K X-ray fluorescence cross-sections for some light elements excited by keV photons

K and K X-ray fluorescence cross-sections have been experimentally determined for the elements Cu, Se, Y, and Mo at excitation energies 23.62, 24.68, 36.82, 43.95, 48.60, and 50.20keV using an X-ray tube with a secondary exciter system as the excitation source. The X-ray tube with a secondary target arrangement was used to obtain high intensity with high degree of monochromatization. Experimental values were compared with the theoretical values using tabulated I ratios based on Hartree-Fock and Hartree-Slater theories calculated by Scofield. The experimental values for all the elements at various excitation energies are in good agreement with the theoretical values.     

Composition of the black crusts from the Saint Denis Basilica, France, as revealed by gas chromatography-mass spectrometry

The organic fraction of black crusts from Saint Denis Basilica, France, is composed of a complex mixture of aliphatic and aromatic compounds. These compounds were studied by two different analytical approaches: tetramethyl ammonium hydroxide (TMAH) thermochemolysis in combination with gas chromatography-mass spectrometry (GC-MS), and solvent extraction, fractionation by silica column, and identification of the fraction components by GC-MS. The first approach, feasible at the microscale level, is able to supply fairly general information on a wide range of compounds. Using the second approach, we were able to separate the complex mixture of compounds into four fractions, enabling a better identification of the extractable compounds. These compounds belong to different classes: aliphatic hydrocarbons (nalkanes, n-alkenes), aliphatic and aromatic carboxylic acids (n-fatty acids, alpha,omega-dicarboxylic acids, and benzenecarboxylic acids), polycyclic aromatic hydrocarbons (PAH), and molecular biomarkers (isoprenoid hydrocarbons, diterpenoids, and triterpenoids). With each approach, similar classes of compounds were identified, although TMAH thermochemolysis failed to identify compounds present at low concentrations in black crusts. The two proposed methodological approaches are complementary, particularly in the study of polar fractions.     

The laser-induced discoloration of stonework; a comparative study on its origins and remedies

For understanding the phenomena associated with the discoloration observed in some cases of infrared laser cleaned stonework surfaces, a comparative study of three different types and morphologies of pollution encrustation and stone substrates was undertaken. Fragments originating from monuments with historic and/or artistic value, bearing homogeneous thin soiling on Pentelic marble (Athens, Greece), thick encrustation on Hontoria limestone (Burgos, Spain) and compact thin crust on gypsum decorations (Athens, Greece), have been studied on the basis of their composition and origin, together with the conditions that may induce yellowing effects upon their laser cleaning with IR wavelengths. While irradiation in the UV (i.e. at 355 nm) could not effectively remove the encrustations studied, irradiation at 1,064 nm was found efficient to remove all the studied pollution accumulations. Discoloration towards yellow was evident in all cases and at different levels, including the samples with intentional patination layer. To the limit of Raman detection no chemical alterations were detected on the irradiated areas while the presence of yellow polar compounds in all the pollution crusts studied supports the argument that the discoloration of the stone surfaces upon their IR irradiation may be due to the uncovering of existing yellow layers as result of the migration of these compounds inwards to the original stone surface. To correct and/or prevent such undesired coloration the use of IR and UV radiation both in sequential and synchronous mode was considered, with positive results.     

Thickness and composition of gold and silver alloys determined by combining EDXRF‐analysis and transmission measurements

Energy‐dispersive X‐ray fluorescence (EDXRF)‐analysis is a technique which in the case of metals analyzes thin surface layers. For example, when gold and silver alloys are analyzed, it typically interests a depth of microns up to a maximum of tens of microns. Therefore, it can give wrong results or be affected by a large indetermination when the sample composition is altered because of surface processes, as often happens when silver alloys are oxidated, and sometimes in the case of gold alloys rich on copper or silver. A complementary technique was therefore developed, of bulk analysis, which uses the same equipment employed for EDXRF‐analysis; the X‐ray beam from the X‐ray tube is monochromatized by means of a tin secondary target, which K lines bracket the silver‐K discontinuity. The sample to be analyzed is positioned between the secondary target and the detector. This technique is able to determine (by measuring the attenuation of tin‐K rays) thickness and/or composition of gold and silver alloys having a thickness of less than about 120 µm for gold and about 0.7 mm for silver. The method was tested with Au–Ag–Cu alloys of known composition and thickness and then applied to gold and silver artifacts from the tomb of the Lady of Cao, which belongs to the Moche pre‐hispanic culture from the North of Peru, and dates about 300 A.D. Copyright © 2014 John Wiley & Sons, Ltd.     

