Search

As part of the 2018 Girl in the Spotlight project, reflectance and molecular fluorescence imaging spectroscopy (RIS, FIS), and macroscale X-ray fluorescence scanning (MA-XRF) were performed on Johannes Vermeer's Girl with a Pearl Earring (c. 1665, Mauritshuis) with the goal of obtaining a comprehensive understanding of the distribution of pigments. Prior analysis of cross-sections in the 1990s, and their recent (re)-examination identified many of the pigments present in the painting. The results from all three imaging methods, along with site-specific fibre optic reflectance spectroscopy, confirmed Vermeer's limited palette and determined how and where each pigment was used. RIS and MA-XRF found the blue region of the headscarf was painted with natural ultramarine and varying amounts of lead white. The yellow part of the headscarf was painted with yellow ochre and lead white, and the border of the headscarf additionally contained ultramarine and lead–tin yellow. The lit side of the jacket was painted with yellow ochre, lead white, and ultramarine, whereas the darker, ruddy blue-green areas that are in relative shadow contained yellow ochre with ultramarine. FIS also mapped a red lake in portions of the shadowed areas at the back of the jacket. The Girl's skin was painted using earths (ochres), lead white, vermilion, and some red lake. Fluorescence emission from red lake was strongest in the lips, where vermilion was also found. The pearl earring was depicted using a scumble and highlight of lead white. In the dark background, the RIS data cube allowed the determination of the visible spectral shape even though the overall reflectance intensity was low (1 to 3%). A reflectance inflection point at ~ 700 nm indicated the presence of indigo, whereas lack of a reflectance peak at green wavelengths in most areas indicated degradation of the yellow pigment previously identified as weld. Some small green areas in the background (i.e. reflectance maximum at 525 nm) were found; these coincided with areas previously protected by old retouchings, and are thus better preserved. The combination of all three spectral imaging modalities provided a more complete understanding of how the colouration of the painting was achieved. [ABSTRACT FROM AUTHOR]

This article highlights a technical examination of The Lamentation of Christ (ca. 1460, Mauritshuis) attributed to Rogier van der Weyden and studio, performed during its recent conservation treatment. The goal of the research was to identify and map pigments used for the final paint and underpaint of the figures using information from non‐invasive chemical mapping and analysis of cross sections, to support the existing attribution of the painting. The results from a MA‐XRF scanner and two hyperspectral reflectance imaging cameras (400–1000 nm; 967–1680 nm) along with those from the analysis of recent paint cross sections and those collected in the 1980s allowed for a comprehensive understanding of the pigments used and their distribution. In general, the results show that the artist achieved a wide variety of colored draperies (robes) of the figures using a limited palette. High‐quality ultramarine and coarse azurite were identified in the different blue draperies, while azurite was also found combined with red lake and lead white to produce the lilac and purple‐toned fabrics. The green robe contains another copper pigment, verdigris, combined with lead‐tin yellow. The various red draperies show subtle differences in hue, obtained by varying the layer stratigraphy and proportions of lead white, vermilion, and red lake. The chemical maps also provided new insights into the original appearance and modeling of some of the draperies, including the unusual brown dress that was found to contain (partly faded) red lake. Comparison with previous technical studies shows that the materials and elaborate build‐ups used to paint The Lamentation are consistent with other paintings by Rogier van der Weyden and his workshop. [ABSTRACT FROM AUTHOR]

Conspectus: Diffuse reflectance hyperspectral imaging, or reflectance imaging spectroscopy, is a sophisticated technique that enables the capture of hundreds of images in contiguous narrow spectral bands (bandwidth < 10 nm), typically in the visible (Vis, 400-750 nm) and the near-infrared (NIR, 750-2500 nm) regions. This sequence of images provides a data set that is called an image-cube or file-cube. Two dimensions of the image-cube are the spatial dimensions of the scene, and the third dimension is the wavelength. In this way, each spatial pixel in the image has an associated reflectance spectrum. This "big data" image-cube allows for the mining of artists' materials and mapping their distribution across the surface of a work of art. Reflectance hyperspectral imaging, introduced in the 1980s by Goetz and co-workers, led to a revolution in the field of remote sensing of the earth and near planets. In the subsequent decades, thanks to rapid advances in solid-state sensor technology, reflectance hyperspectral imaging, once only available to large government laboratories, was extended to new fields of application, such as monitoring agri-foods, pharmaceutical products, the environment, and cultural heritage. In the 2000s, the potential of this noninvasive technology for the study of artworks became evident and, consequently, the methodology is becoming more widely used in the art conservation science field. Typically hyperspectral reflectance image-cubes contain millions of spectra. Many of these spectra are similar, making the reduction of the data set size an important first step. Thus, image-processing tools based on multivariate techniques, such as principal component analysis (PCA), automated classification methods, or expert knowledge systems, that search for known spectral features are often applied. These algorithms seek to reduce the large number of high-quality spectra to a common subset, which allow identifying and mapping artists' materials and alteration products. Hence, reflectance hyperspectral imaging is finding its place as the starting point to find sites on polychrome surfaces for spot analytical techniques, such as X-ray fluorescence, Raman spectroscopy, and Fourier transform infrared spectroscopy. Reflectance hyperspectral imaging can also provide image products that are a mainstay in the art conservation field, such as color-accurate images, broadband near-infrared images, and false-color products. This Account reports on the research activity carried out by two research groups, one at the "Nello Carrara" Institute of Applied Physics of the Italian National Research Council (IFAC-CNR) in Florence and the other at the National Gallery of Art (NGA) in Washington, D.C. Both groups have conducted parallel research, with frequent interchanges, to develop multispectral and hyperspectral imaging systems to study works of art. In the past decade, they have designed and experimented with some of the earliest spectral imaging prototypes for museum applications. In this Account, a brief presentation of the hyperspectral sensor systems is given with case studies showing how reflectance hyperspectral imaging is answering key questions in cultural heritage. [ABSTRACT FROM AUTHOR]

