Impact of sample preparation on mineralogical analysis of zero-valent iron reactive barrier materials

Permeable reactive barriers (PRBs) of zero-valent iron (Fe⁰) are increasingly being used to remediate contaminated ground water. Corrosion of Fe⁰ filings and tbe formation of precipitates can occur when the PRB material comes in contact with ground water and may reduce the lifespan and effectiveness of the barrier. At present, there are no routine procedures for preparing and analyzing the mineral precipitates from Fe⁰ PRB material. These procedures are needed because mineralogical composition of corrosion products used to interpret the barrier processes can change with iron oxidation and sample preparation. The objectives of this study were (i) to investigate a method of preparing Fe⁰ reactive barrier material for mineralogical analysis by X-ray diffraction (XRD), and (ii) to identify Fe mineral phases and rates of transformations induced by different mineralogical preparation techniques. Materials from an in situ Fe⁰ PRB were collected by undisturbed coring and processed for XRD analysis after different times since sampling for three size fractions and by various drying treatments. We found that whole-sample preparation for analysis was necessary because mineral precipitates occurred within the PRB material in different size fractions of the samples. Green rusts quickly disappeared from acetone-dried samples and were not present in air-dried and oven-dried samples Maghemite/magnetite content increased over time and in oven-dried samples, especially after heating to 105°C. We conclude that care must be taken during sample preparation of Fe⁰ PRB material, especially for detection of green rusts, to ensure accurate identification of minerals present within the barrier system.

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.

Reduction of the temperature sensitivity of Halomonas hydrothermalis by iron starvation combined with microaerobic conditions

The limits to biological processes on Earth are determined by physicochemical parameters, such as extremes of temperature and low water availability. Research into microbial extremophiles has enhanced our understanding of the biophysical boundaries which define the biosphere. However, there remains a paucity of information on the degree to which rates of microbial multiplication within extreme environments are determined by the availability of specific chemical elements. Here, we show that iron availability and composition of the gaseous phase (aerobic vs. microaerobic) determine susceptibility of a marine bacterium, Halomonas hydrothermalis, to sub-optimal and elevated temperature and salinity by impacting rates of cell division (but not viability). In particular, iron starvation combined with microaerobic conditions (5 % v/v of O2, 10 % v/v of CO2, reduced pH) reduced sensitivity to temperature across the 13 °C range tested. These data demonstrate that nutrient limitation interacts with physicochemical parameters to determine biological permissiveness for extreme environments. The interplay between resource availability and stress tolerance, therefore, may shape the distribution and ecology of microorganisms within Earth's biosphere.

Endothelial function, antioxidant status and vascular compliance in newly diagnosed HFE C282Y homozygotes

Purpose: This pilot study was aimed to establish techniques for assessing and observing trends in endothelial function, antioxidant status and vascular compliance in newly diagnosed HFE haemochromatosis during the first year of venesection.

Patients/methods: Untreated newly diagnosed HFE haemochromatosis patients were tested for baseline liver function, iron indices, lipid profile, markers of endothelial function, anti-oxidant status and vascular compliance. Following baseline assessment, subjects attended at 6-weeks and at 3, 6, 9 and 12-months for follow-up studies.

Results: Ten patients were recruited (M = 8, F = 2, mean age = 51 years). Venesection significantly increased high density lipoproteins at 12-months (1.25 mmol/L vs. 1.37 mmol/L, p = 0.01). However, venesection did not significantly affect lipid hydroperoxides, intracellular and vascular cell adhesion molecules or high sensitivity C-reactive protein (0.57 mu mol/L vs. 0.51 mu mol/L, p = 0.45, 427.4 ng/ml vs. 307.22 ng/ml, p = 0.54, 517.70 ng/ml vs. 377.50 ng/ml, p = 0.51 and 290.75 mu g/dL vs. 224.26 mu g/dL, p = 0.25). There was also no significant effect of venesection on anti-oxidant status or pulse wave velocity (9.65 m/s vs. 8.74 m/s, p = 0.34).

