The use of Raman microscopy and laser desorption ionization mass spectrometry in the examination of synthetic organic pigments in modern works of art

Synthetic organic pigments are widely used in modern and contemporary works of art. They have been examined by a variety of techniques including spectroscopic methods such as Fourier transform infrared spectroscopy, Raman, and X‐ray powder diffraction as well as chromatographic or mass spectrometric techniques such as pyrolysis‐gas chromatography/mass spectrometry and laser desorption ionization mass spectrometry (LDI–MS). Often, a combination of techniques has been used to examine these pigments. This paper describes use of Raman spectroscopy to create a database of colorants including two pigments not previously reported, PO1 and PO2. Then, using Raman spectroscopy in combination with LDI–MS, samples from modern works of art by artists including Mark Rothko, Barnett Newman, and José de Rivera were examined in order to identify the pigments present. One finding was that Rothko used a variety of red pigments over the course of his career including PR11 which has not been previously reported in artwork, and PO2 found with its positional isomer PR1. Knowledge of the colorants serves to inform conservators about display and treatment decisions. Published 2014. This article is a U.S. Government work and is in the public domain in the USA.     

Analysis of mural paintings using in situ non‐invasive XRF,FTIR spectroscopy and optical microscopy

An analytical protocol consisting of X‐ray fluorescence spectroscopy, optical microscopy and Fourier transform infrared spectroscopy was used to study the origin and the nature of the materials (pigments, binders and coating preparation) of the Fundenii Doamnei church mural paint from Bucharest. The main interest of the present study consisted in the original votive paint from narthex, painted in 1757 in a secco technique. During analysis, an unexpected pigment in the votive paint could be detected by the combined analytical techniques: ultramarine blue. Along with this pigment, the presence of gypsum binder based on egg and flax seed oil could also be evidenced. These results demonstrated a secco execution technique of the votive paint and also the presence of a restoration treatment. Moreover, during the present study, the components of the preparation layer and the constitutive pigments from both 1699 and 1757 years mural paints have been analyzed. Hence, the following pigments could be identified: vermilion, azurite, cinnabar, lead white, ochre, natural umber and gold, by using the combination of the analytical techniques. The novelty of our results consists in detecting the composition of the materials used in this church painting (fresco and a secco) during these 254 years since its first restoration. The results of these investigations pointed to the suitability of the non‐destructive and semi‐destructive analytical techniques in the complex characterization of the paints realized in different techniques, at different periods. Copyright © 2013 John Wiley & Sons, Ltd.     

Correction for the effect of soil moisture on in situ XRF analysis using low‐energy background

X‐ray fluorescence (XRF) analyses are affected by many matrix and geometrical factors that, generally, are possible to handle in laboratory conditions. However, when in situ analyses are considered, constraints in the measurement conditions make more difficult to handle some factors, such as moisture, affecting the measurement accuracy. Efforts have been made to correct some of the effects by inserting some steps in the sample preparation process. The problem is that each step added in this process, aiming a better precision and accuracy, makes the in situ measurement harder and longer to accomplish, influencing negatively the intrinsic advantages of the in situ measurement. In this work, we propose a method to correct the effect of soil moisture on in situ XRF analysis using low‐energy background. The method demands a simple calibration, after which a long drying procedure is not necessary before measuring the samples. Copyright © 2012 John Wiley & Sons, Ltd.     

SR XRF Analysis for studying plants in an area of geological heterogeneity

X-ray fluorescence analysis using synchrotron radiation is applied to determine the elemental composition in the leaves of Pentaphylloides fruticosa (L.) O.Schwarz (bush cinquefoil) and Lonicera caerulea subsp. altaica ((Pall.) Gladkova) (blue honeysuckle) growing in a geologically active area. It is found that in the studied period, the total content of microelements increases in the Pentaphylloides fruticosa leaves in the area of geological heterogeneity than that in the control one, and on the contrary, it decreases in Lonicera caerulea. The relationship between Fe/Mn, Ca/Sr, Cu/Zn, and K/Rb ratios and the geochemical and geophysical features of the environment and element accumulation by different types of plants is established. It is noted that two types of bushes under study react differently to changes in the geochemical and geophysical characteristics of the environment.     