Historic works on paper, illuminated (painted) or unpainted manuscripts, and textiles are fragile and nearly impossible to sample. Non-invasive techniques such as visible microscopy, X-ray fluorescence, Raman, and reflectance spectroscopy are commonly used to determine the artist material present. Recently, nonlinear optical ultrafast pump-probe microscopy was shown to provide non-invasive, high-resolution mapping of pigments in historic paintings to investigate paint stratigraphy. In this paper, we combine our pump-probe contrast with nonlinear fluorescence and second-harmonic generation contrasts exhibited by fibrous supports composed of natural bio-materials (cellulose, collagen, or lignin). Hence, our multi-modal nonlinear microscope is able to simultaneously investigate pigments in conjunction with their support in three dimensions with micrometer-scale spatial resolution. Here we examine the utility of nonlinear pump-probe microscopy by studying a series of mock-up samples, including indigo-dyed cotton cloth, ultramarine blue painted on various types of paper, and papers painted with mixtures and layers of the two pigments. In each case we find that we can combine pump-probe pigment contrast with nonlinear optical fiber contrast to obtain spatial information that is otherwise unavailable to the conservator. [ABSTRACT FROM AUTHOR]

Background: Imaging spectroscopy, the collection of spatially co-registered images in many contiguous spectral bands, has been developed for remote sensing of the Earth utilizing reflectance or luminescence. In this paper we summarize findings on the application of imaging spectroscopy to works of art in order to identify and map artists' pigments, improve the visualization of preparatory sketches, and identify non-original material. Methods: Two types of novel hyperspectral cameras, one operating from the visible to near-infrared (VNIR, 400- 900 nm) and the other in the shortwave infrared (SWIR, 950-1700 nm), have been used to collect diffuse reflectance spectral image cubes from a variety of paintings. The resulting cubes (400-1700 nm, 310 spectral bands) were calibrated to reflectance and the resulting spectra compared with point-based spectra collected with a fiber reflectance spectrometer (350-2500 nm). In addition, a calibrated multispectral camera (600-950 nm, eight spectral bands) was used to obtain luminescence spectral image cubes after exciting paintings at blue wavelengths. Results: False-color images obtained from the SWIR imaging system are shown to give improved visualization of changes from paintings having large and complex reworkings, e.g. Pablo Picasso's The Tragedy (1903). False-color images and reflectance spectra allowed definitive identification of restoration in a late 13th century Sienese painting that cannot be seen by traditional infrared reflectography. Spectral image processing on the reflectance image cubes have been used to identify the primary pigments or pigment mixtures. For example, the primary pigments and their distribution in Picasso's Peonies (1901) was determined and compared with x-ray fluorescence (XRF) analysis and scanning electron microscopy-energy dispersive x-ray spectroscopy (SEM-EDS). Conclusion: The results show that the combination of both the SWIR reflectance data and the luminescence data provides a more robust ability to assign the pigments than with visible spectroscopy alone. Also highlighted is the utility of reflectance imaging spectroscopy in the SWIR region to better reveal specific paint changes, including changes in the drawings and markings made by the original artist, or changes made by a subsequent conservator such as a fill. [ABSTRACT FROM AUTHOR]

There is growing interest in bringing non-invasive laboratory-based analytical imaging tools to field sites to study wall paintings in order to collect molecular information on the macroscale. Analytical imaging tools, such as reflectance imaging spectrometry, have provided a wealth of information about artist materials and working methods, as well as painting conditions. Currently, scientific analyses of wall paintings have been limited to point-measurement techniques such as reflectance spectroscopy (near-ultraviolet, visible, near-infrared, and mid-infrared), X-ray fluorescence, and Raman spectroscopy. Macroscale data collection methods have been limited to multispectral imaging in reflectance and luminescence modes, which lacks sufficient spectral bands to allow for the mapping and identification of artist materials of interest. The development of laboratory-based reflectance and elemental imaging spectrometers and scanning systems has sparked interest in developing truly portable versions, which can be brought to field sites to study wall paintings where there is insufficient space or electrical power for laboratory instruments. This paper presents the design and testing of a simple hyperspectral system consisting of a 2D spatial spot scanning spectrometer, which provides high spectral resolution diffuse reflectance spectra from 350 to 2500 nm with high signal to noise and moderate spatial resolution (few mm). This spectral range at high spectral resolution was found to provide robust chemical specificity sufficient to identify and map many artists' materials, as well as the byproducts of weathering and conservation coatings across the surface of ancient and Byzantine Cypriot wall paintings. Here, we present a detailed description of the hyperspectral system, its performance, and examples of its use to study wall paintings from Roman tombs in Cyprus. The spectral/spatial image processing workflow to make maps of pigments and constituent painting materials is also discussed. This type of configurable hyperspectral system and the imaging processing workflow offer a new tool for the field study of wall paintings and other immovable heritage. [ABSTRACT FROM AUTHOR]

A paradigm using multispectral visible and near-infrared imaging spectroscopy is presented to semi-automatically create unbiased spectral maps that guide the site selection for in situ analytical methods (e.g. fiber optic reflectance spectroscopy and X-ray fluorescence) in order to identify and map pigments in illuminated manuscripts. This approach uses low spectral resolution imaging spectroscopy to create maps of areas having the same spectral characteristics. This paradigm is demonstrated by analysis of the illuminated manuscript leaf Christ in Majesty with Twelve Apostles (workshop of Pacino di Buonaguida, c. 1320). Using this approach the primary pigments are mapped and identified as azurite, lead-tin yellow, red lead, a red lake (likely insect-derived), a copper-containing green, brown iron oxide, and lead white. Moreover, small amounts of natural ultramarine were found to be used to enhance the blue fields around Christ, and a red lake was used to highlight different colors. These results suggest that the proposed paradigm offers an improved approach to the comprehensive study of illuminated manuscripts by comparison with site-specific analytical methods alone. The choice of broad spectral bands proves successful, given the limited palette in illuminated manuscripts, and permits operation at the low light intensity required for examination of manuscripts. [ABSTRACT FROM AUTHOR]

