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.

A Microscopic Study of Iron and Manganese Oxide Distribution in Soils from East Tennessee (U.S.A.)

Soils and saprolites developed from interbedded shales and limestones of the Conasauga Group are widespread in the Valley and Ridge Province of East Tennessee. Thin sections from four soil profiles were examined by petrographic and scanning electron microscopy including backscatter electron and energy-dispersive X-ray analyses. Iron and manganese released by weathering had migrated differentially downward and precipitated as crystalline and noncrystalline oxides. Oxides were observed as nodules, granular particulates, pore fillings, and coatings on other minerals, packing voids, vesicles, channels, and chambers. Iron oxides formed predominantly as coatings on packing-void walls and on laminated clays in vesicles and channels. Manganese oxides occurred as an early replacement phase of packing voids and of fracture-filling carbonate minerals. Iron oxides were dominant in moderately well-drained and oxidized horizons of the soil solum, whereas manganese oxides were abundant in the oxidized and moderately leached saprolite zone where the water table fluctuates seasonally. Therefore, a manganese enrichment zone, on a bulk soil basis, occurred generally below the iron oxide zone in the soil profile. Such differential migration and accumulation of iron and manganese have been controlled by localized soil microenvironments. Micromorphologic features observed in this study are important in land-use evaluation for hazardous waste disposal. © 1990.

Multiferroic Iron Oxide Thin Films at Room Temperature

Multiferroic behaviour at room temperature is demonstrated in ε-Fe2O3. The simple composition of this new ferromagnetic ferroelectric oxide and the discovery of a robust path for its thin film growth by using suitable seed layers may boost the exploitation of ε-Fe2O3 in novel devices.

What defines a geochemical map? Implications for environmental assessment.

The environmental quality of land is often assessed by the calculation of threshold values which aim to differentiate between concentrations of elements based on whether the soils are in residential or industrial sites. In Europe, for example, soil guideline values exist for agricultural and grazing land. A threshold is often set to differentiate between concentrations of the element that naturally occur in the soil and concentrations that result from diffuse anthropogenic sources. Regional geochemistry and, in particular, single component geochemical maps are increasingly being used to determine these baseline environmental assessments. The key question raised in this paper is whether the geochemical map can provide an accurate interpretation on its own. Implicit is the thought that single component geochemical maps represent absolute abundances. However,because of the compositional (closed) nature of the data univariate geochemical maps cannot be compared directly with one another.. As a result, any interpretation based on them is vulnerable to spurious correlation problems. What does this mean for soil geochemistry mapping, baseline quality documentation, soil resource assessment or risk evaluation? Despite the limitation of relative abundances, individual raw geochemical maps are deemed fundamental to several applications of geochemical maps including environmental assessments. However, element toxicity is related to its bioavailable concentration, which is lowered if its source is mixed with another source. Elements interact, for example under reducing conditions with iron oxides, its solid state is lost and arsenic becomes soluble and mobile. Both of these matters may be more adequately dealt with if a single component map is not interpreted in isolation to determine baseline and threshold assessments. A range of alternative compositionally compliant representations based on log-ratio and log-contrast approaches are explored to supplement the classical single component maps for environmental assessment. Case study examples are shown based on the Tellus soil geochemical dataset, covering Northern Ireland and the results of in vitro oral bioaccessibility testing carried out on a sub-set of archived Tellus Survey shallow soils following the Unified BARGE (Bioaccessibility Research Group of Europe).

Do spectral gamma ray data really reflect humid-arid palaeoclimates? A test from the Palaeogene Interbasaltic weathered horizons at the Giant’s Causeway, N.Ireland

Since 1999, the rapid, inexpensive and non-destructive use of Th/K and Th/U ratios from spectral gamma ray measurements have been used as a proxy for changes in palaeo-hinterland weathering. This model is tested here by analysis of in situ palaeoweathering horizons where clay mineral contents are well-known. A residual palaeoweathered horizon of Palaeogene laterite (developed on basalt) has been logged at 14 locations across N. Ireland using spectral gamma ray detectors. The results are compared to published elemental and mineralogical data. While the model of K and U loss during the early stages of weathering to smectite and kaolinite is supported, the formation (during progressively more advanced weathering) of gibbsite and iron oxides has reversed the predicted pattern and caused U and Th retention in the weathering profile. The severity (duration, humidity) of weathering and palaeoweathering may be estimated using Th/K ratios as a proxy. The use of Th/U ratios is more problematic should detrital gibbsite (or similar clays) or iron oxides be detected. Mineralogical analysis is needed in order to evaluate the hosts for K, U and Th: nonetheless, the spectral gamma ray machine offers a real-time, inexpensive and effective tool for the preliminary or conjunctive assessment of degrees of weathering or palaeoweathering.

