raman bands are taken in consideration as features to perform Random Forest (RF). Features selection based on Gini Contrast score was carried out on the measured dataset to determine the Raman bands ratios with higher predictive power. These were used as polymorphic markers, in order to establish an easy and accessible method for the identification. Three different ratios and the presence of a characteristic vibrational band allowed the identification of the crystal modification in pigments powder as well as in unaged and aged paint films.
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Photochemical degradation of commercial polyvinyl acetate (PVAc) homopolymer and PVAc paints mixed with burnt umber, cobalt blue, cadmium red dark, nickel azo yellow and titanium white commonly used for artworks were studied by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) and Fourier transform infrared spectroscopy-attenuated total reflectance (FTIR-ATR). Py-GC/MS with single-shot technique was used for the characterization of the thermal degradation of PVAc at different temperatures, while the double-shot technique of Py-GC/MS was used to reveal the differences in the specimens before and after UV ageing, including the changes of detectable amounts of deacetylation product - acetic acid and plasticizers such as diethyl phthalate (DEP). Furthermore, the relative concentration of the pyrolysis products of the paint samples could be measured and compared in the second step of the double-shot Py-GC/MS, which are highly dependent on the presence of pigments and the ageing status of PVAc paints.
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The lightfastness declarations of several different commercial acrylic paints and different quality series were tested by artificial UV ageing. To evaluate their lightfastness declarations, three acrylic colours (cadmium red, ultramarine blue and chromium oxide green) from six companies (Lascaux, Liquitex, Lukas, Rembrandt, Schmincke, and Winsor & Newton) were analysed before and after UV exposure. Characterisation and identification of these materials were carried out with Py-GC/MS, FTIR-ATR analyses, and colour measurements. Particular attention was focused on the Py-GC/MS measurements and on comparison of the single-shot method for pyrolysis of polymers and the double-shot mode which enables a unique combination of pyrolysis methods for analysis of polymers and thermal desorption for documentation of the volatile compounds. Depending on the particular company and the specific value of the lightfastness declaration, different binding media (i.e. poly(EA/MMA), poly(nBA/MMA), and poly(2-EHA/MMA)), and fillers (i.e. kaolinite, calcium carbonate, barite, and talc) were characterised and identified by Py-GC/MS and FTIR-ATR analyses. After UV exposure, several alteration processes with consequent formation of volatile compounds or new products were observed by both techniques, especially for the blue paints. In particular, the double-shot mode of Py-GC/MS enabled the detection of oxidation products, which could not be detected with the single-shot mode. Comparison of the lightfastness declarations for each of the blue, green, and red paints and the noted alterations broadly agreed for most of the paints.
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This study characterizes and identifies two different acrylic binding media such as Plextol® D498 and Primal® AC33, which are widely used in modern and contemporary art. In order to investigate their fast photooxidative deterioration when exposed to ultraviolet (UV) light, ageing studies on these materials were carried out. For this purpose, pure synthetic materials but also mixed with different inorganic pigments were identified and characterized before and after UV exposure by means of pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). Particular attention was paid to the comparison of two different analytical methods: (1) single-shot method based on a pyrolysis for the analysis of polymers and (2) double-shot method, which allows a unique combination of thermal desorption for the analysis of volatile compounds and pyrolysis of the polymers themselves. These analyses have been complemented by Fourier transform infrared spectroscopy-attenuated total reflectance (FTIR-ATR) studies. The comparison of the results obtained from unaged samples and UV-aged clearly showed material alterations as well as the formation of new products, which were recorded by FTIR-ATR. Generally, these changes were more pronounced when the acrylic binding media were mixed with pigments. The double-shot technique of Py-GC/MS additionally allowed the detection of the phenolic antioxidant in unaged Plextol® D498, but no oxidation products could be identified by Py-GC/MS in all samples.
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A detailed understanding of the stability of glasses toward liquid or atmospheric attack is of considerable importance for preserving numerous objects of our cultural heritage. Glasses produced in the ancient periods (Egyptian, Greek, or Roman glasses), as well as modern glass, can be classified as soda-lime-silica glasses. In contrast, potash was used as a flux in medieval Northern Europe for the production of window panes for churches and cathedrals. The particular chemical composition of these potash-lime-silica glasses (low in silica and rich in alkali and alkaline earth components), in combination with increased levels of acidifying gases (such as SO(2), CO(2), NO(x), or O(3)) and airborne particulate matter in today's urban or industrial atmospheres, has resulted in severe degradation of important cultural relics, particularly over the last century. Rapid developments in the fields of microelectronics and computer sciences, however, have contributed to the development of a variety of nondestructive, surface analytical techniques for the scientific investigation and material characterization of these unique and valuable objects. These methods include scanning electron microscopy in combination with energy- or wavelength-dispersive spectrometry (SEM/EDX or SEM/WDX), secondary ion mass spectrometry (SIMS), and atomic force microscopy (AFM). In this Account, we address glass analysis and weathering mechanisms, exploring the possibilities (and limitations) of modern analytical techniques. Corrosion by liquid substances is well investigated in the glass literature. In a tremendous number of case studies, the basic reaction between aqueous solutions and the glass surfaces was identified as an ion-exchange reaction between hydrogen-bearing species of the attacking liquid and the alkali and alkaline earth ions in the glass, causing a depletion of the latter in the outermost surface layers. Although mechanistic analogies to liquid corrosion are obvious, atmospheric attack on glass ("weathering") is much more complex due to the multiphase system (atmosphere, water film, glass surface, and bulk glass) and added complexities (such as relative humidity and atmospheric pollutant concentration). Weathered medieval stained glass objects, as well as artifacts under controlled museum conditions, typically have less transparent or translucent surfaces, often with a thick weathering crust on top, consisting of sulfates of the glass constituents K, Ca, Na, or Mg. In this Account, we try to answer questions about glass analysis and weathering in three main categories. (i) Which chemical reactions are involved in the weathering of glass surfaces? (ii) Which internal factors (such as the glass composition or surface properties) play a dominant role for the weathering process? Can certain environmental or climatic factors be identified as more harmful for glasses than others? Is it possible to set up a quantitative relationship or at least an approximation between the degree of weathering and the factors described above? (iii) What are the consequences for the restoration and conservation strategies of endangered glass objects? How can a severe threat to precious glass objects be avoided, or at least minimized, to preserve these artifacts of our cultural heritage for future generations?