Raman spectroscopy of inorganic materials in art and archaeology: spectroscopic analysis of historical mysteries

Author(s):  
Howell G.M. Edwards
Author(s):  
Elizabeth A. Carter ◽  
Fernando Rull Perez ◽  
Jesús Medina Garcia ◽  
Howell G. M. Edwards

Raman spectroscopy has been used to study fragments of early Visigothic historiated manuscripts from the important mediaeval library at Santo Domingo de Silos which were a part of a Beato dating from the tenth to the mid-eleventh centuries. These fragments are from some of the oldest manuscripts in the scriptorium of the monastery. In this study, a comparison is made between the pigments and inks used on these manuscripts and those used in a previous study of the unique Visigothic Beato de Valcavado in Santa Cruz, Valladolid, completed in the year 970, which is noted for its quality of execution as well as its content and is remarkable eschatologically in being identifiable as the complete work of only a single scribe. For comparative purposes, the pigments and inks used in the Silos Monastery Beato and a series of historiated early manuscripts from mediaeval times through to the Renaissance also held in the monastic library were analysed. Raman spectroscopy identified a range of mineral and organic pigments such as cinnabar, orpiment, minium, azurite and indigo. In addition, a number of admixtures were found, for example, indigo and orpiment to produce vergaut (green) and a mixture of cinnabar with iron-gall ink and cerussite to produce darker and lighter shades of red. Some interesting conclusions were drawn about the use of iron-gall and carbon-based inks. This article is part of the themed issue ‘Raman spectroscopy in art and archaeology’.


Author(s):  
Howell G. M. Edwards ◽  
Dolores Elkin ◽  
Marta S. Maier

Specimens from underwater archaeological excavations have rarely been analysed by Raman spectroscopy probably due to the problems associated with the presence of water and the use of alternative techniques. The discovery of the remains of the Royal Navy warship HMS Swift off the coast of Patagonia, South America, which was wrecked in 1770 while undertaking a survey from its base in the Falkland/Malvinas Islands, has afforded the opportunity for a first-pass Raman spectroscopic study of the contents of several glass jars from a wooden chest, some of which had suffered deterioration of their contents owing to leakage through their stoppers. From the Raman spectroscopic data, it was possible to identify organic compounds such as anthraquinone and copal resin, which were empirically used as materia medica in the eighteenth century to treat shipboard diseases; it seems very likely, therefore, that the wooden chest belonged to the barber-surgeon on the ship. Spectra were obtained from the wet and desiccated samples, but several samples from containers that had leaked were found to contain only minerals, such as aragonite and sediment. This article is part of the themed issue ‘Raman spectroscopy in art and archaeology’.


2021 ◽  
Vol 8 (1) ◽  
pp. 12
Author(s):  
Francesco Niccoli ◽  
Mario D’Acunto

Over the last decade, Raman spectroscopy was demonstrated as a label-free and destructive optical spectroscopy that was able to improve diagnostic accuracy in cancer diagnosis. This ability is principally based on the great amount of biochemical information produced by the Raman scattering while investigating biological tissues. However, to achieve the relevant clinical requirements, the spectroscopic analysis and its ability to grade cancer tissues require sophisticated multivariate statistics. In this paper, we critically review multivariate statistics methods analyzed in light of their ability to process datasets generated by Raman spectroscopy in chondrogenic tumors, where distinguishing between enchondroma and the first grade of malignancy is a critical problem for pathologists.


Heritage ◽  
2020 ◽  
Vol 3 (4) ◽  
pp. 1148-1161
Author(s):  
Christopher Brooke ◽  
Howell Edwards ◽  
Peter Vandenabeele ◽  
Sylvia Lycke ◽  
Michelle Pepper

An organ case from Lincoln, England, designed by the architect Temple Moore in 1907 was examined during conservation work using Raman spectroscopy in order to analyze the decorative paint composition. Samples from the six principal colours were extracted and examined using a Bruker Senterra R200-L spectrometer. The results are the first known formal analysis of a painted scheme by this architect, and they reveal a mixture of commonly used pigments for the period and the unexpected use of simpler, earth pigments, along with an unusual admixture in the red, along with an organic additive. The findings are of importance to both the conservation of Temple Moore’s artwork, in understanding the experimentation used in early twentieth-century England, and in furthering our knowledge of ecclesiastical decorative artwork of the late nineteenth and early twentieth centuries.


