Abstract: Indoor and outdoor concentrations of atmospheric gaseous pollutants as well as composition, size, and morphology of particulate matter have been investigated at the monastery of San Jerónimo in Granada (Southern Spain). Complementary micro- and nano-analytical techniques were applied; elemental and mineralogical composition and morphological characteristics of particulate matter were investigated combining electron probe microanalysis at the single particle level, and bulk aerosol samples were analyzed using energy-dispersive X-ray fluorescence, X-ray diffraction, scanning electron microscopy with energy-dispersive X-ray analyzer and transmission electron microscopy (TEM). Microclimatic conditions at the monastery were monitored, and gas concentrations were assessed by means of diffusion tubes subsequently analyzed with ion chromatography. Results revealed high abundances of soil dust particles (aluminosilicates, calcite, dolomite, quartz), salt aerosols (chlorides, sulfates and ammonium-rich salts), and NO2 and SO2 both outdoors and indoors. Amorphous black carbon particles had surprisingly high abundances for Granada, a non-industrialized city. The composition of indoor particles corresponds to severe weathering affecting the construction materials and artworks inside the church; moreover their composition promotes a feedback process that intensifies the deterioration. Chemical reactions between chloride-rich salts and pigments from paintings were confirmed by TEM analyses. Indoors, blackening of surface decorative materials is fostered by particle re-suspension due to cleaning habits in the monastery (i.e. dusting). This is the first air quality study performed in a monument in the city of Granada with the aim of developing a strategy for preventive conservation.

Abstract: Since antiquity, the red pigment mercury sulfide (α-HgS), called cinnabar in its natural form or vermilion red when synthetic, was very often used in frescoes and paintings, even if it was known to suffer occasionally from degradation. The paint hereby acquires a black or silver-grey aspect. The chemical characterization of these alteration products is rather challenging mainly because of the micrometric size and heterogeneity of the surface layers that develop and that are responsible for the color change. Methods such as electron microscopy, synchrotron-based microscopic X-ray fluorescence, microscopic X-ray absorption near edge spectroscopy, Raman microscopy and secondary ion microscopy have been previously employed to identify the (Hg- and S-) compounds present and to study their co-localization. Next to these, also microscopic X-ray diffraction (XRD) (either by making use of laboratory X-ray sources or when used at a synchrotron facility) allows the identification of the crystal phases that are present in degraded HgS paint layers. In this paper we employ these various forms of micro-XRD to analyze degraded red paint in different paintings and compare the results with other X-ray based methods. Whereas the elemental analyses of the degradation products revealed, next to mercury and sulfur, the presence of chlorine, X-ray diffraction allowed the identification, next to α-HgS, of the Hg and S-containing compound calomel (Hg2Cl2) but also of the Hg, S and Cl-containing minerals corderoite (α-Hg3S2Cl2) and kenhsuite (γ-Hg3S2Cl2). These observations are consistent with X-ray absorption spectroscopy measurements performed at the S- and Cl-edges.

Abstract: Elemental distribution maps are of great interest in the study of historical paintings, as they allow to investigate the pigment use of the artist, to image changes made in the painting during or after its creation and in some cases to reveal discarded paintings that were later over painted. Yet a method that allows to record such maps of a broad range of elements in a fast, non-destructive and in situ manner is not yet commonly available; a dedicated mobile scanning XRF instrument might fill this gap. In this paper we present three self-built scanning macro-XRF instruments, each based on the experience gained with its precursor. These instruments are compared in terms of sensitivity and limits of detection, which includes a discussion of the use of polycapillary optics and pinhole collimators as beam defining devices. Furthermore, the imaging capabilities of the instruments are demonstrated in three exemplary cases: (parts of) historical paintings from the 15th to the 19th century are examined. These cases illustrate the value of element specific distribution maps in the study of historical paintings and allow in the case of Vincent van Gogh's Patch of Grass a direct comparison between in situ and synchrotron based scanning macro-XRF.

Abstract: Carboxylic acids and sodium carboxylates are used to protect metals against aqueous and atmospheric corrosion. In this paper, we describe the application of a layer of copper carboxylate on the surface of a copper electrode by means of cyclic voltammetry technique and tests which measure the corresponding resistance to aqueous corrosion. Unlike the soaking process, which also forms a film on the surface, the use of cyclic voltammetry allows one to follow the deposition process of the copper carboxylates onto the electrode. The modified electrodes have been characterised with infrared spectroscopy. In addition, the corrosion resistance of the film has been investigated using polarisation resistance and Tafel plot measurements.

Abstract: Many western manuscripts were written using iron gall inks. These inks can damage the paper via two major mechanisms: (a) acid hydrolysis, enhanced by humidity, and (b) oxidative depolymerization provoked by the presence of oxygen and free iron(II) ions. The degradation of unsized Whatman paper impregnated with different combinations of iron sulfate, gallic acid, and gum arabic was studied at room temperature in order to assess the relative importance of each mechanism. The samples were stored in various environments including a dry and/or an oxygen-free atmosphere. The cellulose depolymerization was monitored by viscometry and related to changes in the oxidation state of iron, determined by X-ray absorption near-edge spectrometry. The results indicate that residual amounts of oxygen (less than 0.1%) promote cellulose depolymerization, whereas the level of relative humidity has no impact. The cellulose depolymerization also appears closely correlated to oxidative mechanisms. Regarding the oxidation of iron, it only occurs in the simultaneous presence of oxygen and moisture, suggesting the occurrence of rustlike oxidative mechanisms. Finally, the presence of gallic acid has a strong influence, which is only partially explained by its capacity to reduce iron(III) to iron(II).

