Protective performances of two anti-graffiti treatments towards sulfite and sulfate formation in SO2 polluted model environment

Specific strategies for protection are being developed to counter both the staining and corrosive effects of polluted air in cities, as well as to allow for efficient removal of unwanted graffiti paintings. These protection strategies employ molecules with tailored functionalities, e.g. being hydrophobic, while maintaining porosity for molecular water vapour permeation.The present study employs SO₂ and water to probe the behaviors of two anti-graffiti treatments, a water-base fluoroalkylsiloxane (“Protectosil Antigraffiti” marketed by Degussa) and an organically modified silicate (Ormosil) synthesized from a polymer chain (polydimethyl siloxane, PDMS) and two network forming alkoxides (Zr propoxide and methyl triethoxy silane, MTES) dissolved in n-propanol, on five building materials, comprising limestone, aged lime mortar, hydrated cement mortar, granite, and brick material.The materials were exposed to a synthetic atmosphere for 20 h in a climate chamber, 0.78 ± 0.03 ppm of SO₂ and 95% RH. Diffuse reflectance Fourier transform infrared (DR-FTIR) spectra were registered before and after exposure in the climate chamber in the cases of both treated and untreated samples. DR-FTIR, scanning electron microscope (SEM) images and energy dispersive X-ray (EDX) analyses, suggest the anti-graffiti Ormosil to suppress formation of calcium sulfite hemihydrate (the primary initial product of the reaction of calcium compounds with SO₂ and water) on carbonate materials (limestone and lime mortar).In case of the granite, brick and cement mortar, Ormosil has a negligible influence on the SO₂ capture. While no sulfite formation was detected by DR-FTIR, gypsum is inferred to form due to metal oxides and minority compounds catalysed oxidation of sulfite to sulfate. In case of brick, this understanding finds support from SEM images as well as EDX. A priori presence of gypsum in hydrated cement mortars prevents positive identification by SEM. However, support for sulfur accumulation in hydrated cement mortar is provided by means of EDX.In case of a second anti-graffiti considered, Protectosil, no influence of the anti-graffiti treatment on the SO₂ uptake of any of the building materials was observed.     

Performance of Pleurotus ostreatus Mushrooms and Spent Substrate for the Biosorption of Cd(II) From Aqueous Solution

The capacities of Pleurotus ostreatus mushroom and spent substrate were evaluated for the biosorption of cadmium (II) from aqueous solution in order to select the most efficient material for bioremediation. The optimum sorption conditions were optimized, including the pH of the aqueous solution, contact time, biomass dosage, initial metal concentration, and temperature. The sorption of cadmium on both biosorbents was also evaluated by several kinetic, equilibrium, and thermodynamic models. The possible heavy metal biosorption mechanisms were evaluated through point of zero charge (pH_pzc), Fourier-transform infrared (FTIR) spectroscopy and scanning electron microscopy coupled with energy dispersive X-ray microanalysis (SEM-EDX). Based on the results of column studies, the effectiveness of the P. ostreatus spent substrate was confirmed as a biosorbent for Cd(II) removal from aqueous solutions.     

Sequestration of Aqueous Lead(II) Using Modified and Unmodified Red Onion Skin

The efficacy of onion skins, both unmodified and chemically modified with thioglycolic acid, was investigated as alternative low-cost adsorbents for the sequestration of aqueous lead(II) ions from aqueous solution. The adsorbents were characterised using Fourier transform infrared spectroscopy and scanning electron microscopy – energy dispersive X-ray spectroscopy. Adsorption experiments were performed using batch sorption processes. The effects of contact time, pH, initial Pb(II) concentration, adsorbent dose, and temperature were investigated. Optimum sorption conditions were found at pH 4 and a 150?min equilibrium time for the modified onion skin and unmodified onion skin. The Langmuir, Freundlich, Dubinin-Radushkevich and Temkin models were used to characterize the equilibrium experimental results. The equilibrium process was best described by the Freundlich isotherm. The maximum adsorption capacities of 4.878 and 6.173?mg/g were obtained for modified and unmodified adsorbents, respectively, using the Langmuir model. Kinetic studies indicated that the sorption of Pb(II) ions followed a pseudo-second-order model. Thermodynamic parameters such as standard enthalpy change (ΔH°), entropy change (ΔS°), and free energy change (ΔG°) were evaluated from the sorption experimental measurements. The results showed that the sorption process of Pb(II) ions on unmodified and modified onion skins was feasible and exothermic under the conditions used in this study. The sorption process followed the mechanism of physisorption.     

