Physicochemical characteristics of calcined MnFe2O4 solid nanospheres and their catalytic activity to oxidize para-nitrophenol with peroxymonosulfate and n-C7 asphaltenes with air.

Manganese ferrite solid nanospheres (MSNs) were prepared by a solvothermal method and calcined at various temperatures up to 500 °C. Their surface area, morphology, particle size, weight change during calcination, surface coordination number of metal ions, oxidation state, crystal structure, crystallite size, and magnetic properties were studied. The MSNs were used as catalysts to activate potassium peroxymonosulfate (PMS) for the oxidative degradation of para-nitrophenol (PNP) from water and for the oxidation of n-C7 asphaltenes in flowing air at atmospheric (0.084 MPa) and high pressure (6 MPa). Mn was in oxidation states (II) and (III) at calcination temperature of 200 °C, and the crystalline structure corresponded to jacobsite. Mn was in oxidation states (III) and (IV) at 350 °C and in oxidation states (II), (III), and (IV) at 500 °C, and the crystalline structure was maghemite at both temperatures. MSN catalysts generated hydroxyl (HO·) and sulfate (SO4·-) radicals in the PMS activation and generated HO· radicals in the n-C7 asphaltene oxidation. In both reactions, the best catalyst was MSN calcined at 350 °C (MSN350), because it has the highest concentration of Mn(III) in octahedral B sites, which are directly exposed to the catalyst surface, and the largest total and lattice oxygen contents, favoring oxygen mobility for Mn redox cycles. The MSN350 sample reduces the decomposition temperature of n-C7 asphaltenes from 430 to 210 °C at 0.084 MPa and from 370 to 200 °C at 6.0 MPa. In addition, it reduces the effective activation energy by approximately 77.6% in the second combustion (SC) region, where high-temperature oxidation reactions take place.

Effect of calcination temperature of a copper ferrite synthesized by a sol-gel method on its structural characteristics and performance as Fenton catalyst to remove gallic acid from water.

A copper ferrite synthesized by a sol-gel combustion method was calcined at different temperatures up to 800°C, determining changes in its structural characteristics and magnetic measurements and studying its catalytic performance in gallic acid removal by Fenton reaction. The main objective was to study the effect of the calcination temperature of copper ferrite on its crystalline phase formation and transformation, activity and metal ion leaching. The cubic-to-tetragonal transformation of the spinel occurred via its reaction with the CuO phase, displacing Fe3+ ions in B (octahedral) sites out of the spinel structure by the following reaction: 2Fe3+B+3CuO→Fe2O3+3Cu2+B. The catalysts showed superparamagnetic or substantial superparamagnetic behaviour. At higher calcination temperatures, catalyst activity was lower, and Cu ion leaching was markedly decreased. There was no Fe ion leaching with any catalyst. The as-prepared catalyst showed better catalytic performance than a commercial copper ferrite. Leached Cu ions acted as homogeneous catalysts, and their contribution to the overall removal mechanism was examined. Cu2O present in the as-prepared catalysts made only a small contribution to their activity. Finally, the reutilization of various catalysts was studied by performing different catalytic cycles.

Contribution of the microbial communities detected on an oil painting on canvas to its biodeterioration.

In this study, we investigated the microbial community (bacteria and fungi) colonising an oil painting on canvas, which showed visible signs of biodeterioration. A combined strategy, comprising culture-dependent and -independent techniques, was selected. The results derived from the two techniques were disparate. Most of the isolated bacterial strains belonged to related species of the phylum Firmicutes, as Bacillus sp. and Paenisporosarcina sp., whereas the majority of the non-cultivable members of the bacterial community were shown to be related to species of the phylum Proteobacteria, as Stenotrophomonas sp. Fungal communities also showed discrepancies: the isolated fungal strains belonged to different genera of the order Eurotiales, as Penicillium and Eurotium, and the non-cultivable belonged to species of the order Pleosporales and Saccharomycetales. The cultivable microorganisms, which exhibited enzymatic activities related to the deterioration processes, were selected to evaluate their biodeteriorative potential on canvas paintings; namely Arthrobacter sp. as the representative bacterium and Penicillium sp. as the representative fungus. With this aim, a sample taken from the painting studied in this work was examined to determine the stratigraphic sequence of its cross-section. From this information, "mock paintings," simulating the structure of the original painting, were prepared, inoculated with the selected bacterial and fungal strains, and subsequently examined by micro-Fourier Transform Infrared spectroscopy, in order to determine their potential susceptibility to microbial degradation. The FTIR-spectra revealed that neither Arthrobacter sp. nor Penicillium sp. alone, were able to induce chemical changes on the various materials used to prepare "mock paintings." Only when inoculated together, could a synergistic effect on the FTIR-spectra be observed, in the form of a variation in band position on the spectrum.