Influence of and correction for moisture in rocks,soils and sediments on in situ XRF analysis

This paper discusses the influence of water contained in rocks, soils and sediments on in situ XRF analysis with a portable XRF analyzer. Water in natural rocks, soil and sediments absorbs the characteristic x‐rays from the elements and also causes the primary radiation from the excitation sources to scatter, which results in a decrease in the intensity of characteristic x‐rays and an increase in the intensity of scattered x‐rays in a fluorescence spectrum. A method for correcting for the influence of the water on the analysis of wet samples is proposed, based on the fact that the intensity of scattered radiation is directly proportional to the water content of wet samples. Tests on a set of wet soil samples showed that the method can effectively correct for the influence of the water in wet samples up to a 20% water content. The method was also applied to the analysis of soil with an IED‐2000P XRF analyzer in a copper prospecting area in Yunnan, China. The results show satisfactory agreement of the results for Cu, Zn and Sr analyses before and after rain. Copyright © 2004 John Wiley & Sons, Ltd.     

The potential of UV femtosecond laser ablation for varnish removal in the restoration of painted works of art

Despite significant advances, laser ablation with nanosecond pulses presents limitations in dealing with the restoration of classes of painted works of art, such as paintings with a very thin layer of varnish. Femtosecond laser processing promises the means for overcoming such limitations. To this end, femtosecond ablation of two typical varnishes, dammar and mastic, is examined. For these varnishes, processing by Ti:Sapphire irradiation (800 nm) turns out to be ineffective. In contrast, irradiation with 248 nm ∼500 fs laser pulses results in a higher etching resolution (etching rates of ∼1 μm/pulse or less). For irradiation with few laser pulses at moderate laser fluences, etched morphology is far smoother than in the processing with nanosecond laser pulses. Furthermore, chemical modifications are considerably reduced (by nearly an order of magnitude), and exhibit a number of additional novel differences. Both etching rates and extent of chemical modifications are largely independent of varnish absorptivity. In all, femtosecond UV laser irradiation is indicated to hold a high potential, offering new perspectives for the restoration of painted works of art. Finally, a tentative model is advanced accounting in a consistent way for the observations.     

X-radiography of cultural heritage materials using handheld XRF spectrometers

This study investigated the feasibility, repeatability, and limitations of using handheld X-ray fluorescence spectrometers to perform radiography with thorough safety measures. Radiography is a well-established nondestructive technique commonly used in the field of cultural heritage preservation but not easily accessible to many. Equipped with X-ray generating tubes, handheld spectrometers could potentially assist performing radiographic tasks off-site due to their portability and increasing availability. These spectrometers are designed to work at close range within a limited voltage range and wattage, so the exposure settings should be modified for the spectrometers to generate big enough X-ray beams to irradiate the artifacts and enough radiation to penetrate through them to produce useful radiographs. Using a Bruker Tracer 5i, the effective beam spread angle, which was computed from several test shots, was used to determine the constant relation between the area of irradiation and the X-ray source to image-receptor distance. Based on inverse square law and the total wattage limitation of the spectrometer, current and exposure time were recalculated to produce informative radiographs. Because of the limitations of the tested spectrometer, this method is best applicable to an area smaller than 9 cm, with the scanning distance shorter than half a meter. The spectrometer cannot be used to radiograph materials that require higher voltage than it can produce.     

Raman spectroscopy of synthetic organic pigments used in 20th century works of art

Raman microscopy allows a non‐destructive characterisation of inorganic and organic painting materials such as pigments and organic dyestuffs. The objectives of this study are the more recent organic pigments typically present in paintings and other art works from the 20th century. More than 20 organic synthetic pigments from different chemical classes could be identified by Raman spectroscopy using different excitation wavelengths (457.9, 476.5, 487.9, 514.5, 632.8, and 1064 nm). To evaluate the performance for real paint samples, varying paint mixtures of the Hansa Yellow pigment PY 3 and the binding medium Mowilith, a polyvinyl acetate (PVAC) compound, were characterised; PY 3 was determined at a 1 wt% level in the binder. In addition, commercial tube paints containing the quinacridone violet PV 19 were studied. The pigment was clearly identified in all of these more complex oil and acrylic paints. Finally, alizarin (PR 83) and a green copper phthalocyanine pigment (PG 7) could unambiguously be identified by Raman microscopy in the painting ‘Woman with mandolin in yellow and red’ of Max Beckmann dating 1950. The discovery of a red naphthol AS pigment by Raman spectroscopy in a sample from the ‘Three field workers’ by Georg Baselitz (1964/1965) demonstrated that in some cases complementary chromatographic methods are needed for a comprehensive identification of the organic pigments. Copyright © 2008 John Wiley & Sons, Ltd.     