The modification of microscopically rough surfaces by commonly used varnishes and resultant changes in light reflection from these surfaces were studied using laser scanning confocal microscopy, stylus profilometry and specular gloss and distinctness-of-image gloss measurements. Natural resins as well as synthetic low molecular weight and polymeric resins were studied. The molecular weights of the resins were determined using size-exclusion chromatography. All the low molecular weight resins, with weight-average molecular weights in the range 800-6500, including the natural resins, essentially produced smooth surfaces and eliminated high-frequency as well as low-frequency roughness, while polymeric resins, with weight-average molecular weights between about 25000 and 210000, produced rougher surfaces, eliminating high-frequency roughness but not all low-frequency roughness. The spatial frequency range of the roughness of the polymeric coatings decreased with increasing molecular weight. As a result, low molecular weight varnishes reduced small-angle scattering about the specular reflection to a greater extent than the polymeric coatings. Polymeric varnishes, therefore, demonstrated lower specular gloss and, in particular, lower distinctness-of-image gloss. Distinctness-of-image gloss values showed good correlation with the weight-average molecular weights of the resins. The power spectral density of the surfaces coated with low molecular weight resins showed a sharper falloff at low spatial frequencies than the polymeric resins. [ABSTRACT FROM AUTHOR]

Visible and infrared reflectance imaging spectroscopy is one of the several non-invasive techniques used during Operation Night Watch for the study of Rembrandt's iconic masterpiece The Night Watch (1642). The goals of this project include the identification and mapping of the artists' materials, providing information about the painting technique used as well as documenting the painting's current state and ultimately determining the possible conservation plan. The large size of the painting (3.78 m by 4.53 m) and the diversity of the technical investigations being performed make Operation Night Watch the largest research project ever undertaken at the Rijksmuseum. To construct a complete reflectance image cube at a high spatial resolution (168 µm2) and spectral resolution (2.54 to 6 nm), the painting was imaged with two high-sensitivity line scanning hyperspectral cameras (VNIR 400 to 1000 nm, 2.54 nm, and SWIR 900 to 2500 nm, 6 nm). Given the large size of the painting, a custom computer-controlled 3-D imaging frame was constructed to move each camera, along with lights, across the painting surface. A third axis, normal to the painting, was added along with a distance-sensing system which kept the cameras in focus during the scanning. A total of 200 hyperspectral image swaths were collected, mosaicked and registered to a high-resolution color image to sub-pixel accuracy using a novel registration algorithm. The preliminary analysis of the VNIR and SWIR reflectance images has identified many of the pigments used and their distribution across the painting. The SWIR, in particular, has provided an improved visualization of the preparatory sketches and changes in the painted composition. These data sets, when combined with the results from the other spectral imaging modalities and paint sample analyses, will provide the most complete understanding of the materials and painting techniques used by Rembrandt in The Night Watch. [ABSTRACT FROM AUTHOR]

To obtain a better understanding of the variations in the appearance of paintings brought about by different varnishes, their ability to form an optically smooth film over rough surfaces was studied using laser scanning confocal microscopy and stylus profilometry, as well as gloss and distinctness-of-image gloss measurements. Two different varnishes, one made with a low molecular weight resin and having low viscosity, and another made with a polymer of high molecular weight and having high viscosity, were applied over glass plates that had been given surface roughness in the micrometer range. Measurement of the topography showed that the polymeric resin eliminated mid-to-high spatial frequency roughness of the ground glass but did not eliminate roughness of lower spatial frequencies. The results are discussed in terms of the surface state of the varnish, using concepts such as root-mean-square roughness, total integrated scattering and the power spectral density. These observations indicate that both varnishes reduce the wide-angle light scattering by the rough substrates, but only the varnish made with the low molecular weight resin reduces the small-angle scattering about the specular reflection. This suggests that the smoothness of the varnished surface depends both on the molecular weight of the resin and on the spatial frequencies of the surface roughness of the surface beneath it. A model for the drying of varnishes is presented that takes the spatial frequency dependence into account. [ABSTRACT FROM AUTHOR]

Investigates the effects of bridged retinals on the photocyle in bacteriorhodopsin mutants (leucine-93) defective in protein-retinal coupling. Effect of the bridged retinals on decay of the oxygen intermediate in the leucine-93 mutant; Effect on the acceleration of photocycle of the leucine-93-->alanine mutant.

Abstract. The photophysical properties of Sn-protoporphyrin and two of its synthetic analogues, Sn-mesoporphyrin and Sn-diiododeuteroporphyrin, were examined. All three compounds are potent competitive inhibitors of heme oxygenase, the rate-limiting enzyme in the catabolism of heme to bilirubin, and can suppress completely or diminish significantly experimentally induced or naturally occurring forms of jaundice in animals or man. The results of these studies show that all three compounds have long-lived triplet states which are quenched by molecular oxygen both in solution and when incorporated in liposomes. However, the addition of quenching groups such as iodine to the porphyrin macrocycle results in a marked (approximately 60%) decrease in the triplet yield and a threefold decrease in the triplet lifetime. The triplet yield was shown to be independent of the excitation wavelength, and as a result, the metalloporphyrins were extremely poor photosensitizers when excited in the spectral region commonly used in phototherapy. In the presence of serum albumin, the triplet state of Sn-protoporphyrin was not quenched by oxygen. These results indicate that Sn-porphyrins can be custom designed with considerably reduced photosensitizing properties for potential clinical use as inhibitors of bilirubin production. Pediatrics 1988;81:498-504; photobiology, Sn-porphyrin, neonatal hyperbilirubinemia. [ABSTRACT FROM AUTHOR]

