Dual isotope system analysis of lead white in artworks.

Isotopic studies are gaining much interest in heritage science, as they can provide insight into a material's age and provenance. Radiocarbon (14C) dating affords a time frame for the materials being studied, thus providing a historical context, whereas the specific pattern of lead isotope ratios may be used to set geographical constraints on the source of the original materials. Both methods require invasive sampling from the object, and henceforth limits their respective application. With the focus on lead white paint (2PbCO3·Pb(OH)2), in this study we extract the time of production of the pigment from the carbonate anion by radiocarbon dating while its origin is traced by lead isotope analysis on the cation. The methodology was applied to 12 British and 8 Swiss paintings from the 18th to 20th century, with known dates and provenance. The 14C analysis of the lead white in combination with the organic binder and canvas alone places all objects between the 17th and 20th centuries, which is in agreement with their signed date, wheras the lead isotope analysis of all samples are consistent with lead ores from European deposits. In most of the cases the combined results are consistent with the art historical data and prove that isotope analysis is intrinsic to the object. This feasibility study conducted on paintings of known age demonstrates the possibility to maximize the information output from lead white paint, thus increasing the benefits of a single sampling.

Using illusions to understand hallucinations: differences in perceptual performances on illusory figures may underscore specific visuoperceptual impairments in Parkinson's disease.

Visual hallucinations are prevalent, potentially disabling symptoms of Parkinson's Disease. Multiple impairments in bottom-up sensory processing and top-down perceptual modulation are implicated in the pathophysiology of these phenomena. In healthy individuals, visual illusions are elicited by illusory figures through parametric manipulations of geometrical configurations, contrast, color, or spatial relationships between stimuli. These illusory percepts provide insight on the physiologic processes subserving conscious and unconscious perception. In this exploratory, cross-sectional, controlled study, perceptual performance on illusory figures was assessed on 11 PD patients with hallucinations, 10 non-hallucinating PD patients, and 10 age-matched healthy individuals. In order to characterize potential neural substrates of perceptual performances, patients' brain metabolic patterns on FDG PET were also analyzed. Illusions relying on attentional modulation and global perception were attenuated in PD patients without hallucinations. This pattern was no longer recognizable in hallucinating patients. Conversely, illusory effects normally counteracted by figure to background segregation and overlapping figures recognition were enhanced in PD patients with hallucinations. FDG PET findings further suggest that perceptual differences between PD patients might be linked to abnormal top-down perceptual modulation.

Evaluation of an alternative biotreatment for the extraction of harmful iron and sulfur species from waterlogged wood.

An innovative bioextraction method was tested and compared to common chemical extraction for the preservation of waterlogged archeological wood (WAW) artifacts. During burial, WAW artifacts accumulate iron and sulfur species forming iron sulfides. These compounds are harmless in the burial environment, where the oxygen content is low. But upon excavation, the WAW undergoes the oxidation of these compounds, and thus, irreversible physical and chemical damages occur. Fresh and archeological oak and pine samples were selected as representative species of WAW artifacts. Fresh samples were previously artificially contaminated to ascertain the presence of iron and sulfur. Thiobacillus denitrificans and natural iron chelators, called siderophores, were investigated to extract iron and sulfur as a 2-step biological treatment (BT) and compared to sodium persulfate-EDTA as chemical treatment (CT). Consolidation and freeze-drying were performed on the samples after BT and CT as traditional conservation protocols. BT and CT efficiency was evaluated through Raman, inductively coupled plasma-optical emission (ICP-OES), and Fourier transformed infrared (FTIR) spectroscopies. Raman and ICP showed that most of the iron and sulfur was extracted after BT, while some sulfur species remained present on CT samples. None of the extraction methods resulted in a degradation of the wood, as ascertained by FTIR analyses. Yet, all samples presented visual modifications after conservation. Pine samples treated with BT illustrated the oxidation of the species. Present principal component analysis (PCA) and analysis of variance (ANOVA) which were selected as statistical approaches and validated BT as a promising alternative extraction method, with encouraging extraction rates and less alteration of the sample appearance.

Investigation of Biogenic Passivating Layers on Corroded Iron.

This study evaluates mechanisms of biogenic mineral formation induced by bacterial iron reduction for the stabilization of corroded iron. As an example, the Desulfitobacterium hafniense strain TCE1 was employed to treat corroded coupons presenting urban natural atmospheric corrosion, and spectroscopic investigations were performed on the samples' cross-sections to evaluate the corrosion stratigraphy. The treated samples presented a protective continuous layer of iron phosphates (vivianite Fe2+3(PO4)2·8H2O and barbosalite Fe2+Fe3+2(PO4)2(OH)2), which covered 92% of the surface and was associated with a decrease in the thickness of the original corrosion layer. The results allow us to better understand the conversion of reactive corrosion products into stable biogenic minerals, as well as to identify important criteria for the design of a green alternative treatment for the stabilization of corroded iron.

Early stage of weathering of medieval-like potash-lime model glass: evaluation of key factors.

PURPOSE: Throughout history, a consequent part of the medieval stained glass windows have been lost, mostly because of deliberate or accidental mechanic destruction during war or revolution, but, in some cases, did not withstand the test of time simply because of their low durability. Indeed, the glasses that remain nowadays are for many in a poor state of conservation and are heavily deteriorated. Under general exposure conditions, stained glass windows undergo different kinds of weathering processes that modify their optical properties, chemistry, and structure: congruent dissolution, leaching, and particle deposition (the combination of those two leading together to the formation of neocrystallisations and eventually crusts). Previous research has studied the weathering forms and the mechanisms from which they are originated, some others identified the main environmental parameters responsible for the deterioration and highlighted that both intrinsic (glass composition) and extrinsic (environmental parameters) factors influence glass degradation. Nevertheless, a clear quantification of the impact of the different deterioration extrinsic factors has not been performed. METHODS: By analysing the results obtained with model glass (durable and nondurable) exposed in the field, this paper proposes a simple mathematical computation evaluating the contribution of the different weathering factors for the early stages of exposure of the stained glasses. RESULTS: In the case of non durable glass, water runoff was identified as the main factor inducing the leaching (83.4 ± 2.6% contribution), followed by gas (6.4 ± 1.5%) and particle deposition (6.8 ± 2.2%) and adsorbed water (3.4 ± 0.6%). Moreover, it was shown that the extrinsic stimuli superimposes with the impact of glass composition to the weathering. CONCLUSIONS: Those results show that the role played by dry deposition, even if less important than that of the wet deposition, cannot be neglected.

Wet and dry atmospheric deposition on TiO(2) coated glass.

To prevent the soiling of glass window used in the built environment, the use TiO(2) coated products appears an important application matter. To test the cleaning efficiency and the sustainability of self-cleaning glass, a field experiment was conducted under real life condition, on a site representative of the background urban pollution. Samples of float glass, used as reference, and commercialized TiO(2) coated glasses were exposed to dry and wet atmospheric deposition during two years. The crossed optical, chemical and microscopic evaluations performed, after withdrawal, allowed highlighting a sensible difference between the reference and the self-cleaning substrate in terms of accumulation, nature, abundance and geometry of the deposit. This experiment conducted in real site emphasized on the efficacy of self-cleaning glass to reduce the maintenance cost.