Oxidative dehydrogenation of propane with N2O over Fe-ZSM-5 and Fe-SiO2: Influence of the iron species and acid sites

A series of iron containing zeolites with varying Si/Al ratios (11.5-140) and low iron content (similar to 0.9 wt.% Fe) have been synthesised by solid-state ion exchange with commercially available zeolites and tested, for the first time, in the oxidative dehydrogenation of propane (ODHP) with N2O. The samples were characterised by XRD, N-2-Adsorption, NH3-TPD and DR-UV-vis spectroscopy. The acidity of the Fe-ZSM-5 can be controlled by high temperature and steam treatments and Si/Al ratio. The selectivity and yield of propene were found to be the highest over Fe-ZSM-5 with low Al contents and reduced acidity. The initial propene yield over Fe-ZSM-5 was significantly higher than that of Fe-SiO2 since the presence of weak and/or medium acid sites together with oligonuclear iron species and iron oxides on the ZSM-5 are found to enhance the N2O activation. The coking of Fe-ZSM-5 catalysts could also be controlled by reduction of the surface acidity of ZSM-5 and by the use of O-2 in addition to N2O as the oxidant. Fe-ZSM-5 zeolites prepared with solid-state method have been shown to have comparable activity and better stability towards coking compared with Fe-ZSM-5 zeolites prepared by liquid ion exchange and hydrothermal synthesis methods. (C) 2012 Elsevier B.V. All rights reserved.

Age-Associated Changes of Brain Copper, Iron, and Zinc in Alzheimer's Disease and Dementia with Lewy Bodies

Disease-, age-, and gender-associated changes in brain copper, iron, and zinc were assessed in postmortem neocortical tissue (Brodmann area 7) from patients with moderate Alzheimer's disease (AD) (n = 14), severe AD (n = 28), dementia with Lewy bodies (n = 15), and normal age-matched control subjects (n = 26). Copper was lower (20%; p < 0.001) and iron higher (10–16%; p < 0.001) in severe AD compared with controls. Intriguingly significant Group*Age interactions were observed for both copper and iron, suggesting gradual age-associated decline of these metals in healthy non-cognitively impaired individuals. Zinc was unaffected in any disease pathologies and no age-associated changes were apparent. Age-associated changes in brain elements warrant further investigation.

Mineralogical Characteristics and Transformations during Long-Term Operation of a Zerovalent Iron Reactive Barrier

Design and operation of Fe⁰ permeable reactive barriers (PRBs) can be improved by understanding the long-term mineralogical transformations that occur within PRBs. Changes in mineral precipitates, cementation, and corrosion of Fe⁰ filings within an in situ pilot-scale PRB were examined after the first 30 months of operation and compared with results of a previous study of the PRB conducted 15 months earlier using X-ray diffraction and scanning electron microscopy employing energy dispersive X-ray and backscatter electron analyses. Iron (oxy)hydroxides, aragonite, and maghemite and/or magnetite occurred throughout the cores collected 30 mo after installation. Goethite, lepidocrocite, mackinawite, aragonite, calcite, and siderite were associated with oxidized and cemented areas, while green rusts were detected in more reduced zones. Basic differences from our last detailed investigation include (i) mackinawite crystallized from amorphous FeS, (ii) aragonite transformed into calcite, (iii) akaganeite transformed to goethite and lepidocrocite, (iv) iron (oxy)hydroxides and calcium and iron carbonate minerals increased, (v) cementation was greater in the more recent study, and (vi) oxidation, corrosion, and disintegration of Fe⁰ filings were greater, especially in cemented areas, in the more recent study. If the degree of corrosion and cementation that was observed from 15 to 30 mo after installation continues, certain portions of the PRB (i.e., up-gradient entrance of the ground water to the Fe⁰ section of the PRB) may last less than five more years, thus reducing the effectiveness of the PRB to mitigate contaminants.

Effect of Rapid Thermal Annealing on the Structure and Magnetic Properties of Chemical Vapour Deposition Cobalt Layers

Future read heads in hard disc storage require high conformal coatings of metal magnetic layers over high aspect ratio profiles. This paper describes pioneering work on the use of MOCVD for the deposition of cobalt layers. While pure cobalt layers could be deposited at 400C their magnetic properties are poor. It was found that the magnetic properties of the layers could be significantly enhanced with an optimised rapid thermal anneal. This work was sponsored by Seagate Technology and led to a follow up PhD studentship on the co-deposition of cobalt and iron by MOCVD.