2018 ◽  
Vol 11 ◽  
pp. 117954411775405 ◽  
Author(s):  
J Renwick Beattie ◽  
Diane Feskanich ◽  
M Clare Caraher ◽  
Mark R Towler

Studies have shown that Raman spectroscopic analysis of fingernail clippings can help differentiate between post-menopausal women who have and who have not suffered a fracture. However, all studies to date have been retrospective in nature, comparing the proteins in nails sourced from women, post-fracture. The objective of this study was to investigate the potential of a prospective test for hip fracture based on spectroscopic analysis of nail tissue. Archived toenail samples from post-menopausal women aged 50 to 63 years in the Nurses’ Health Study were obtained and analysed by Raman spectroscopy. Nails were matched case-controls sourced from 161 women; 82 who underwent a hip fracture up to 20 years after nail collection and 81 age-matched controls. A number of clinical risk factors (CRFs) from the Fracture Risk Assessment (FRAX) tool had been assessed at toenail collection. Using 80% of the spectra, models were developed for increasing time periods between nail collection and fracture. Scores were calculated from these models for the other 20% of the sample and the ability of the score to predict hip fracture was tested in model with and without the CRFs by comparing the odds ratios (ORs) per 1 SD increase in standardised predictive values. The Raman score successfully distinguished between hip fracture cases and controls. With only the score as a predictor, a statistically significant OR of 2.2 (95% confidence interval [CI]: 1.5-3.1) was found for hip fracture for up to 20 years after collection. The OR increased to 3.8 (2.6-5.4) when the CRFs were added to the model. For fractures limited to 13 years after collection, the OR was 6.3 (3.0-13.1) for the score alone. The test based on Raman spectroscopy has potential for identifying individuals who may suffer hip fractures several years in advance. Higher powered studies are required to evaluate the predictive capability of this test.


1973 ◽  
Vol 22 (1) ◽  
pp. 38-40 ◽  
Author(s):  
Tomas Hirschfeld ◽  
E.R. Schildkraut ◽  
Harvey Tannenbaum ◽  
David Tanenbaum

The Analyst ◽  
2016 ◽  
Vol 141 (21) ◽  
pp. 6104-6115 ◽  
Author(s):  
Di Yan ◽  
Christian Domes ◽  
Robert Domes ◽  
Timea Frosch ◽  
Jürgen Popp ◽  
...  

Fiber enhanced resonance Raman spectroscopy (FERS) is introduced for chemically selective and ultrasensitive analysis of the biomolecules hematin, hemoglobin, biliverdin, and bilirubin, as well as intact red blood cells.


2002 ◽  
Vol 56 (9) ◽  
pp. 1115-1121 ◽  
Author(s):  
Pei He ◽  
Shivashanker Bitla ◽  
Doug Bousfield ◽  
Carl P. Tripp

An overview of the use of Raman spectroscopy for compositional mapping of paper coatings is presented. Raman spectroscopy is able to give the spatial distribution of pigments and binders in coated papers containing kaolin, anatase, and styrene butadiene (SB). Moreover, there are subtle differences in the Raman spectra of two forms of calcite, ground (GCC) and precipitated calcium carbonate (PCC), and these differences can be used to monitor the spatial distribution of coatings containing mixtures of PCC and GCC. Surface compositional mapping is relatively straightforward and is demonstrated with measurements of SB/CaCO3 ratios in mottled regions in printed coatings and the measurement of the same pigment/binder ratio in both thin and thick coated regions. For depth profiling, microtome methods are preferred, whereas the data obtained using confocal-based methods do not work.


1997 ◽  
Vol 3 (S2) ◽  
pp. 951-952
Author(s):  
K. Siangchaew ◽  
D. Arayasantiparb ◽  
M. Libera

The spatially-resolved structure and composition of amorphous or semicrystalline polymer-polymer interfaces are poorly understood. The absence of atomic-level periodicity precludes many of the transmission electron-optical techniques that have been so fruitful in studying interfaces in polycrystalline inorganic materials. Similarly, there has been relatively little work done on spatially-resolved spectroscopic analysis of polymer-polymer interfaces to determine chemical widths, largely because of concerns over electron-beam damage. Digital microscope control and parallel spectral acquisition provide for low-dose exposure, quantification of dose, and efficient data collection which open new windows to study polymer interfaces.This research is studying various multiphase polymer systems by focused-probe spectroscopic analysis to identify appropriate spectral features, data acquisition protocols, and background-modeling/data-processing algorithms in order to establish chemical widths characteristic of specific polymer-polymer interfaces (1). This research uses a 200keV Philips CM20 FEG TEM/STEM with a Gatan 666 PEELS spectrometer and an Emispec digital data acquisition/control system.


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