Prior studies have shown the improved ability to identify artists’ pigments by combining results from X-ray fluorescence (XRF), which provides elemental information, with reflectance spectroscopy in the visible to near infrared (400-1000 nm) that provides information on electronic transitions. Extending the spectral range of reflectance spectroscopy into the UV, 350-400 nm, allows identification of several white pigments since their electronic transitions occur in this region (e.g., zinc white and rutile and anatase forms of titanium white). Extending the range further into the infrared, out to 2500 nm, provides information on vibrational transitions of various functional groups, such as hydroxyl, carbonate, and methyl groups. This allows better identification of mineral-based pigments and some paint binders. The combination of elemental information with electronic and vibrational transitions provides a more robust method to identify artists’ materials in situ. The collection of both sets of spectral information across works of art, such as paintings and works on paper, allows generating a more complete map of artists’ materials. Here, we describe a 2-D scanner that simultaneously collects XRF spectra and reflectance spectra from 350 to 2500 nm across the surfaces of works of art. The scanner consists of a stationary, single pixel XRF spectrometer and fiber optic reflectance spectrometer along with a 2-D position-controlled easel that moves the artwork in front of the two detection systems. The dual-mode scanner has been tested on a variety of works of art from illuminated manuscripts (0.1 × 0.1 m2) to paintings as large as 1.7 × 1.9 m2. The scanner is described and two sets of results are presented. The first is the XRF scanning of a large warped panel painting by Andrea del Sarto titled Charity. The second is a combined XRF and reflectance scan of Georges Seurat’s painting titled Haymakers at Montfermeil. The XRF was collected at 1 mm spatial sampling and the reflectance spectral data at 3 mm. Combining the results from the data sets was found to enhance the identification of pigments as well as yield distribution maps, in spite of the relatively low reflectance spatial sampling. The elemental and reflectance maps allowed the identification and mapping of lead white, cobalt blue, viridian, ochres, and likely chrome yellow. The maps also provide information on the mixing of pigments. While the reflectance image cube has 10-20× larger spatial samples than desired, the elimination of having to use two hyperspectral cameras to cover the range from 400 to 2500 nm makes for a low cost dual modality scanner. [ABSTRACT FROM AUTHOR]

The soft modelling of the skin tones in Vermeer's Girl with a Pearl Earring (Mauritshuis) has been remarked upon by art historians, and is their main argument to date this painting to c. 1665. This paper describes the materials and techniques Vermeer used to accomplish the smooth flesh tones and facial features of the Girl, which were investigated as part of the 2018 Girl in the Spotlight research project. It combines macroscopic X-ray fluorescence imaging (MA-XRF), reflectance imaging spectroscopy (RIS), and 3D digital microscopy. Vermeer built up the face, beginning with distinct areas of light and dark. He then smoothly blended the final layers to create almost seamless transitions. The combination of advanced imaging techniques highlighted that Vermeer built the soft contour around her face by leaving a 'gap' between the background and the skin. It also revealed details that were otherwise not visible with the naked eye, such as the eyelashes. Macroscopic imaging was complemented by the study of paint cross-sections using: light microscopy, SEM–EDX, FIB-STEM, synchrotron radiation µ-XRPD and FTIR–ATR. Vermeer intentionally used different qualities or grades of lead white in the flesh paints, showing different hydrocerussite/cerussite ratios and particle sizes. Lead isotope analysis showed that the geographic source of lead, from which the different types of lead white were manufactured, was the same: the region of Peak District of Derbyshire, UK. Finally, cross-section analysis identified the formation of new lead species in the paints: lead soaps and palmierite (K2Pb(SO4)2), associated with the red lake. [ABSTRACT FROM AUTHOR]

Focuses on the Wildlife Conservation Society's (WCS) involvement in the protection and researches on jaguar wild cats and humpback whales. Amount donated by Jaguar Cars to WCS to fund surveys on jaguar's status around the world; Population and distribution study on humpback whales in Madagascar.

A previous preliminary study of 15th-century Venetian manuscript fragments by the Master of the Murano Gradual identified the presence of cobalt in many ultramarine blue areas, suggesting the presence of smalt. This would represent an early use of this glassy pigment in Venetian illuminated manuscripts. Whereas sampling has been used to identify smalt in 15th century paintings, only non-invasive methods can be used on manuscripts due to their small size and fragile nature. Here we investigated four non-invasive analysis techniques to identify small amounts of smalt in the presence of ultramarine, including single-point and scanning XRF spectroscopy, UV–vis-NIR-SWIR reflectance spectroscopy (FORS), Raman spectroscopy, and external reflection FT-IR spectroscopy. This was done by studying paint mock-ups of ultramarine and smalt mixtures with and without the presence of a white pigment on parchment. The results showed molecular spectroscopy techniques (reflectance, Raman, and FTIR) require at least ~ 30–40% smalt by percent mass when in the presence of ultramarine in order to detect its presence, whereas elemental XRF spectroscopy can detect cobalt (and thus infer the presence of smalt) at the ~ 1% level. To further explore the inference of smalt by XRF, additional XRF analysis was conducted to specifically look for elements associated with cobalt minerals (i.e. nickel, arsenic, bismuth, etc.). High spatial resolution XRF scanning (60–100 μm X-ray spot size) was used to look for cobalt in smalt particles which are typically larger than those of ultramarine. These two XRF analysis approaches worked well with the mock-up paint samples, and were subsequently applied to the manuscripts for which molecular spectroscopy methods yielded no unambiguous evidence for smalt. The data underscore the challenges of conclusively identifying smalt in complex paint systems when samples are not available, but do suggest that the Master of the Murano illuminated manuscript fragments contain smalt, but perhaps not in a form or amount researchers are used to seeing in paintings. [ABSTRACT FROM AUTHOR]

The layering structure of a painting contains awealth of information about the artist's choice of materials and working methods, but currently, no 3D noninvasive method exists to replace the taking of small paint samples in the study of the stratigraphy. Here, we adapt femtosecond pump-probe imaging, previously shown in tissue, to the case of the color palette in paintings, where chromophores have much greater variety. We show that combining the contrasts of multispectral and multidelay pump-probe spectroscopy permits nondestructive 3D imaging of paintings with molecular and structural contrast, even for pigments with linear absorption spectra that are broad and relatively featureless. We show virtual crosssectioning capabilities in mockup paintings, with pigment separation and nondestructive imaging on an intact 14th century painting (The Crucifixion by Puccio Capanna). Our approach makes it possible to extract microscopic information for a broad range of applications to cultural heritage. [ABSTRACT FROM AUTHOR]

