Non-invasive and non-destructive micro-XRF and micro-Raman analysis of a decorative wallpaper from the beginning of the 19th century

Non-destructive and non-invasive micro-Raman fibre optic and micro-XRF analyses were performed to study a wallpaper from the beginning of the 19th century. The complementarity of these two non-destructive techniques is shown in this work. The analysed artwork is considered one of the most beautiful wallpapers ever manufactured according to the catalogues and books; it is known as Chasse de Compiègne, manufactured by Jacquemart, Paris, in 1812. During the analysis, an unexpected pigment was detected by both analytical techniques: lead-tin yellow type II. This pigment was used until ca. 1750, when other yellow pigments replaced it, thus it is very difficult to find it in paintings afterwards. Together with this pigment, red lead, Prussian blue, brochantite, yellow iron oxide, calcium carbonate, vermilion, carbon black of animal origin (bone black), lead white, and raw and burnt sienna were also determined by combining the analytical information provided by both techniques. A possible degradation of brochantite to antlerite is also discussed.     

Raman spectroscopic analysis of human remains from a seventh century cist burial on Anglesey,UK

Specimens from human remains exhibiting unusual preservation excavated from a seventh century stone cist burial at Towyn y Capel in Anglesey, UK, have been analysed using Raman spectroscopy with near-infrared laser excitation at 1,064 and 785 nm. Specimens of hair and bone provided evidence for severe degradation and microbial colonisation. The deposits within the stone cist showed that some microbially mediated compounds had been formed. Analysis of crystals found at the interface between the hair and the skeletal neck vertebrae revealed a mixture of newberyite and haematite, associated with decomposition products of the hair and bone. An interesting differential degradation was noted in the specimens analysed which could be related to the air-void and the presence of plant root inclusions into the stone cist. This is the first time that Raman spectroscopy has been used in the forensic archaeological evaluation of burial remains in complex and dynamic environments.     

Analysis by raman spectroscopy and XRF of glass beads from excavations in the harbor area of rio de janeiro,Brazil

In this paper, nine beads from excavations in the Valongo Wharf, located in the harbor area of Rio de Janeiro, Brazil that were utilized as ornaments by Africans and Afrodescendants during the 19th century were analyzed by Raman and X-Ray Fluorescence (XRF) spectroscopy. All samples in the analysis showed Raman spectra with two bands of maximum intensity around 1000 and 500 cm⁻¹ related to the maximum stretching (ν_max) and bending mode (δ), respectively, of the tetrahedral network of the SiO₄ present in the glass matrix. However, there is variation in the intensity and position of the bands that are directly associated with the burning process and the raw material utilized in the manufacture of the beads. Based on the polymerization index (I_p = A₅₀₀/A₁₀₀₀), it is possible to relate these two parameters. By establishing a correlation among the I_p and the ν_max band, the beads were classified into groups. The results reveal that the beads’ base paste exhibits differences, allowing their classification into groups according to the manufacturing process. Based on the combination of the elemental characterization and Raman spectroscopy results, it was also possible to conclude that European and Asian countries are the possible origins of the beads.     

Analysis of a coloured Dutch map from the eighteenth century: the need for a multi-analytical spectroscopic approach using portable instrumentation

A Dutch map from the eighteenth century was multi-analytically analysed making use of energy dispersive X-ray fluorescence (EDXRF), Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR), Raman and scanning electron microscopy coupled to energy dispersive spectrometry (SEM-EDS). The cellulosic support was characterised and its state of conservation was evaluated. Besides, paramagnetic impurities were detected together with copper metallic chips. The colours present in some areas of the map were also analysed. Vermilion, carbon black and organic pigments were found. Surprisingly, in the green areas, the rare presence of the mineral moolooite (copper oxalate) was detected. A possible biological attack is discussed in order to explain the presence of such compound. Almost all of the techniques used in the analysis were portable, non-destructive and non-invasive, which is very desirable when analysing objects belonging to Cultural Heritage. The need for a multi-analytical approach using portable instrumentation is also discussed.     

Determination of P/Al ratio in phosphorus-doped aluminium oxide thin films by XRF,RBS and FTIR

Phosphorus-doped aluminium oxide thin films were deposited in a flow-type ALE reactor from AlCl₃, H₂O and from either P₂O₅ or trimethyl-phosphate. Structural information of the films was obtained from Fourier transform infrared (FTIR) spectra. Rutherford backscattering spectroscopy (RBS) was used to quantitatively determine the composition of the films. The P/Al intensity ratios calculated from X-ray fluorescence (XRF) results were in a linear relation with the P/Al concentration ratios calculated from RBS results. For comparison, the intensity ratios of the phosphorus peak (P=O) at about 1250 cm^–1 and the aluminium peak (Al-O) at about 950 cm^–1 were determined from the IR absorption spectra. The calibration of FTIR peak intensities was done by plotting the intensity ratios of phosphorus and aluminium peaks against the P/Al concentration ratios measured by RBS. FTIR gave also a linear calibration curve with RBS but the method is less suitable for routine analysis of P/Al ratio than XRF.     