Assessing microscale heterogeneity in batches of reference materials using microbeam XRF

Principal component analysis (PCA), microbeam X‐ray fluorescence spectrometry (µXRF), and Monte Carlo simulations are used to illustrate a methodology for assessing the sample microheterogeneity for large sets of materials. PCA is demonstrated to determine a minimum sample size that can be used without concern that sample heterogeneity is contributing significantly to measurement uncertainty. Sampling methodology is critical for constructing an accurate PCA model of material heterogeneity, and the amount of data required is discussed using both empirical data and simulated data generated using a Monte Carlo approach. Random data collection is compared to rastering across a sample as typically done with microanalytical techniques. The use of random data collection is shown to reduce analysis time by one order of magnitude for some samples without significantly reducing the quality of data for estimating minimum sample size. Examples are shown for Standard Reference Material (SRM) 1635a Trace Elements in Coal (subbituminous) and SRM 1729 Tin Alloy (97Sn‐3Pb) with estimated minimum sample sizes of 2 mg and 640 µg, respectively. Published 2011. This article is a US Government work and is in the public domain in the USA.     

Study of a tabernacle with a remarkable architectural structure: In situ examination using Raman spectroscopy

In order to characterize ornamental stones and gemstones from the monstrance ‘Tabernáculo de la Colegiata de S. Pedro’ in Lerma, Burgos, a Raman spectroscopy in situ non‐destructive study has been performed on these materials. The Raman spectra obtained correspond to cornalline‐like chalcedony, nephrite jade, quartz veinlets, agates with moganite and jasper, together with goethite showing several degrees of alteration. Various types of marble and lapis lazuli were identified. The lapis lazuli samples show different Raman spectra depending on the blue–white chromatic gradient, due to the variations in the sulfur concentration. Raman spectroscopy allows for the correlation of the presence of radical molecular ions S₂⁻, S₃⁻ and SO₄²⁻, with the colour centres and colouration of lapis lazuli. Two varieties of marble are present, one of brown tones with greyish‐white incrustations and another with alternating white and black veinlets with yellow inclusions. In the former, white masses of microcrystalline calcite appear together with quartz inclusions, around which brown halos of goethite develop as an alteration product. In the latter, they show calcite in the white veinlets and calcite with graphite in the black ones. The mineralogical analysis of ornamentals stones on art objects allows determining their degree of conservation and the extension of the deterioration, in order to establish strategies for the cleaning and restoration. These results are an important factor to date the object and for shedding light about its authorship. Furthermore, it could eventually help to establish connections between the tabernacle‐monstrance and other tabernacles in Castilla y León. Copyright © 2013 John Wiley & Sons, Ltd.     

HERAS: A helium jet to prevent damage on works of art in Raman experiments

Raman spectroscopy is often used for non‐destructive analysis of works of art, polymers and biological materials, but in some cases, the laser beam can cause damages on the surface being studied due to the deposited beam energy. When possible, such damage can be prevented by minimizing laser intensity or acquisition time, but this is usually available only on high sensitivity bench‐top spectrometers. Portable Raman spectrometers are commonly not so flexible and an alternative is needed to ensure the safe study of sensitive works of art and other fragile materials. A helium jet aimed directly at the laser spot may prevent this damage from occurring and, in some cases, helps improving the Raman spectra. We designed a simple system (HERAS, Helium Raman System) consisting of a pinhole collimator, coupled to a helium line and a gas mass flux control and tested it on pyroxylin, vermilion and ochre paint references and pigment samples, using a 785 nm portable Raman spectrometer at various laser powers. Experimental conditions slightly differ for each sample, but small burns on the surface were avoided in all cases and only some ablation was observed on the most sensitive materials. The use of this coupled system allows the non‐destructive application of Raman to a wider variety of materials, while the technique remains portable. This setup may be used in bench‐top apparatus as well. Copyright © 2013 John Wiley & Sons, Ltd.     

The first in situ Raman spectroscopic study of San rock art in South Africa: procedures and preliminary results

Southern Africa has a rich heritage of hunter‐gatherer, herder and farmer rock art traditions made by using both painted and engraved techniques. Until now, there have been only a handful of studies on the chemical analysis of the paint, as all previous types of analysis required the removal of pigment samples from the sites a practice which has been avoided. Raman spectroscopy is an ideal techniques to analyse the paint non‐destructively and also offers the possibility of in situ work with portable instruments. This article describes the procedures and reports the preliminary results of the first in situ Raman spectroscopic study of rock art in South Africa (also a first worldwide), where we, first, evaluate the capability of a Raman portable instrument in very difficult conditions, second, analyse the paints in order to contribute to a better knowledge of the technology used and, third, evaluate the possible contribution of in situ analyses in conservation studies. The paintings from two different rock art sites were studied. The instrument proved to be highly suitable for in situ analyses in physically very challenging conditions. Most of the pigments and alteration products previously detected under laboratory conditions were identified, thereby giving information on both the pigments and conservation state of the paintings. A layered structure of alteration products and pigment was identified in situ for the first time by controlling the laser power, thereby obtaining the same results as in mapping experiments of cross sections of paint. Copyright © 2010 John Wiley & Sons, Ltd.     