Imaging spectroscopy (IS) is an important tool in the comprehensive technical analysis required of archaeological paintings. The complexity of pigment mixtures, diverse artistic practices and painting technologies, and the often-fragile and weathered nature of these objects render macroscale, non-invasive chemical mapping an essential component of the analytical protocol. Furthermore, the use of pigments such as Egyptian blue and madder lake, featuring diagnostic photoluminescence emission, provides motivation to perform photoluminescence mapping on the macroscale. This work demonstrates and advances new applications of dual-mode imaging spectroscopy and data analysis approaches for ancient painting. Both reflectance (RIS) and luminescence (LIS) modes were utilized for the study of a Roman Egyptian funerary portrait from second century CE Egypt. The first derivative of the RIS image cube was analyzed and found to significantly improve materials separation, identification, and the extent of mapping. Egyptian blue and madder lake were mapped across a decorated surface using their luminescence spectral signatures in the region of 540–1000 nm as endmembers in LIS analyses. Linear unmixing of the LIS endmembers and subsequent derivative analyses resulted in an improved separation and mapping of the luminescence pigments. RIS and LIS studies, combined with complementary, single-spot collection elemental and molecular spectroscopy, were able to successfully characterize the portrait's painting materials and binding media used by the ancient artist, providing key insight into their material use, stylistic practices, and technological choices. [ABSTRACT FROM AUTHOR]

Abstract: Modification of the visual appearance when a rough surface is covered by a varnish is mostly attributed to the levelling of the substrate surface, which depends on the molecular weight of the varnish. The topography of varnished surfaces, however, has never been measured directly. Surfaces of varnishes applied over glass substrates of varying roughness were studied, therefore, using mechanical profilometry. Two different varnishes made with a low and a high molecular weight resin were studied. Both varnishes lower the r.m.s. roughness of the substrates and filter the high spatial frequencies. These results are amplified for the varnish containing the low molecular weight resin. The light reflected by the varnished samples is modelled from these topographical data. Its angular distribution, calculated from the probability density of slopes is presented, taking into account separately the air/varnish and the varnish/substrate interfaces. These analyses are presented in a back-scattering configuration. They show that varnishing significantly reduces the angular width of the reflected light and that this effect is magnified for the low molecular weight resin. Modelling furthermore shows that the influence of the roughness of the varnish/substrate interface is negligible in the total reflected light. [Copyright &y& Elsevier]

Scientific imaging of a large fragile work of art can be especially challenging, but especially rewarding to better grasp the complexity and changes that have occurred during its creation and lifetime. Here, noninvasive imaging, macro X-ray fluorescence (MAXRF) imaging spectroscopy and reflectance imaging spectroscopy, from the visible to the near infrared spectral range, are utilized to document a 14-m-long Japanese narrative handscroll, The Miraculous Interventions of Jizō Bosatsu. Due to the scroll's age and its handling during past use as a teaching tool, it has a number of conservation needs and shows evidence of past repairs. The scroll has extensive and severe creasing, breaks and tears, as well as unstable and powdering pigments. Microscopic observation and scientific analyses were performed both to document the current condition of the scroll and to better understand its long history. Combining RIS and MAXRF allowed for pigment characterization through elemental and molecular information. While RIS and MAXRF previously have been applied to the study of other painted materials, their application to East Asian paintings is rare. The obstacles of the scroll's length and fragile uneven surface were overcome by optimizing the setups of the two imaging systems. The MAXRF and RIS analyses, here focused on a select scene of the scroll, found certain original pigments common in early Japanese scroll paintings were used frequently, such as vermilion, iron-based compounds (yellow and red ochres), and copper-containing greens, while others occurred sparingly, such as azurite and red lead. A chloride-containing lead-based white pigment was employed. Faded organic colorants, notably indigo as well as an organic yellow/brown, could be detected but their vibrancy has been muted over the centuries. In the case of indigo, it may be visibly observed in some areas; however, analysis revealed its previously unknown presence mixed with a copper green in a select area. This focused study sets a foundation for further studies on both this object and other Asian works of art. [ABSTRACT FROM AUTHOR]

A series of experiments is described, the aim of which is to identify the optimum spectral band and detector configuration for the visualization of underdrawings. First, the visualization of underdrawings is investigated using three detector systems operating in different infrared spectral bands from 0.9 to 2-5µm. Visibility analysis is applied to the examination of eight test panels, each having a rectangle of paint covering six different underdrawing materials. These data demonstrate that the combined optical properties of the pigment and the underdrawing material determine which spectral band gives the optimum visualization of the underdrawing. The peak visibilities of different combinations occur between 1.0 and 2.5gm. These results suggest that camera systems having uniform spectral responsivity across the l.0 to 2.5pro band would be most useful for infrared reflectography (IRR). Second, the imaging properties of each camera system are investigated. Comparison of the modulation transfer function (MTF) and signal-to-noise ratio for the vidicon and the platinum silicide (PtSi) camera systems shows that the latter is much closer to a theoretically perfect system. Finally, the applicability of the visibility studies and MTF modeling to the IRR application is demonstrated by the examination of two paintings with the PtSi camera, which renders dramatically improved images of underdrawings and paint changes, as compared to reflectograms obtained with the vidicon camera. The implications of this study, including the potential use of infrared reflectography as a method of non-destructive analysis, are discussed. [ABSTRACT FROM AUTHOR]