An extensive colour palette in Roman villas in Burgos,Northern Spain: a Raman spectroscopic analysis

Seventy-five specimens from thirty fragments of Roman villa wall-paintings from sites in Burgos Castilla y Leon, Spain, have been analysed by Raman spectroscopy. This is the first time that a Raman spectrocopic study of Roman wall-paintings from Spain has been reported. The extensive range of tonalities and colour compositions contrasts with the results found in other provinces of the Roman Empire, for example Romano-British villas. Calcite, aragonite, haematite, caput mortuum, cinnabar, limonite, goethite, cuprorivaite, lazurite, green earth, carbon and verdigris have been found as pigments. Some mineral mixtures with different tonalities have been made using different strategies to those more usually found. Of particular interest is the assignation of the Tarna mine for the origin of the cinnabar used for obtaining the red colour in some specimens analysed here. The wide range of colours, tonalities and minerals found in some of the sites studied in this work is suggestive of a high social status for the community.     

DFT studies of the structure, vibrational and NMR spectra of 2-amino-pyridine betaine monohydrate

Four of the most stable conformers of 2-amino-pyridine betaine (1-carboxymethyl-2-amino-pyridinium inner salt) monohydrates, 2-NH₂PB·H₂O, and one anhydrous were analyzed by the B3LYP/6-31G(d,p) calculations and compared with the X-ray data. Two types of optimized conformers can be distinguished: (a) with NH₂ and COO groups and (b) an imino tautomer with NH and COOH groups. A common feature of the optimized molecules are intramolecular hydrogen bonds between the COO⁻ and H₂N or COOH and HN groups. In the crystal both NH₂ and COO groups participate in intermolecular hydrogen bonds. The probable assignments of the anharmonic experimental solid state vibrational frequencies of 2-NH₂PB·H₂O and 2-ND₂PB·D₂O (conformer 2) based on the calculated B3LYP/6-31G(d,p) harmonic frequencies have been made. Correlations between experimental chemical shifts for 2-NH₂PB, its hydrochloride and 1-carboxyethyl-2-amino-pyridinium inner salt (¹³C and ¹H in D₂O) and GIAO/B3LYP/6-31G(d,p) calculated isotropic shielding constants, δ_exp=a+bσ_calc, are reported. Good linear regression between experimental and theoretical results for ¹³C was obtained. Only in 2-NH₂PB the hydrogen at -position is outside the linear correlation.     

Role of hydration in the phase transition of polypeptides investigated by NMR and Raman spectroscopy

NMR, Raman spectroscopy and ab initio quantum-chemical calculations have been employed to investigate the role of the hydration water in the inverse temperature transition of elastin-derived biopolymers represented by poly(Gly-Val-Gly-Val-Pro) and poly(Ala-Val-Gly-Val-Pro). Temperature and concentration dependences of the Raman spectra measured for water solutions of polymers and of a low-molecular-weight model have been correlated with the vibrational frequencies calculated at the DFT (B3LYP) and MP2 levels for the peptide segment surrounded by a growing number of water molecules. The results indicate strong hydration before the transition that, in addition to water hydrogen-bonded to amide groups, includes hydrophobic hydration of non-polar groups by a dynamic cluster of several water molecules. According to ¹H longitudinal and transverse relaxation of HOD signals in D₂O solutions, the number of water molecules motionally correlated with the polymer is about 4 per one amino acid residue.     

Studies of wall painting fragments from Kaiping Diaolou by SEM/EDX, micro Raman and FT-IR spectroscopy

The multi-technique analytical approach has proved to be a very effective tool for the analysis of artwork, as demonstrated by various studies. In this work, four micro-analysis methods were used to analyze the wall painting fragments in Kaiping Diaolou, a world cultural heritage enlisted in 2007. Field-emission scanning electron microscopy (FE-SEM), energy dispersive X-ray micro-analysis (EDX), combined with micro Raman and Fourier transform infrared (FT-IR) spectroscopy, provided a vast amount of information concerning the raw materials present in the pigments, organic binder, plasters and mortars of the wall painting. Four types of pigments (goethite, lazurite, chromium green and calcite) were identified on the surface layer of the wall paintings. The substrate under the pigment layer was found to be composed of cubic-like calcite (CaCO₃), micro-rod bundle-shaped syngenite (K₂Ca(SO₄)₂·H₂O), gypsum (CaSO₄·2H₂O) and silica (SiO₂). The organic binder can be attributed to animal glue (such as egg) and drying oil by micro FT-IR spectroscopy. These analysis results can provide important information for the conservation and restoration of the Kaiping Diaolou.     