Analytical investigation of calcium oxalate films on marble monuments

This paper describes an analytical approach to investigate the origin of oxalate films on marble. Calcium oxalate films were collected on buildings of historical importance in Lucca and Pisa (Italy) and characterised by optical microscopy (OM), scanning electron microscopy-energy dispersive X-ray spectrometry (SEM-EDX), Fourier transform infrared (FTIR) spectroscopy (equipped with diamond cell), and gas chromatography-mass spectrometry (GC-MS). The morphology of the films was investigated by optical and electronic microscopy. FTIR analyses highlighted the presence of calcium oxalate (both as whewellite and weddellite), gypsum, calcite, nitrates, silicates and apatite, while EDX maps showed the distribution of elements. Several samples showed traces of organic compounds, identified by GC-MS as paraffin wax, lipids of animal origin and egg. The correlation between organic material and oxalate contents suggests the origin of the films from degradation processes of past surface treatment.     

Large‐Area Elemental Imaging Reveals Van Eyck's Original Paint Layers on the Ghent Altarpiece (1432), Rescoping Its Conservation Treatment

A combination of large‐scale and micro‐scale elemental imaging, yielding elemental distribution maps obtained by, respectively non‐invasive macroscopic X‐ray fluorescence (MA‐XRF) and by secondary electron microscopy/energy dispersive X‐ray analysis (SEM‐EDX) and synchrotron radiation‐based micro‐XRF (SR μ‐XRF) imaging was employed to reorient and optimize the conservation strategy of van Eyck's renowned Ghent Altarpiece. By exploiting the penetrative properties of X‐rays together with the elemental specificity offered by XRF, it was possible to visualize the original paint layers by van Eyck hidden below the overpainted surface and to simultaneously assess their condition. The distribution of the high‐energy Pb‐L and Hg‐L emission lines revealed the exact location of hidden paint losses, while Fe‐K maps demonstrated how and where these lacunae were filled‐up using an iron‐containing material. The chemical maps nourished the scholarly debate on the overpaint removal with objective, chemical arguments, leading to the decision to remove all skillfully applied overpaints, hitherto interpreted as work by van Eyck. MA‐XRF was also employed for monitoring the removal of the overpaint during the treatment phase. To gather complementary information on the in‐depth layer build‐up, SEM‐EDX and SR μ‐XRF imaging was used on paint cross sections to record micro‐scale elemental maps.     

垃圾焚烧飞灰颗粒的微观形态特征及能谱研究

利用SEM/EDX，观察了垃圾焚烧飞灰颗粒的微观形态特征，探讨了其主要组成元素及其质量分数。实验结果表明，飞灰颗粒形态多样化，其中以不规则形状聚合体居多，球形体、絮状集合体相对较少，少数颗粒为棒状集合体。球形飞灰颗粒很少有重金属分布，不规则形状聚合体或絮状集合体的表面易分布重金属。从飞灰颗粒表面、内部组成元素的质量分数来看，Si、Ca、Al为主要元素。飞灰颗粒表面、内部有重金属Pb、Cu等分布，局部测定点其质量分数可高达16.2%和14.5%。     

SEM-EDX study of the crystal structure of the condensed combustion products of the aluminum nanopowder burned in air under the different pressures

The experimental results of combustion of aluminum nanopowder (ANP) in air and AlN crystals formation process were studied. The air pressure during the combustion process significantly affected the crystals growth mechanism. Crystals with the different morphology (whiskers, hexagonal crystals, rods) were found in the condensed combustion products.     

Compositional analysis of Tuscan glass samples: in search of raw material fingerprints

SEM-EDX quantitative analyses were performed on 91 samples of vessel glass originating from a number of sites throughout Tuscany. A comparison with Venetian glass data is made in order to evaluate differences in glassmaking materials. The compositions of the samples provide clues about the different raw materials used in relation to recipes that changed slightly during the period covering the late Middle Ages to early Renaissance. Two kinds of ash used as a fluxing agent were identified, one of which is of east Mediterranean origin while the other is likely to be Spanish. Two types of silica sources were also found. One of these was recognized as being quartziferous river pebbles, while the other is proposed to be local sand.     

Characterization of Green Paints in Ming and Qianlong Dynasties’ Lin’xi Pavilion by Complimentary Techniques

During conservation of the painted ceiling decoration of Lin’xi Pavilion in the Forbidden City, two distinct paint campaigns were isolated as a unique case study into architectural paint materials during both the Ming and Qing dynasties. Paint samples and cross sections from both paint generations were analyzed with SEM-EDX, time of flight-secondary ion mass spectrometry (ToF-SIMS), XRD, FTIR, and Raman spectroscopies. Similar organic and inorganic materials characteristic of these time periods were identified. The pigments of interest found in both paint generations were botallackite and atacamite polymorphs. This suggests a shift from natural mineral sources to synthetic copper-based pigments for these larger architectural projects.