• While much progress has been made in developing hyperspectral cameras for collecting high quality reflectance image cubes from works of art, little work has been done to create optimized image analysis tools to mine these rich and large data sets. • Automated convex geometry algorithms are good candidates for pigment classification of reflectance imaging spectroscopy (RIS) data from paintings. • The proposed Maximum Distance (MaxD) algorithm performs well with automatic classification of paintings from RIS data cubes. Significant reduction in computation time, as well as a lack of tunable parameters makes this method desirable. • Spectral libraries have great use for visually comparing spectral features to help with pigment identification. Direct matching by algorithm is problematic because of normal variations in hue, scattering and the fact most paint layers are not optical thick enough in the near infrared. Knowledge of pigments and their distribution in paintings can inform conservators and scholars to better understand, and conserve these objects. In recent years, a variety of macro-scale non-contact imaging modalities have been applied to paintings to create classification/material maps. One modality, reflectance imaging spectroscopy (RIS) captures the diffuse reflectance spectral signatures of the artists' materials present in the objects which can be used for classification (by defining regions of the image cube that have the same spectral reflectance signature). In Cultural Heritage Science the ENVI spectral hourglass wizard (ENVI-SHW) has been used to create classification maps from RIS. This method is slow and requires an expert user input during the processing in order to find the reflectance spectra that define the spectral classes (spectral endmembers or exemplars). The pigments are then deduced from spectral features in endmember spectra and from other non-invasive analytical chemical analysis of sites defined by the RIS maps. This paper explores the potential of more automated algorithms, such as maximum distance (MaxD), that are based on the theory of convex hulls for doing these classifications as well as spectral matching algorithms to an optimal spectral library. While all of these algorithms were developed for Remote Sensing community, MaxD and the library matching examine all the spectra in the reflectance image cube, require little user input, and are reproducible and fast. The results from the analysis of reflectance image cubes (400 to 950 nm) of three paintings with MaxD and a spectral library matching algorithm are presented and compared to those obtained with the ENVI-SHW algorithm. The three paintings analyzed are the central panels from illuminated leafs, two from the Laudario of Sant'Agnese (c. 1340) painted by the Master of the Dominican Effigies, namely The Nativity with the Annunciation to the Shepherds and, Christ and the Virgin Enthroned with Forty Saints , and one cutting from a leaf from a Choir book, Saint Francis Receiving the Stigmata , painted by Cosmè Tura (c. 1470s). Specifically, the results include the spectral endmembers recovered from each method as well as the associated classification maps. The findings from this study show that the MaxD algorithm was able to find the majority of the reflectance spectral endmembers with little user input. [ABSTRACT FROM AUTHOR]

After the publication of the original article [1], the authors identified two errors in Table 1. [ABSTRACT FROM AUTHOR]

The article highlights the using of an elemental (x-ray fluorescence) and molecular (infrared reflectance) imaging spectroscopies in the way two complementary modalities which provided a more complete picture of the development and changes made to the Lamb. It mentions the extraction and characterization of microsamples by light microscopy and microchemical testing.

Vincent van Gogh used fugitive red lake pigments that have faded in some paintings. Mapping their distribution is key to understanding how his paintings have changed with time. While red lake pigments can be identified from microsamples, in situ identification and mapping remain challenging. This paper explores the ability of molecular fluorescence imaging spectroscopy to identify and, more importantly, map residual non‐degraded red lakes. The high sensitivity of this method enabled identification of the emission spectra of eosin (tetrabromine fluorescein) lake mixed with lead or zinc white at lower concentrations than elemental X‐ray fluorescence (XRF) spectroscopy used on account of bromine. The molecular fluorescence mapping of residual eosin and two carmine red lakes in van Gogh's The Olive Orchard is demonstrated and compared with XRF imaging spectroscopy. The red lakes are consistent with the composition of paint tubes known to have been used by van Gogh. [ABSTRACT FROM AUTHOR]

Vincent van Gogh used fugitive red lake pigments that have faded in some paintings. Mapping their distribution is key to understanding how his paintings have changed with time. While red lake pigments can be identified from microsamples, in situ identification and mapping remain challenging. This paper explores the ability of molecular fluorescence imaging spectroscopy to identify and, more importantly, map residual non‐degraded red lakes. The high sensitivity of this method enabled identification of the emission spectra of eosin (tetrabromine fluorescein) lake mixed with lead or zinc white at lower concentrations than elemental X‐ray fluorescence (XRF) spectroscopy used on account of bromine. The molecular fluorescence mapping of residual eosin and two carmine red lakes in van Gogh's The Olive Orchard is demonstrated and compared with XRF imaging spectroscopy. The red lakes are consistent with the composition of paint tubes known to have been used by van Gogh. [ABSTRACT FROM AUTHOR]

The size, shape, and application techniques of gold leaf in fourteenth- and fifteenth-century gold ground panel paintings attributed to artists working in Florence, Siena, and Fabriano was directly visualized using in situ scanning macro X-ray fluorescence spectroscopy (MA-XRF). The resulting gold (Au) Lα (9.712 keV) element distribution maps are of sufficient spatial resolution to enable an accurate and reproducible measurement of the shape and size of individual gold leaves. The resulting leaf measurements are discussed in the context of historical guild regulations, in particular, the 1403 reforms to the statutes of the Florentine Guild of Doctors and Apothecaries (Arte dei medici e speziale), which standardized the dimensions of gold leaf produced in Florence. The dimensions of the gold leaf from Florentine paintings created before and after the 1403 reforms were compared to each other as well as to gold ground paintings created in Siena and Fabriano. The results revealed the gold leaf squares in fourteenth-century Florentine and Sienese panels had side lengths averaging about 8 cm. In contrast, the gold leaf squares used in the fifteenth-century Florentine and Sienese paintings were smaller, with side lengths measuring about 7 cm. In addition, the degree of overlap between adjacent gold leaves was also measured. The amount of overlap was found to vary between artists, and the degree of overlap was consistent within the oeuvre of a specific artist. Taken together, these results suggest that the dimensions of the gold leaves found in panel paintings relate to the place of production on the Italian peninsula and the period in which they were created, while the degree of overlap relates to the individual hand of a gilder or artist/workshop. [ABSTRACT FROM AUTHOR]