Black soiling of an architectural limestone during two-year term exposure to urban air in the city of Granada (S Spain).

A two-year term aging test was carried out on a building limestone under different urban conditions in the city of Granada (Southern Spain) to assess its Cultural Heritage sustainability. For this purpose stone tablets were placed vertically at four sites with contrasting local pollution micro-environments and exposure conditions (rain-sheltered and unsheltered). The back (rain-sheltered) and the front (rain-unsheltered) faces of the stone tablets were studied for each site. The soiling process (surface blackening) was monitored through lightness (ΔL*) and chroma changes (ΔC*). Additionally atmospheric particles deposited on the stone surfaces and on PM10 filters during the exposure time were studied through a multianalytical approach including scanning electron microscopy (SEM-EDX), transmission electron microscopy (TEM) and micro-Raman spectroscopy. The identified atmospheric particles (responsible for stone soiling) were mainly soot and soil dust particles; also fly ash and aged salt particles were found. The soiling process was related to surface texture, exposure conditions and proximity to dense traffic streets. On the front faces of all stones, black soiling and surface roughness promoted by differential erosion between micritic and sparitic calcite were noticed. Moreover, it was found that surface roughness enhanced a feedback process that triggers further black soiling. The calculated effective area coverage (EAC) by light absorbing dust ranged from 10.2 to 20.4%, exceeding by far the established value of 2% EAC (limit perceptible to the human eye). Soiling coefficients (SC) were estimated based on square-root and bounded exponential fittings. Estimated black carbon (BC) concentration resulted in relatively similar SC for all studied sites and thus predicts the soiling process better than using particulate matter (PM10) concentration.

High dietary intake of retinol leads to bone marrow hypoxia and diaphyseal endosteal mineralization in rats.

Vitamin A (retinol) is the only molecule known to induce spontaneous fractures in laboratory animals and we have identified retinol as a risk factor for fracture in humans. Since subsequent observational studies in humans and old animal data both show that high retinol intake appears to only have small effects on bone mineral density (BMD) we undertook a mechanistic study of how excess retinol reduces bone diameter while leaving BMD essentially unaffected. We fed growing rats high doses of retinol for only 1 week. Bone analysis involved antibody-based methods, histology, pQCT, biomechanics and bone compartment-specific PCR together with Fourier Transform Infrared Spectroscopy of bone mineral. Excess dietary retinol induced weakening of bones with little apparent effect on BMD. Periosteal osteoclasts increased but unexpectedly endosteal osteoclasts disappeared and there was a reduction of osteoclastic serum markers. There was also a lack of capillary erythrocytes, endothelial cells and serum retinol transport protein in the endosteal/marrow compartment. A further indication of reduced endosteal/marrow blood flow was the increased expression of hypoxia-associated genes. Also, in contrast to the inhibitory effects in vitro, the marrow of retinol-treated rats showed increased expression of osteogenic genes. Finally, we show that hypervitaminotic bones have a higher degree of mineralization, which is in line with biomechanical data of preserved stiffness in spite of thinner bones. Together these novel findings suggest that a rapid primary effect of excess retinol on bone tissue is the impairment of endosteal/marrow blood flow leading to hypoxia and pathological endosteal mineralization.