Crossing forest thresholds: inertia and collapse in a Holocene sequence from south-central Spain

A Holocene palaeoecological sequence from Villaverde, south-central Spain, is presented. The pollen stratigraphy is used to infer past vegetation changes within a catchment area that represents the boundary between semi-arid, plateau and mountain vegetation. From c. 9700–7530 cal. yr BP, Pinus is dominant, probably as a result of a combination of a relatively dry climate and natural fire disturbance. From c. 7530–5900 cal. yr BP, moderate invasion by Quercus appears to be a migrational response following increased moisture and temperature, but in part shaped by competitive adjustments. From c. 5900–5000 cal. yr BP, the pine forests are replaced by deciduous-Quercus forests with an important contribution from Corylus, Betula, Fraxinus and Alnus. Mediterranean-type forests spread from c. 5000 to 1920 cal. yr BP coincident with expansions of Artemisia, Juniperus and other xerophytes. From c. 1920–1160 cal. yr BP, Pinus becomes dominant after a disturbance- mediated invasion of the oak forests. Human impact upon the regional landscape was negligible during the Neolithic, and limited in the Bronze and Iron Ages. Local deforestation and the expansion of agro-pastoral activities occur after c. 1600 cal. yr BP.

A proteomic analysis of thioacetamide-induced hepatotoxicity and cirrhosis in rat livers

Thioacetamide (TAA) administration is an established technique for generating rat models of liver fibrosis and cirrhosis. Oxidative stress is believed to be involved as TAA-induced liver fibrosis is initiated by thioacetamide S-oxide, which is derived from the biotransformation of TAA by the microsomal flavine-adenine dinucleotide (FAD)-containing monooxygense (FMO) and cytochrome P450 systems. A two-dimensional gel electrophoresis-mass spectrometry approach was applied to analyze the protein profiles of livers of rats administered with sublethal doses of TAA for 3, 6 and 10 weeks respectively. With this approach, 59 protein spots whose expression levels changed significantly upon TAA administration were identified, including three novel proteins. These proteins were then sorted according to their common biochemical properties and functions, so that pathways involved in the pathogenesis of rat liver fibrosis due to TAA-induced toxicity could be elucidated. As a result, it was found that TAA-administration down-regulated the enzymes of the primary metabolic pathways such as fatty acid beta-oxidation, branched chain amino acids and methionine breakdown. This phenomenon is suggestive of the depletion of succinyl-CoA which affects heme and iron metabolism. Up-regulated proteins, on the other hand, are related to oxidative stress and lipid peroxidation. Finally, these proteomics data and the data obtained from the scientific literature were integrated into an

An investigation into the effect of thickness of titanium dioxide and gold-silver nanoparticle titanium dioxide composite thin-films on photocatalytic activity and photo-induced oxygen production in a sacrificial system

Thin films of titanium dioxide and titanium dioxide with incorporated gold and silver nanoparticles were deposited onto glass microscope slides, steel and titanium foil coupons by two sol-gel dip-coating methods. The film's photocatalytic activity and ability to evolve oxygen in a sacrificial solution were assessed. It was found that photocatalytic activity increased with film thickness (from 50 to 500 nm thick samples) for the photocatalytic degradation of methylene blue in solution and resazurin redox dye in an intelligent ink dye deposited on the surface. Contrastingly, an optimum film thickness of similar to 200 nm for both composite and pure films of titanium dioxide was found for water oxidation, using persulfate (S2O82-) as a sacrificial electron acceptor. The nanoparticle composite films showed significantly higher activity in oxygen evolution studies compared with plain TiO2 films.

The lateritic profile of Balkouin, Burkina Faso: geochemistry, mineralogy and genesis

This study reports on the geochemical and mineralogical characterization of a lateritic profile cropping out in the Balkouin area, Central Burkina Faso, aimed at obtaining a better understanding of the processes responsible for the formation of the laterite itself and the constraints to its development. The lateritic profile rests on a Paleoproterozoic basement mostly composed of granodioritic rocks related to the Eburnean magmatic cycle passing upwards to saprolite and consists of four main composite horizons (bottom to top): kaolinite and clay-rich horizons, mottled laterite and iron-rich duricrust. In order to achieve such a goal, a multi-disciplinary analytical approach was adopted, which includes inductively coupled plasma (ICP) atomic emission and mass spectrometries (ICP-AES and ICP-MS respectively), X-ray powder diffraction (XRPD), scanning electron microscopy with energy dispersive spectrometry (SEM-EDS) and micro-Raman spectroscopy.