Multilayered artifacts in the pre-Columbian metallurgy from the North of Peru

Three types of alloys were recognized when analyzing pre-Columbian artifacts from the North of Peru: gold, silver, and copper alloys; gilded copper and silver; silvered copper; tumbaga, i.e., copper or silver enriched on gold at the surface by depletion gilding. In this paper, a method is described to differentiate gold alloys from gilded copper and from copper–gold tumbaga, and silver alloys from silvered copper and copper–silver tumbaga. This method is based on the use of energy-dispersive X-ray fluorescence, i.e., on a sophisticated analysis of XRF-spectra carrying out an accurate determination of Cu(K _α /K _β ), Ag(K _α /K _β ), Au(L _α /L _β ), and Au-L _α /Cu-K _α or Ag-K _α /Cu-K _α ratios. That implies a dedicated software for the quantitative determination of the area of X-ray peaks. This method was first checked by a relevant number of standard samples and then it was applied to pre-Columbian alloys from the North of Peru.     

The nature of black stains in Lascaux Cave,France, as revealed by surface‐enhanced Raman spectroscopy

We used surface‐enhanced Raman spectroscopy to investigate the chemical composition of the black stains threatening the rock‐art paintings of Lascaux Cave, Montignac, France. The stains are mainly composed of melanin from the fungus Ochroconis sp. and the faecal pellets of the collembolan Folsomia candida. Surface‐enhanced Raman spectroscopy is a useful technique for revealing the structure of unknown macromolecules in cultural heritage research. Copyright © 2011 John Wiley & Sons, Ltd.     

Biomedical applications of energy dispersive X-ray fluorescence

An X-ray fluorescence method for in vitro analysis of trace elements in biological samples is presented. The method is characterised by the use of an X-ray tube with secondary targets as a monoenergetic radiation source, and by thin specimens. The method has been applied to the analysis of blood serum samples, gunshot residue and urinary calculi.     

Microbial diversity in biodeteriorated monuments as studied by denaturing gradient gel electrophoresis

Studies of the microorganisms living on cultural assets and their potential damaging effects begin with an understanding of the microbial diversity present in such samples. Recently, molecular techniques have started to attract considerable interest since they do not require the culture of microorganisms in order to detect their presence. The basic protocol followed during microbial diversity analysis on cultural heritage assets utilizes electrophoretic techniques for separating highly homologous sequences. At present, Denaturing Gradient Gel Electrophoresis (DGGE) is the most frequently reported technique for separating DNA fragments during microbial diversity studies of art objects. In this report, we describe DGGE profiling techniques, show the most common applications, and present some examples of their use in microbial diversity studies on cultural heritage.     

Analysis of Pre-Columbian objetcs from Cupisnique, one of the oldest culture from Perú, using a portable X-ray fluorescence equipment

Cupisnique (2000–200 BC) is one of the first complex societies that developed in the Jetequepeque valley in the “Formative period.” It includes several settlements: Puémape on the coast, Limoncarro in middle valley, Montegrande and Tembladera in the upper valley, and Kuntur Wasi in San Pablo. Currently the valley comprises two provinces, Pacasmayo and Chepen in the La Libertad region, north of Lima. Consideration should be given to cupisniques as premetallurgical culture, and the only used metal was gold, which is present in the native state, on the soil surface or shallow, and attracted attention because of color, brightness, weight, ductility, and inalterability. We analyzed three Cupisnique metal objects belonging to the Larco Museum of Lima designated with No. 4 (pectoral), No. 7 (pendant), and No. 12 (bracelet), using a portable energy-dispersive X-ray fluorescence equipment. Mean value for the pectoral were Au (62 %), Ag (23 %), Cu (15 %); for the pendant, Au (81 %), Ag (16.5 %), Cu (2.5 %); and for the bracelet, Au (69.1 %), Ag (20 %), and Cu (10.9 %).