FT-IR, Raman and NMR Spectra, Molecular Geometry, Vibrational Assignments, ab initio and Density Functional Theory Calculations for Diethyl Phthalate

Phthalate acid esters (PAEs) possess endocrine disruptive effects and can produce reproductive and developmental toxicities. In this paper, both experimental and theoretical studies on FT-IR, Raman and 1H NMR spectra of diethyl phthalate (DEP) have been carried out. The geometrical structure of DEP was optimized at the HF/6-31G*, HF/6-311G**, B3LYP/6-31G*, and B3LYP/6-311G** levels, respectively. The harmonic vibrational frequencies, IR intensity, Raman activity and 1H NMR chemical shifts have been computed at the B3LYP/6-31G* and B3LYP/6-311G** levels. Anharmonic corrections to frequencies were obtained by means of second-order perturbation theory (PT2) at the B3LYP/6-31G* level. Based on potential energy distribution (PED), the vibrational assignments have also been performed. The theoretical calculation values were compared with the experimental observations and the results indicate they are in excellent agreement.     

In situ analysis of mediaeval wall paintings: a challenge for mobile Raman spectroscopy

Raman spectroscopy is an analytical technique, which is gaining attention as a molecular technique for the investigation of objects of art. Especially the non-destructive properties of the method make this application suitable for the in situ analysis of artefacts. However, although using mobile, fibre optics Raman instrumentation for this type of research seems to be straightforward, some practical obstacles may hamper the investigation. In this paper, pitfalls and solutions are described when applying a dedicated spectrometer to the analysis of mediaeval wall paintings. It is shown how some practical problems may be overcome, and the results of the analysis are presented. Although the mediaeval wall paintings from the chapel of the castle of Ponthoz are well-preserved, still some interesting degradation phenomena could be observed: the identification of a black degradation product, likely to be meta-cinnabar, a degradation product of the red pigment vermilion (HgS); the formation of gypsum (CaSO₄·2H₂O) as a weathering product of calcium carbonate (CaCO₃); the observation of copper(II)hydroxychlorides.     

Experimental and theoretical IR,Raman, NMR spectra of 2‐, 3‐, and 4‐nitrobenzoic acids

The influence of the position of nitro group toward the carboxylic group on the vibration structure of the molecule was estimated. Optimized geometrical structures were calculated (HF, B3PW91, B3LYP). Experimental and theoretical FT‐IR, FT‐Raman, and nuclear magnetic resonance (NMR) spectra of the title compounds were recorded and analyzed. The most important vibrational bands of nitro and carboxyl groups and the benzene ring were assigned. Wavenumbers and intensities for the three acids studied were compared and discussed. Data of chemical shifts in ¹H and ¹³C NMR spectra of 2‐, 3‐, and 4‐nitrobenzoic acids were analyzed in comparison with benzoic acid molecule. The calculated parameters are compared with experimental characteristics of these molecules. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

Direct determination of the concentration dependence of diffusivities using combined model-based Raman and NMR experiments

Diffusion in liquids can still be predicted only with high uncertainty due to a lack of sufficient experimental data. Diffusion experiments are complex and time-consuming. Furthermore, the determination of the concentration dependence of the diffusion coefficients requires usually several experiments even for binary mixtures. A powerful model identification framework based on two fast experimental techniques is presented here. Raman inter-diffusion experiments in combination with a novel incremental identification technique establish the concentration dependence directly from the data without requiring a priori specification of the model structure. In regions where this technique is sensitive to error noise, it is complemented with NMR intra-diffusion measurements. Models describing the concentration dependence are identified in two steps. Based on the combined data suitable model candidates are proposed and initialized through basic curve fitting in the first identification step. A statistically sound dynamic optimization step yields the final model parameters. The methodology is exemplarily used to determine the diffusion coefficient in the mixture ethyl acetate–cyclohexane in the full concentration space.     

1H NMR及Raman光谱法研究十二烷基甜菜碱缔合体系的微观结构

采用＾１ＨＮＭＲ法研究了十二烷基甜菜碱,苯甲醇,水形成胶束的微观结构,推测苯甲醇在胶束中的增溶位置,发现在由Ｏ／Ｗ向Ｗ／Ｏ型的转变过程中存在过渡结构,其分子排列有序,光学上呈向向同性,称之为拟液晶结构。     

Characterization of Japanese color sticks by energy dispersive X-ray fluorescence,X-ray diffraction and Fourier transform infrared analysis

This work comprises the use of energy dispersive X-ray fluorescence (EDXRF), X-ray diffraction (XRD) and Fourier transformed infrared (FTIR) techniques for the study of the composition of twentieth century traditional Japanese color sticks. By using the combination of analytical techniques it was possible to obtain information on inorganic and organic pigments, binders and fillers present in the sticks. The colorant materials identified in the sticks were zinc and titanium white, chrome yellow, yellow and red ochre, vermillion, alizarin, indigo, Prussian and synthetic ultramarine blue. The results also showed that calcite and barite were used as inorganic mineral fillers while Arabic gum was the medium used. EDXRF offered great potential for such investigations since it allowed the identification of the elements present in the sample preserving its integrity. However, this information alone was not enough to clearly identify some of the materials in study and therefore it was necessary to use XRD and FTIR techniques.     