The geochemical data, and particularly the immobile elements distribution and REE patterns, show that the Balkouin laterite is the product of an in situ lateritization process that involved a strong depletion of the more soluble elements (K, Mg, Ca, Na, Rb, Sr and Ba) and an enrichment in Fe; Si was also removed, particularly in the uppermost horizons. All along the profile the change in composition is coupled with important changes in mineralogy. In particular, the saprolite is characterized by occurrence of abundant albitic plagioclase, quartz and nontronite; kaolinite is apparently absent. The transition to the overlying lateritic profile marks the breakdown of plagioclase and nontronite, thus allowing kaolinite to become one of the major components upwards, together with goethite and quartz. The upper part of the profile is strongly enriched in hematite (+ kaolinite). Ti oxides (at least in part as anatase) and apatite are typical accessory phases, while free aluminum hydroxides are notably absent. Mass change calculations emphasize the extent of the mass loss, which exceeds 50 wt% (and often 70 wt%) for almost all horizons; only Fe was significantly concentrated in the residual system.

The geochemical and mineralogical features suggest that the lateritic profile is the product of a continuous process that gradually developed from the bedrock upwards, in agreement with the Schellmann classic genetic model. The laterite formation must have occurred at low pH (? 4.5) and high Eh (? 0.4) values, i.e., under acidic and oxidizing environments, which allowed strongly selective leaching conditions. The lack of gibbsite and bohemite is in agreement with the compositional data: the occurrence of quartz (± amorphous silica) all along the profile was an inhibiting factor for the formation of free aluminum hydroxides.

Stability and performance enhancements of Electrokinetic-Fenton soil remediation

Electrokinetic process is a potential in situ soil remediation process which transports the contaminants via electromigration and electroosmosis. For organic compounds contaminated soil, Fenton’s reagent is utilized as a flushing agent in electrokinetic process (Electrokinetic-Fenton) so that removal of organic contaminants could be achieved by in situ oxidation/destruction. However, this process is not applied widely in industries as the stability issue for Fenton’s reagent is the main drawback. The aim of this mini review is to summarize the developments of Electrokinetic-Fenton process on enhancing the stability of Fenton’s reagent and process efficiency in past decades. Generally, the enhancements are conducted via four paths: (1) chemical stabilization to delay H2O2 decomposition, (2) increase of oxidant availability by monitoring injection method for Fenton’s reagent, (3) electrodes operation and iron catalysts and (4) operating conditions such as voltage gradient, electrolytes and H2O2 concentration. In addition, the types of soils and contaminants are also showing significant effect as the soil with low acid buffering capacity, adequate iron concentration, low organic matter content and low aromatic ring organic contaminants generally gives better efficiency.

Atmospheric pressure chemical vapour deposition of boron doped titanium dioxide for photocatalytic water reduction and oxidation

Boron-doped titanium dioxide (B-TiO) films were deposited by atmospheric pressure chemical vapour deposition of titanium(iv) chloride, ethyl acetate and tri-isopropyl borate on steel and fluorine-doped-tin oxide substrates at 500, 550 and 600 °C, respectively. The films were characterised using powder X-ray diffraction (PXRD), which showed anatase phase TiO at lower deposition temperatures (500 and 550 °C) and rutile at higher deposition temperatures (600 °C). X-ray photoelectron spectroscopy (XPS) showed a dopant level of 0.9 at% B in an O-substitutional position. The ability of the films to reduce water was tested in a sacrificial system using 365 nm UV light with an irradiance of 2 mW cm. Hydrogen production rates of B-TiO at 24 μL cm h far exceeded undoped TiO at 2.6 μL cm h. The B-TiO samples were also shown to be active for water oxidation in a sacrificial solution. Photocurrent density tests also revealed that B-doped samples performed better, with an earlier onset of photocurrent. © 2013 The Owner Societies.

Rationale for and implementation of age-neutral HRM in divergent institutional contexts–examples from Britain and Germany

Owing to demographic change as well as international and national pressures,
organisations will have to abandon oftentimes prevalent youth-centric HRM practices in favour of age-neutral HRM that is inclusive of the entire workforce, regardless of age. In order to do so, organisations turn to ‘best practice’ guides. These, however, do not tend to differentiate recommendations by country and/or sector. Based on research in eight case study organisations in the chemical, steel and retail sectors as well as in public schools in Germany and Britain, this chapter argues that the rationale for and the implementation of age-neutral HRM practices differ by national institutional and sectoral context as well as by the relative influence of social partners. Hence, organisations planning to implement age-neutral HRM should take organisational, institutional and sectoral peculiarities into account when doing so.