Conclusions: Venesection significantly reduced high density lipoproteins but was not associated with significant changes in endothelial function, anti-oxidant status or vascular compliance. Larger studies using this established methodology are required to clarify this relationship further. 

Density Functional Theory Study of Iron and Cobalt Carbides for Fischer-Tropsch Synthesis

Carbides are important phases in heterogeneous catalysis. However, the understanding of carbide phases is inadequate: Fe and Co are the two commercial catalysts for Fischer-Tropsch (FT) synthesis, and experimental work showed that Fe carbide is the active phase in FT synthesis, whereas the appearance of Co carbide is considered as a possible deactivation cause, TO understand very different catalytic roles of carbides, all the key elementary steps in FT synthesis, that is, CO dissociation, C(1) hydrogenation, and C(1)+C(1) coupling, are extensively investigated on both carbide surfaces using first principles calculations. In particular, the most important issues in FT synthesis, the activity and methane selectivity, on the carbide surfaces are quantitatively determined and analyzed. They are also discussed together with metallic Fe and Co surfaces. It is found that (i) Fe carbide is more active than metallic Fe and has similar methane selectivity to Fe, being consistent with the experiments; and (ii) Co carbide is less active than Co and has higher methane selectivity, providing evidence on the molecular level to support the suggestion that the formation of Co carbide is a cause of relatively high methane selectivity and deactivation on Co catalysts.

Deregulation of genes related to iron and mitochondrial metabolism in refractory anemia with ring sideroblasts

The presence of SF3B1 gene mutations is a hallmark of refractory anemia with ring sideroblasts (RARS). However, the mechanisms responsible for iron accumulation that characterize the Myelodysplastic Syndrome with ring sideroblasts (MDS-RS) are not completely understood. In order to gain insight in the molecular basis of MDS-RS, an integrative study of the expression and mutational status of genes related to iron and mitochondrial metabolism was carried out. A total of 231 low-risk MDS patients and 81 controls were studied. Gene expression analysis revealed that iron metabolism and mitochondrial function had the highest number of genes deregulated in RARS patients compared to controls and the refractory cytopenias with unilineage dysplasia (RCUD). Thus mitochondrial transporters SLC25 (SLC25A37 and SLC25A38) and ALAD genes were over-expressed in RARS. Moreover, significant differences were observed between patients with SF3B1 mutations and patients without the mutations. The deregulation of genes involved in iron and mitochondrial metabolism provides new insights in our knowledge of MDS-RS. New variants that could be involved in the pathogenesis of these diseases have been identified.

Expanded iron uta spectra - Probing the thermal stability limits in AGN clouds

The Fe unresolved transition arrays (UTAs) produce prominent features in the 15-17 Å wavelength range in the spectra of active galactic nuclei (AGNs). Here, we present new calculations of the energies and oscillator strengths of inner-shell lines from Fe XIV, Fe XV, and Fe XVI. These are crucial ions since they are dominant at inflection points in the gas thermal stability curve, and UTA excitation followed by autoionization is an important ionization mechanism for these species. We incorporate these, and data reported in previous papers, into the plasma simulation code Cloudy. This updated physics is subsequently employed to reconsider the thermally stable phases in absorbing media in AGNs. We show how the absorption profile of the Fe XIV UTA depends on density, due to the changing populations of levels within the ground configuration. © 2013. The American Astronomical Society. All rights reserved.

King David’s City at Khirbet Qeiyafa: Results of the Second Radiocarbon Dating Project

Fifteen samples of burnt olive pits discovered inside a jar in the destruction layer of the Iron Age city of Khirbet Qeiyafa were analyzed by accelerator mass spectrometry (AMS) radiocarbon dating. Of these, four were halved and sent to two different laboratories to minimize laboratory bias. The dating of these samples is ~1000 BC. Khirbet Qeiyafa is currently the earliest known example of a fortified city in the Kingdom of Judah and contributes direct evidence to the heated debate on the biblical narrative relating to King David. Was he the real historical ruler of an urbanized state-level society in the early 10th century BC or was this level of social development reached only at the end of the 8th century BC? We can conclude that there were indeed fortified centers in the Davidic kingdom from the studies presented. In addition, the dating of Khirbet Qeiyafa has far-reaching implications for the entire Levant. The discovery of Cypriot pottery at the site connects the 14C datings to Cyprus and the renewal of maritime trade between the island and the mainland in the Iron Age. A stone temple model from Khirbet Qeiyafa, decorated with triglyphs and a recessed doorframe, points to an early date for the development of this typical royal architecture of the Iron Age Levant.