Abstract: Microscale mid‐infrared (mid‐IR) imaging spectroscopy is used for the mapping of chemical functional groups. The extension to macroscale imaging requires that either the mid‐IR radiation reflected off or that emitted by the object be greater than the radiation from the thermal background. Reflectance spectra can be obtained using an active IR source to increase the amount of radiation reflected off the object, but rapid heating of greater than 4 °C can occur, which is a problem for paintings. Rather than using an active source, by placing a highly reflective tube between the painting and camera and introducing a low temperature source, thermal radiation from the room can be reduced, allowing the IR radiation emitted by the painting to dominate. Thus, emissivity spectra of the object can be recovered. Using this technique, mid‐IR emissivity image cubes of paintings were collected at high collection rates with a low‐noise, line‐scanning imaging spectrometer, which allowed pigments and paint binders to be identified and mapped. [ABSTRACT FROM AUTHOR]

Abstract: Microscale mid‐infrared (mid‐IR) imaging spectroscopy is used for the mapping of chemical functional groups. The extension to macroscale imaging requires that either the mid‐IR radiation reflected off or that emitted by the object be greater than the radiation from the thermal background. Reflectance spectra can be obtained using an active IR source to increase the amount of radiation reflected off the object, but rapid heating of greater than 4 °C can occur, which is a problem for paintings. Rather than using an active source, by placing a highly reflective tube between the painting and camera and introducing a low temperature source, thermal radiation from the room can be reduced, allowing the IR radiation emitted by the painting to dominate. Thus, emissivity spectra of the object can be recovered. Using this technique, mid‐IR emissivity image cubes of paintings were collected at high collection rates with a low‐noise, line‐scanning imaging spectrometer, which allowed pigments and paint binders to be identified and mapped. [ABSTRACT FROM AUTHOR]

Two imaging modalities based on molecular and elemental spectroscopy were used to characterize a painting by Cosimo Tura. Visible-to-near-infrared (400-1680 nm) reflectance imaging spectroscopy (RIS) and X-ray fluorescence (XRF) imaging spectroscopy were employed to identify pigments and determine their spatial distribution with higher confidence than from either technique alone. For example, Mary's red robe was modeled through the distribution of an insect-derived red lake (RIS map) and lead white (XRF lead map), rather than a layer of red lake on vermilion. The RIS image cube was also used to isolate the preparatory design by mapping the reflectance spectra associated with it. In conjunction with results from an earlier RIS study (1650-2500 nm) to map and identify the binding media, a more thorough understanding was gained of the materials and techniques used in the painting. [ABSTRACT FROM AUTHOR]

Two imaging modalities based on molecular and elemental spectroscopy were used to characterize a painting by Cosimo Tura. Visible-to-near-infrared (400-1680 nm) reflectance imaging spectroscopy (RIS) and X-ray fluorescence (XRF) imaging spectroscopy were employed to identify pigments and determine their spatial distribution with higher confidence than from either technique alone. For example, Mary's red robe was modeled through the distribution of an insect-derived red lake (RIS map) and lead white (XRF lead map), rather than a layer of red lake on vermilion. The RIS image cube was also used to isolate the preparatory design by mapping the reflectance spectra associated with it. In conjunction with results from an earlier RIS study (1650-2500 nm) to map and identify the binding media, a more thorough understanding was gained of the materials and techniques used in the painting. [ABSTRACT FROM AUTHOR]

In situ chemical imaging techniques are being developed to provide information on the spatial distribution of artists' pigments used in polychrome works of art such as paintings. The new methods include reflectance imaging spectroscopy and X-ray fluorescence mapping. Results from these new methods have extended the knowledge obtained from site-specific chemical analyses widely in use. While these mapping methods have aided in determining the distribution of pigments, there is a growing interest to develop methods capable of identifying and mapping organic paint binders as well. Near infrared (NIR) reflectance spectroscopy has been extensively used in the remote sensing field as well as in the chemical industry to detect organic compounds. NIR spectroscopy provides a rapid method to assay organics by utilizing vibrational overtones and combination bands of fundamental absorptions that occur in the mid-IR. Here we explore the utility of NIR reflectance imaging spectroscopy to map organic binders in situ by examining a series of panel paintings known to have been painted using distemper (animal skin glue) and tempera (egg yolk) binders as determined by amino acid analysis of samples taken from multiple sites on the panels. In this report we demonstrate the success in identifying and mapping these binders by NIR reflectance imaging spectroscopy in situ. Three of the four panel paintings from Cosimo Tura's The Annunciation with Saint Francis and Saint Louis of Toulouse (ca. 1475) are imaged using a highly sensitive, line-scanning hyperspectral imaging camera. The results show an animal skin glue binder was used for the blue skies and blue robe of the Virgin Mary, and egg yolk tempera was used for the red robes and brown landscape. The mapping results show evidence for the use of both egg yolk and animal skin glue in the faces of the figures. The strongest absorption associated with lipidic egg yolk features visually correlates with areas that appear to have white highlights. The results are in agreement with prior site-specific amino acid analysis, underscoring the synergy of both methods. The work here demonstrates that NIR reflectance imaging spectroscopy is a useful technique that can identify and map paint binding media based on differences in chemical composition. [ABSTRACT FROM AUTHOR]

To better understand and preserve works of art, knowledge is needed about the pigments used to create the artwork. Various noninvasive techniques have been used previously to create pigment maps, such as combining X-ray fluorescence and hyperspectral imaging data. Unfortunately, most museums have limited funding for the expense of specialized research equipment, such as hyperspectral reflectance imaging systems. However, many museums have hand-held point X-ray fluorescence systems attached to motorized easels for scanning artwork. To assist museums in acquiring data that can produce similar results to that of HSI systems, while minimizing equipment costs, this study designed and modeled a prototype system to demonstrate the expected performance of a low-cost multispectral system that can be attached to existing motorized easels. We show that multispectral systems with a well-chosen set of spectral bands can often produce classification maps with value on par with hyperspectral systems. This study analyzed the potential for capturing data with a point scanning system through predefined filters. By applying the system and noise modeling parameters to HSI data captured from a 14th-Century illumination, the study reveals that the proposed multispectral imaging system is a viable option for this need. [ABSTRACT FROM AUTHOR]