Deep weathering of calcareous sedimentary rock and the redistribution of iron and manganese in soil and saprolite

Iron and Mn redistribute in soil and saprolite during weathering. The geological weathering fronts ofcalcareous sedimentary rock were investigated by examining the bulk density, porosity, and distribution ofCa, Fe, and Mn. Core samples were taken ofsoil, saprolite, and bedrock material from both summit (HHMS-4B) and sideslope (HHMS-5A) positions on an interbedded Nolichucky shale and Maryville limestone landform in Solid Waste Storage Area 6 (SWSA-6). This is a low-level radioactive solids waste disposal site on the Dept. ofEnergy (DOE) Oak Ridge Reservation in Roane County Tennessee. This work was initiated because data about the properties of highly weathered sedimentary rock on this site were limited. The core samples were analyzed for pH, calcium carbonate equivalence (CCE), hydroxylamine-extractable (HA) Mn, and dithionite-citrate (CBD)-extractable Fe and Mn. Low pH values occurred from the soil surface down to the depth of the oxidized and leached saprolite in both cores. The CCE and HA-extractable Mn results were also influenced by the weathering that has occurred in these zones. Extractable Mn oxide was higher at a lower depth in the oxidized and leached saprolite compared with the Fe oxide, which was higher in the overlying soil solum. Amounts of Mn oxides were higher in the sideslope core (HHMS-5A) than in the summit core (HHMS-4B). Iron was more abundant in the deeper weathered summit core, but the highest value, 39.4 g kg-1, was found at 1.8 to 2.4 m in the sideslope core. The zone encompassing the oxidized and partially leached saprolite down to the unoxidized and unleached bedrock had higher densities and larger quantities of CaCO3 than the soil solum and oxidized and leached saprolite. The overlying soil and oxidized and leached saprolite had lower pH and CCE values and were higher in Fe and Mn oxides than the oxidized and unleached saprolite. The distribution of Fe and Mn is important when evaluating soil and saprolite for hazardous waste disposal site assessment.

Task-specific ionic liquid for solubilizing metal oxides

Protonated betaine bis(trifluoromethylsulfonyl) imide is an ionic liquid with the ability to dissolve large quantities of metal oxides. This metal-solubilizing power is selective. Soluble are oxides of the trivalent rare earths, uranium(VI) oxide, zinc(II) oxide, cadmium( II) oxide, mercury( II) oxide, nickel( II) oxide, copper(II) oxide, palladium(II) oxide, lead(II) oxide, manganese( II) oxide, and silver( I) oxide. Insoluble or very poorly soluble are iron(III), manganese(IV), and cobalt oxides, as well as aluminum oxide and silicon dioxide. The metals can be stripped from the ionic liquid by treatment of the ionic liquid with an acidic aqueous solution. After transfer of the metal ions to the aqueous phase, the ionic liquid can be recycled for reuse. Betainium bis( trifluoromethylsulfonyl) imide forms one phase with water at high temperatures, whereas phase separation occurs below 55.5 degrees C ( temperature switch behavior). The mixtures of the ionic liquid with water also show a pH-dependent phase behavior: two phases occur at low pH, whereas one phase is present under neutral or alkaline conditions. The structures, the energetics, and the charge distribution of the betaine cation and the bis( trifluoromethylsulfonyl) imide anion, as well as the cation-anion pairs, were studied by density functional theory calculations.

Arsenic sequestration in iron plaque, its accumulation and speciation in mature rice plants (Oryza sativa L.)

A compartmented soil-glass bead culture system was used to investigate characteristics of iron plaque and arsenic accumulation and speciation in mature rice plants with different capacities of forming iron plaque on their roots. X-ray absorption near-edge structure spectra and extended X-ray absorption fine structure were utilized to identify the mineralogical characteristics of iron plaque and arsenic sequestration in plaque on the rice roots. Iron plaque was dominated by (oxyhydr)oxides, which were composed of ferrihydrite (81-100%), with a minor amount of goethite (19%) fitted in one of the samples. Sequential extraction and XANES data showed that arsenic in iron plaque was sequestered mainly with amorphous and crystalline iron (oxyhydr)oxides, and that arsenate was the predominant species. There was significant variation in iron plaque formation between genotypes, and the distribution of arsenic in different components of mature rice plants followed the following order: iron plaque > root > straw > husk > grain for all genotypes. Arsenic accumulation in grain differed significantly among genotypes. Inorganic arsenic and dimethylarsinic acid (DMA) were the main arsenic species in rice grain for six genotypes, and there were large genotypic differences in levels of DMA and inorganic arsenic in grain.