Transfusion and Treatment of severe anaemia in African children (TRACT): a study protocol for a randomised controlled trial

BACKGROUND: In sub-Saharan Africa, where infectious diseases and nutritional deficiencies are common, severe anaemia is a common cause of paediatric hospital admission, yet the evidence to support current treatment recommendations is limited. To avert overuse of blood products, the World Health Organisation advocates a conservative transfusion policy and recommends iron, folate and anti-helminthics at discharge. Outcomes are unsatisfactory with high rates of in-hospital mortality (9-10 %), 6-month mortality and relapse (6 %). A definitive trial to establish best transfusion and treatment strategies to prevent both early and delayed mortality and relapse is warranted.

METHODS/DESIGN: TRACT is a multicentre randomised controlled trial of 3954 children aged 2 months to 12 years admitted to hospital with severe anaemia (haemoglobin < 6 g/dl). Children will be enrolled over 2 years in 4 centres in Uganda and Malawi and followed for 6 months. The trial will simultaneously evaluate (in a factorial trial with a 3 x 2 x 2 design) 3 ways to reduce short-term and longer-term mortality and morbidity following admission to hospital with severe anaemia in African children. The trial will compare: (i) R1: liberal transfusion (30 ml/kg whole blood) versus conservative transfusion (20 ml/kg) versus no transfusion (control). The control is only for children with uncomplicated severe anaemia (haemoglobin 4-6 g/dl); (ii) R2: post-discharge multi-vitamin multi-mineral supplementation (including folate and iron) versus routine care (folate and iron) for 3 months; (iii) R3: post-discharge cotrimoxazole prophylaxis for 3 months versus no prophylaxis. All randomisations are open. Enrolment to the trial started September 2014 and is currently ongoing. Primary outcome is cumulative mortality to 4 weeks for the transfusion strategy comparisons, and to 6 months for the nutritional support/antibiotic prophylaxis comparisons. Secondary outcomes include mortality, morbidity (haematological correction, nutritional and infectious), safety and cost-effectiveness.

DISCUSSION: If confirmed by the trial, a cheap and widely available 'bundle' of effective interventions, directed at immediate and downstream consequences of severe anaemia, could lead to substantial reductions in mortality in a substantial number of African children hospitalised with severe anaemia every year, if widely implemented.

Oxidation and tensile behavior of ferritic/martensitic steels after exposure to lead-bismuth eutectic

Two ferritic/martensitic steels, T91 steel and newly developed SIMP steel, were subject to tensile test after being oxidized in the liquid lead-bismuth eutectic (LBE) at 873 K for 500 h, 1000 h and 2000 h. Tensile tests were also carried out on the steels only thermally aged at 873 K. The result shows that thermal aging has no effect. Exposure to LBE at 873 K leads to a slight decrease in strength, but a large decrease in elongation when tested at 873 K. When tested at 873 K after 2000 h exposure, the tensile strength of T91 decreases slightly, and elongation from 39% to 21%. For SIMP, the decreases are slightly and from 44% to 28%, for tensile strength and elongation, respectively. The room temperature strength has slightly larger percentage reductions after the LBE exposure, but the elongation changes little.

Detection of H2O and Evidence for TiO/VO in an Ultra-hot Exoplanet Atmosphere

We present a primary transit observation for the ultra-hot (T eq ~ 2400 K) gas giant expolanet WASP-121b, made using the Hubble Space Telescope Wide Field Camera 3 in spectroscopic mode across the 1.12–1.64 μm wavelength range. The 1.4 μm water absorption band is detected at high confidence (5.4σ) in the planetary atmosphere. We also reanalyze ground-based photometric light curves taken in the B, r', and z' filters. Significantly deeper transits are measured in these optical bandpasses relative to the near-infrared wavelengths. We conclude that scattering by high-altitude haze alone is unlikely to account for this difference and instead interpret it as evidence for titanium oxide and vanadium oxide absorption. Enhanced opacity is also inferred across the 1.12–1.3 μm wavelength range, possibly due to iron hydride absorption. If confirmed, WASP-121b will be the first exoplanet with titanium oxide, vanadium oxide, and iron hydride detected in transmission. The latter are important species in M/L dwarfs and their presence is likely to have a significant effect on the overall physics and chemistry of the atmosphere, including the production of a strong thermal inversion.