Spectral imaging modalities, including reflectance and X-ray fluorescence, play an important role in conservation science. In reflectance hyperspectral imaging, the data are classified into areas having similar spectra and turned into labeled pigment maps using spectral features and fusing with other information. Direct classification and labeling remain challenging because many paints are intimate pigment mixtures that require a non-linear unmixing model for a robust solution. Neural networks have been successful in modeling non-linear mixtures in remote sensing with large training datasets. For paintings, however, existing spectral databases are small and do not encompass the diversity encountered. Given that painting practices are relatively consistent within schools of artistic practices, we tested the suitability of using reflectance spectra from a subgroup of well-characterized paintings to build a large database to train a one-dimensional (spectral) convolutional neural network. The labeled pigment maps produced were found to be robust within similar styles of paintings. [ABSTRACT FROM AUTHOR]

The initial steps that Johannes Vermeer took to create Girl with a Pearl Earring (c. 1665) are, partially or completely, hidden beneath the painted surface. Vermeer's painting technique involved applying underlayers that vary in colour and thickness, on top of which he applied the upper paint layer(s). To investigate the painting's genesis, the Girl was examined using non-invasive scientific imaging as part of the project The Girl in the Spotlight (2018). This was complemented by the re-examination of existing paint cross-sections using microscopic analytical techniques, including focused ion beam-scanning transmission electron microscopy (FIB-STEM). The weave of the canvas, visible in the X-radiograph, was examined using a new computer-assisted thread-level canvas analysis algorithm to measure the thread spacing and thread angles. The canvas was primed with a warm light grey ground, although probably not by Vermeer himself. The tinted ground provided neutral base tone upon which he began to lay in areas of light and shade in his composition, and some outlines around the figure. Multispectral infrared reflectography(MS-IRR) images in four spectral bands spanning the spectral range from 900 to 2500 nm were collected of the painting at high spatial resolution (50 µm/pixel). Visible 3D digital microscopy visualised the underlayers where Vermeer left them visible around the perimeter of the figure as a contour, and where the upper paint layers are thin. These infrared reflectograms and visible micrographs identified three distinct preparatory phases of Girl with a Pearl Earring: the ground, fine black outlines, and underlayers. Some pentimenti were also detected, including a change in the position of her ear. The combination of examination methods showed that the materials beneath the surface played an important role in establishing the three-dimensional space, fall of light, and the eventual colour in different areas of the painting. [ABSTRACT FROM AUTHOR]

The artist Odilon Redon (1840–1916) was a French symbolist known for both the dark, surreal prints and drawings he created in the first half of his career, as well as the colorful pastel works that characterized the second half of his career. This study examines two drawings by Redon in the J. Paul Getty Museum collection—Apparition (ca. 1880–1890) and Head within an Aureole (ca. 1894–1895)—executed during the period in his career in which he was transitioning between these two modes. In order to better understand the materials the artist chose and the methods by which he applied them, two noninvasive, macroscopic characterization techniques—macro X-ray fluorescence (MA-XRF) scanning and reflectance imaging spectroscopy (RIS)—were employed. These techniques allowed the materials present to be distinguished and the relationship between their applications visualized. Coupled with fiber optic reflectance spectroscopy (FORS) and Raman microspectroscopy with principal component analysis (PCA), these results give new insight into the materials and methods used by Redon. Six distinct black drawing materials and a yellow pastel were identified in Apparition, underscoring the complexity of Redon's noir drawings. As he began using color pastel more frequently he seemed to use a simplified black palette; in Head within an Aureole the artist used only two black drawing materials and three color pastels (two pink and one blue). This research provides a framework for future noninvasive technical analysis of works by Redon in other collections as well as mixed media drawings more generally. [ABSTRACT FROM AUTHOR]

Late paintings of Rembrandt van Rijn (1606-1669) offer intriguing problems for both art historians and conservation scientists. In the research presented here, the key question addressed is whether observed stylistic differences in paint handling can be correlated with material differences. In Saul and David, in the collection of the Royal Picture Gallery Mauritshuis in The Hague, NL, the stylistic differences between the loose brushwork of Saul’s cloak and the more detailed depiction of his turban and the figure of David have been associated with at least two painting stages since the late 1960s, but the attribution of each stage has been debated in the art historical literature. Stylistic evaluation of the paint handling in the two stages, based on magnified surface examination, is further described here. One of the research goals was to determine whether the stylistic differences could be further differentiated with macroscale and microscale methods of material analysis. To address this, selected areas of the painting having pronounced stylistic differences were investigated with two macroscopic chemical imaging methods, X-ray fluorescence and reflectance imaging spectroscopies. The pigments used were identified and their spatial distribution was mapped. The mapping results show that the passages rendered in more detail and associated stylistically with the first painting stage, such as the orange-red color of David’s garment or the Greek key design in Saul’s turban, were painted with predominately red ochre mixed with vermilion. The regions of loose, bold brushwork, such as the orange-red slashing strokes in the interior of Saul’s cloak, associated with the second painting stage, were painted with predominately red ochre without vermilion. These macroscale imaging results were confirmed and extended with scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDX) analysis of three cross-sections taken from regions of stylistic differences associated with the two painting stages, including one sample each from the right and left sleeve of David, and one from the interior of Saul’s cloak. SEM-EDX also identified a trace component, barium sulfate, associated with the red ochre of the second stage revisions. Combining mapping information from two spectroscopic imaging methods with localized information from microscopic samples has clearly shown that the stylistic differences observed in the paint handling are affiliated with differences in the chemical composition of the paints. [ABSTRACT FROM AUTHOR]