RESUMEN
Fire is a major hazard for built heritage. The fire at Notre-Dame on April 15, 2019 completely destroyed the woodframe and the lead roof (about 285 tons) almost entirely melted due to high temperatures. A part of the molten lead escaped into the atmosphere in the form of aerosols while the majority remains within cathedral enclosure in the form of deposits, metallic remains, spatters etc. In particular unusual yellowish deposits of lead-rich particles were observed and collected inside the monument (in the nave, near the organ and in St-Eloi Chapel). These were then thoroughly characterized to identify the neoformed lead compounds. Both bulk and local analyses were carried out to obtain particle morphology and size distribution, chemistry and mineralogy of the deposits, from macro to nanoscale. We found that the fire-related deposits all contain high amount of lead (10 to 44 %) mainly in the form of monoxides (litharge and massicot) with other lead-bearing phases (Ca-plumbate, metallic lead, lead sulfates and carbonates, plattnerite) in smaller amount. These lead phases are concentrated in heterogeneous microspheres, at the periphery of terrigenous minerals (calcite, quartz, feldspars) or mixed with anhydrite minerals. The size distribution shows that the fire produced giant particles (> 100 µm in diameter) similar to those found near the fallout from industrial emissions. This study provides a better understanding of the lead contamination pathways following the Notre-Dame cathedral fire and new insights into the reactivity of lead during a fire.
RESUMEN
Nd-YAG QS laser cleaning of soiled stone at 1064 nm can sometimes result in a more yellow appearance compared to other cleaning techniques. Especially in France, this yellowing effect is still considered as a major aesthetic issue by the architects and conservators. One explanation states that the yellowing is linked to the formation of iron-rich nanophase(s) through the laser beam interaction with black crusts that would re-deposit on the cleaned substrate after irradiation. To characterize these nanophases, a model crust containing hematite was elaborated and laser irradiated using a Nd-YAG QS laser. The color of the sample shifted instantaneously from red to a bright yellow and numerous particles were ablated in a visible smoke. Transmission electron microscopy (TEM) was used to examine the morphology and the crystallinity of the neo-formed compounds, both on the surface of the samples and in the ablated materials. In addition, an investigation of the chemical and structural properties of the nanophases was conducted by X-ray dispersive energy (EDX) and electron energy loss (EELS) spectroscopies. It was found that both the surface of the sample and the ablated materials are covered by crystallized nano-spheres and nano-residues, all containing iron and oxygen, sometimes along with calcium and sulfur. In particular an interfacial area containing the four elements was evidenced between some nanostructures and the substrate. Magnetite Fe3O4 was also identified at the nanoscale. This study demonstrates that the laser yellowing of a model crust is linked to the presence of iron-rich nanophases including CaxFeySzOδ nanostructures and magnetite Fe3O4 at the surface after irradiation.
RESUMEN
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.