Abstract: The control of damage to individual environmental particles by a laser beam during Raman spectroscopy carried out in ambient air is generally well understood. The nature and control of damage under vacuum conditions (e.g. in the scanning electron microscopy with energy X-ray detection combined with micro-Raman spectroscopyinterfaced SEM-EDX/MRS) are more complex and less well comprehended. The physical and chemical processes that affect the damage caused to small particles by lasers still remain somewhat unclear, but certainly the atmosphere (vacuum/air) and the beam intensity have very significant influences. Furthermore, it has been determined that some particles (e.g. haematite), although stable under an electron beam, are damaged by the laser beam, hampering their analysis. Additionally, when simultaneous analyses by SEM/EDX and MRS are considered, the correct choice of the collection surface plays a crucial role. As a result, the following collection substrates were tested to determine their influence on the laser beam damage process to the particle: silver and aluminium foils and silicon wafers. A test study was performed using artificial examples of haematite (Fe2O3) particles. Exposure of Fe2O3 particles in vacuum to 514- and 785-nm laser radiation often leads to their melting, transformation and evaporation. The dependence of the damage caused by the laser beam on the particle structure is reported here. Molecular and crystallographic changes have also been revealed. Formation of magnetite (as an effect of re-crystallisation) and Raman inactive structures was detected.

Abstract: Co-adsorption of norfloxacin (Nor) and Cu(II) on montmorillonite at pH 4.5, 7.0 and 9.0 was studied by integrated batch adsorption experiments and extended X-ray absorption fine structure (EXAFS) spectroscopy. Under such pH conditions the dominant species of Nor are cation (Nor+), zwitterion (Nor±), and anion (Nor−), respectively. Results indicated that Nor sorption decreased with an increase of solution pH. The presence of Cu(II) slightly suppressed the Nor+ sorption at pH 4.5, while increased Nor± and Nor−sorption on montmorillonite at pH 7.0 and 9.0, respectively. In contrast, Nor increased Cu(II) adsorption at pH 4.5, but had little effect on the adsorption of Cu(II) on montmorillonite at pH 7.0 and 9.0. Spectroscopic results showed that, at pH 4.5, Nor+ was sorbed on montmorillonite by the formation of outer-sphere montmorilloniteNorCu(II) ternary surface complex. At pH 7.0, montmorilloniteNorCu(II) and montmorilloniteCu(II)Nor ternary surface complexes co-exist. At pH 9.0, montmorilloniteCu(II)Nor ternary surface complex was likely formed, which was different to Cu(II)(Nor)2 precipitate of the solution.

Abstract: Analytical chemistry does play a key role in the chemical characterization of the environment and it appears that X-ray spectrometry, in its many forms, is one of the most relevant analytical techniques in preventive conservation, as it is in cultural heritage research in general. X-ray spectrometry has indeed been the method of choice for the characterization of the inorganic composition of atmospheric aerosols, for a long time. We have, over the last decade, intensively used various forms of X-ray spectrometry, viz., mostly energy-dispersive X-ray fluorescence, e.g. with polarized high-energy beam excitation, and automated electron probe X-ray microanalysis, together with other techniques, to identify particle types and their sources in indoor environments, including museums, while gaseous indoor pollutants were assessed using passive diffusion samplers. In each case, both bulk aerosols and individual aerosol particles were studied. For microanalysis of single particles, we have investigated a dozen techniques, but for wide, real-life applications, automated electron probe X-ray microanalysis is the most rewarding. We have first studied atmospheric aerosols in and around the Correr Museum in Venice, many other museums in Austria, Japan and England, and in the caves with prehistoric rock paintings in Altamira, Spain. Very recently, measurements were done in the Metropolitan Museum of Art in New York and theWawel Castle in Cracow, in Italian and Polish mountain churches, in a number of museums in Belgium and the Netherlands, and in cathedrals with medieval stained glass windows. In the Correr museum, it appeared that the particles most threatening for the Bellini paintings were released by the deteriorating plaster renderings, and this could be avoided by simply improving the rendering on the museum walls. In the Wawel Castle, outdoor pollution particles, like fine soot from diesel traffic, entering via leaks in the windows and doors, and also street-deicing salts and coal burning pollution particles, brought in by visitors, mostly in winter, were found to be most worrisome. Urgent questions that are not solved at this moment pertain to the deposition processes from the atmosphere to the cultural heritage items, the critical surface interactions that take place on these items, and the establishment of suitable particle concentration standards.

Abstract: The application of micro-Raman spectroscopy is discussed for the analysis of structural features of human tooth tissues affected by high doses of external ionizing radiation (0.51.7 Gy) after the nuclear plant catastrophe in Chernobyl in 1986. The results have shown significant changes in the mineral matrix of dental enamel that lead to the decrease of tooth enamel hardness. Destruction of the collagen chain of the organic matrix has been observed for dentin and cementum.

Abstract: The main goal of this work was to determine the chemical composition of building materials used in Turkey by utilizing energy dispersive X-ray fluorescence (EDXRF) spectrometry. Gas concrete, cement, sand, bricks, roofing tiles, marble, lime and gypsum materials were selected as building materials for this research. The chemical contents and their trace concentrations of the selected samples were determined. The most abundant oxides measured were generally SiO2, Al2O3, CaO, MgO, Fe2O3, K2O and SO3 for all samples. While the main chemical component of gas concrete, cement, sand and marble samples were SiO2 and CaO, brick and roofing tile mainly consisted of SiO2 and Al2O3. CaO and SO3 were major component of lime and gypsum samples, respectively. For U and Th concentrations in the samples, activities of 226Ra and 232Th were measured by utilizing gamma spectrometry. ANOVA and Pearson correlation analyses were performed on the studied data for statistical analysis.