Experimental assessment of effectively probed volume in confocal XRF spectrometry using microparticles

Current approaches for assessing a confocal micro-X-rayfluorescence–probing volume involve the use of sharp knife edges, thin films, or wires, which are moved through this volume. The fluorescence radiation excited in the material of the object is measured, and profiles are built to enable the determination of the full width at half maximum in any of the three axes of the excited volume. Such approaches do not provide information on the shape of the volume, and the consequent alignment of both used lenses is made based on the position of the maxima of the registered intensity measurements. The use of particles that are smaller than the interaction volume (isolated enough to prevent the influence of nearby particles) and translated through the interaction volume (3D scan) is presented as an alternative methodology to determine the confocal probing volume. Spherical shaped uranium particles with diameter of 1–3 μm originally produced for scanning electron microscopy analysis calibration purposes were used in this study. The results obtained showed that the effectively probed confocal volume has a distinct prolate spheroidal shape that is longer in the axis of the confocal detector than it is wide on the axes of the plane perpendicular to it. The diameter in the longest axis (tilted accordingly to the angle between the two silicon drift detectors) was found to be approximately 25 μm, whereas the shorter was found about 15 μm each, with a volume of about 3,000 μm³.     

The laser doppler vibrometer as an instrument for nonintrusive diagnostic of works of art: Application to fresco paintings

The purpose of this paper is to present the application of the Laser Doppler Vibrometer as a nonintrusive measurement instrument to detect shape and location of damage in fresco paintings. The paper discusses performance of the measurement instrument and outlines a measurement procedure capable of nonintrusive diagnostic of the state of conservation of works of art, based on frequency response analysis of wall surface vibration induced by acoustic excitation.The procedure for the measurement of wall surface vibration is described. A 2D map of surface vibration amplitude is produced by scanning the measurement point across the surface. This pseudo-image is then processed by image analysis techniques to determine the position and the shape of damaged areas. Experiments are performed on an artificial fresco with induced damage and on a real painting inside a church.     

X荧光分析仪中数字基线估计的研究

在数字化X荧光分析仪中,不稳定的基线电压,会直接影响到仪器的性能,造成能量分辨率下降。基于此,利用卡尔曼滤波算法,对数字化后的X射线荧光信号进行基线估计。由于现有的经典卡尔曼滤波、简化sage-husa和改进sage-husa算法模型进行基线滤波的效果都不佳,因此有必要对现有的算法进行改进和优化。提出双重遗忘法,建立新型的基于sage-husa自适应卡尔曼滤波算法模型。实验结果表明,利用该数学模型进行基线滤波,取得了很好的滤波效果。避免了滤波发散和基线收敛缓慢的问题,实现了脉冲基线恢复,提高了仪器的能量分辨率。     

Measurement of K-shell fluorescence yields for Br and I compounds using radioisotope XRF

K fluorescence yields were measured for I and Br compounds. The samples were excited by γ-rays produced by a Am-241 radioisotope source. The K X-rays emitted by the samples were counted using a Si(Li) detector with a resolution of at . Experimental results were compared with the theoretical values of Br and I elements.     

Assessing silicon deposits in Zilfi province,Saudi Arabia,using XRF and XRD techniques

The aim of this project is to create a geochemical database of the Nafud Desert in Zilfi Province, which lies 260 km northwest of Riyadh, capital of Saudi Arabia, and assess its potential as a silicon mine. The area of study was surveyed during December 2012 collecting 21 geological samples from 7 places (Alsabla, Almatal, Shlwan, Alaaga, Jaway, Magra and Althuare). Elemental composition was determined using X‐ray fluorescence spectrometry, while mineral content and crystallography analysis was performed using X‐ray diffraction. Analysis results revealed that silicon was abundant in the area, in fairly homogeneous amounts. Silica was found in concentrations of around 93% per sampled mass, and silicon concentrations were around 42%, in the surface layers down to the depth of 40 cm. Other elements (Al, K, Ca, Ti, Cr, Mn, Fe, Sr, Zr and Pd ) were present in very low concentrations, except for aluminium oxide, which was present in three areas (Jaway, Magra and Althuare) at concentrations around 5%, while Alsabla samples showed higher concentrations of CaO. Thus, according to the results, the Nafud Desert is a rich source of silicon that can be exploited very cheaply because of the presence of the raw material on the surface. Copyright © 2016 John Wiley & Sons, Ltd.     

白金制品的X射线荧光检验

应用含量归一原理，解决样品形状和大小不确定的问题，可用Ｘ射线荧光法直接测定白金制品成色。