Vibrational spectra, NMR and theoretical studies of the enantiomers and rotamers of alpha-cypermethrin

NMR, infrared and Raman vibrational spectra of alpha-cypermethrin have been measured at room temperature. Infrared spectra were also recorded to low temperature. The spectra were analyzed by means of ab initio calculations. The conformational space of both enantiomers and some rotamers A, B and C of alpha-cypermethrin has been scanned using molecular dynamics and complemented with functional density calculations that optimize the geometry of the lowest-energy conformers of each species as obtained in the simulations. The vibrational frequencies and the 1H and 13C NMR chemical shifts were assigned using functional density calculations. The molecular electrostatic potential maps were obtained and analyzed.     

Cepaic acid, a novel yellow xanthylium pigment from the dried outer scales of the yellow onion Allium cepa

Cepaic acid was isolated as a novel xanthylium yellow pigment from the dried outer scales of the yellow onion Allium cepa Linne. Its structure was elucidated on the basis of ESI-MS and 2D NMR spectroscopy as a 9-carboxy-1,3,6,8-tetrahydroxyxanthylium, which suggests that cepaic acid and other yellow pigments in the dried outer skin of onion were formed by the nucleophilic reaction of phloroglucinol derived from quercetin, a flavonol in onion scales, by autoxidation to glyoxylic acid. To our knowledge, this is the first report of such a pigment in yellow onion.     

Multilevel profiling and identification of Dalbergia odorifera and Dalbergia stevensonii by FTIR,NMR and GC/MS

Chemical differences of the extractives revealed by FTIR methods can be further confirmed by ¹H NMR and ¹³C NMR. Meanwhile, the volatile compounds in the extractives can be identified by GC/MS     

XRF study of archaeological and metallurgical material from an ancient copper-smelting site near Ein-Yahav, Israel

A movable XRF instrument (a bench-top designed machine modified to work in the field for archaeological purposes) was used for analysis of artifacts and sediments during the field study (01–07 April 2003) of a small copper-smelting site in the Negev (about 30 km west of the Feinan complex of ancient copper mines and smelting sites in Jordan). The site consists of a relatively small hill with blackened slopes, covered mainly by crushed copper slag. The surface collection of datable objects (i.e. pottery shards and stone tools) indicated that the site had functioned at the end of the Early Bronze Age and during the Roman/Byzantine time.

The analysis of Cu concentration in the ash and in the ground as well as the analysis of ore and slag, were used as markers for the identification of the operation centers and for locating the remains of the smelting devices used at the end of the Early Bronze Age for smelting copper. The ore in use typically contained 35–45% Cu, up to 1% Mn and up to several percent Fe. The slag contained 13–20% Mn and 1–5% Cu and Fe. From these results we are able to estimate the Cu production scale during the first and most active period on this site, at the end of the Early Bronze Age.     

高岭石结构缺陷的 1H MAS NMR和Raman研究

The structure default of kaolinites was characterized with ¹H MAS NMR and Raman spectra. Although the HI indexes of Suzhou and Maoming kaolinite are similar, their ¹H MAS NMR and Raman spectra are very different. ¹H MAS NMR showed that the hydroxyl proton chemical shifts of Suzhou kaolinite are in the higher field and with larger different between the inner surface hydroxyls protons and inner hydroxyls proton chemical shifts than Maoming kaolinite. Raman spectra showed that the surface hydroxyls stretching vibration bands of Suzhou kaolinite are in the high frequency region, and the half height widths of the bands are 7.0～14 cm^-1. The area ratio S_z/(S_z+S_A), where S_Z and S_A are the areas of bands 3685 cm^-1 and 3695 cm^-1 respectively, is 0.23. But the surface hydroxyls stretching vibration bands of Maoming kaolinite are in the low frequency region, and the half height widths of the bands are 8.9～15.1 cm^-1. The area ratio S_z/(S_z+S_A) is 0.77. Those data proved that Suzhou kaolinite has lower structure default than Maoming kaolinite and ¹H MAS NMR and Raman spectra are effective method for study of kaolinite structure default.