Iron plaque formation, arsenic uptake and speciation in different genotypes of mature rice plants (Oryza sativa L.)

A compartmented soil-glass bead culture system was used to investigate characteristics of iron plaque and arsenic accumulation and speciation in mature rice plants with different capacities of forming iron plaque on their roots. X-ray absorption near-edge structure spectra and extended X-ray absorption fine structure were utilized to identify the mineralogical characteristics of iron plaque and arsenic sequestration in plaque on the rice roots. Iron plaque was dominated by (oxyhydr)oxides, which were composed of ferrihydrite (81-100%), with a minor amount of goethite (19%) fitted in one of the samples. Sequential extraction and XANES data showed that arsenic in iron plaque was sequestered mainly with amorphous and crystalline iron (oxyhydr)oxides, and that arsenate was the predominant species. There was significant variation in iron plaque formation between genotypes, and the distribution of arsenic in different components of mature rice plants followed the following order:? iron plaque > root > straw > husk > grain for all genotypes. Arsenic accumulation in grain differed significantly among genotypes. Inorganic arsenic and dimethylarsinic acid (DMA) were the main arsenic species in rice grain for six genotypes, and there were large genotypic differences in levels of DMA and inorganic arsenic in grain. A compartmented soil-glass bead culture system was used to investigate characteristics of iron plaque and arsenic accumulation and speciation in mature rice plants with different capacities of forming iron plaque on their roots. X-ray absorption near-edge structure spectra and extended X-ray absorption fine structure were utilized to identify the mineralogical characteristics of iron plaque and arsenic sequestration in plaque on the rice roots. Iron plaque was dominated by (oxyhydr)oxides, which were composed of ferrihydrite (81-100%), with a minor amount of goethite (19%) fitted in one of the samples. Sequential extraction and XANES data showed that arsenic in iron plaque was sequestered mainly with amorphous and crystalline iron (oxyhydr)oxides, and that arsenate was the predominant species. There was significant variation in iron plaque formation between genotypes, and the distribution of arsenic in different components of mature rice plants followed the following order:? iron plaque > root > straw > husk > grain for all genotypes. Arsenic accumulation in grain differed significantly among genotypes. Inorganic arsenic and dimethylarsinic acid (DMA) were the main arsenic species in rice grain for six genotypes, and there were large genotypic differences in levels of DMA and inorganic arsenic in grain.

Steam reforming of ethanol over Co3O4–Fe2O3 mixed oxides

Co3O4, Fe2O3 and a mixture of the two oxides Co–Fe (molar ratio of Co3O4/Fe2O3 = 0.67 and atomic ratio of Co/Fe = 1) were prepared by the calcination of cobalt oxalate and/or iron oxalate salts at 500 °C for 2 h in static air using water as a solvent/dispersing agent. The catalysts were studied in the steam reforming of ethanol to investigate the effect of the partial substitution of Co3O4 with Fe2O3 on the catalytic behaviour. The reforming activity over Fe2O3, while initially high, underwent fast deactivation. In comparison, over the Co–Fe catalyst both the H2 yield and stability were higher than that found over the pure Co3O4 or Fe2O3 catalysts. DRIFTS-MS studies under the reaction feed highlighted that the Co–Fe catalyst had increased amounts of adsorbed OH/water; similar to Fe2O3. Increasing the amount of reactive species (water/OH species) adsorbed on the Co–Fe catalyst surface is proposed to facilitate the steam reforming reaction rather than decomposition reactions reducing by-product formation and providing a higher H2 yield.

Adsorption Study using Optimised 3D Organised Mesoporous Silica Coated with Fe and Al Oxides for Specific As(III) and As(V) Removal from Contaminated Synthetic Groundwater

This work presents the possibility of optimising 3D Organised Mesoporous Silica (OMS) coated with both iron and aluminium oxides for the optimal removal of As(III) and As(V) from synthetic contaminated water. The materials developed were fully characterised and were tested for removing arsenic in batch experiments. The effect of total Al to Fe oxides coating on the selective removal of As(III) and As(V) was studied. It was shown that 8% metal coating was the optimal configuration for the coated OMS materials in removing arsenic. The effect of arsenic initial concentration and pH, kinetics and diffusion mechanisms was studied, modelled and discussed. It was shown that the advantage of an organised material over an un-structured sorbent was very limited in terms of kinetic and diffusion under the experimental conditions. It was shown that physisorption was the main adsorption process involved in As removal by the coated OMS. Maximum adsorption capacity of 55 mg As(V).g-1 was noticed at pH 5 for material coated with 8% Al oxides while 35 mg As(V).g-1 was removed at pH 4 for equivalent material coated with Fe oxides.