An in situ ionic-liquid-assisted synthetic approach to iron fluoride/graphene hybrid nanostructures as superior cathode materials for lithium ion batteries

A tactful ionic-liquid (IL)-assisted approach to in situ synthesis of iron fluoride/graphene nanosheet (GNS) hybrid nanostructures is developed. To ensure uniform dispersion and tight anchoring of the iron fluoride on graphene, we employ an IL which serves not only as a green fluoride source for the crystallization of iron fluoride nanoparticles but also as a dispersant of GNSs. Owing to the electron transfer highways created between the nanoparticles and the GNSs, the iron fluoride/GNS hybrid cathodes exhibit a remarkable improvement in both capacity and rate performance (230 mAh g^-1 at 0.1 C and 74 mAh g^-1 at 40 C). The stable adhesion of iron fluoride nanoparticles on GNSs also introduces a significant improvement in long-term cyclic performance (115 mAh g^-1 after 250 cycles even at 10 C). The superior electrochemical performance of these iron fluoride/GNS hybrids as lithium ion battery cathodes is ascribed to the robust structure of the hybrid and the synergies between iron fluoride nanoparticles and graphene. © 2013 American Chemical Society.

Genetic mapping of the rice ionome in leaves and grain:Identification of QTLs for 17 elements including arsenic, cadmium, iron and selenium

Research into the composition of cereal grains is motivated by increased interest in food quality. Here multi-element analysis is conducted on leaves and grain of the Bala x Azucena rice mapping population grown in the field. Quantitative trait loci (QTLs) for the concentration of 17 elements were detected, revealing 36 QTLs for leaves and 41 for grains. Epistasis was detected for most elements. There was very little correlation between leaf and grain element concentrations. For selenium, lead, phosphorus and magnesium QTLs were detected in the same location for both tissues. In general, there were no major QTL clusters, suggesting separate regulation of each element. QTLs for grain iron, zinc, molybdenum and selenium are potential targets for marker assisted selection to improve seed nutritional quality. An epistatic interaction for grain arsenic also looks promising to decrease the concentration of this carcinogenic element. © Springer Science+Business Media B.V. 2009.

Experimental and discrete element modelling of cohesive iron ore fines

In this study, the behaviour of iron ore fines with varying levels of adhesion was investigated using a confined compression test and a uniaxial test. The uniaxial test was conducted using the semi-automated uniaxial EPT tester in which the cohesive strength of a bulk solid is evaluated from an unconfined compression test following a period of consolidation to a pre-defined vertical stress. The iron ore fines were also tested by measuring both the vertical and circumferential strains on the cylindrical container walls under vertical loading in a separate confined compression tester - the K0 tester, to determine the lateral pressure ratio. Discrete Element Method simulations of both experiments were carried out and the predictions were compared with the experimental observations. A recently developed DEM contact model for cohesive solids, an Elasto-Plastic Adhesive model, was used. This particle contact model uses hysteretic non-linear loading and unloading paths and an adhesion parameter which is a function of the maximum contact overlap. The model parameters for the simulations are phenomenologically based to reproduce the key bulk characteristics exhibited by the solid. The simulation results show a good agreement in capturing the stress history dependent behaviour depicted by the flow function of the cohesive iron ore fines while also providing a reasonably good match for the lateral pressure ratio observed during the confined compression K0 tests. This demonstrates the potential for the DEM model to be used in the simulation of bulk handling applications.

Building sandstone surface modification by biofilm and iron precipitation: emerging block-scale heterogeneity and system response

Stone surfaces are sensitive to their environment. This means that they will often respond to exposure conditions by manifesting a change in surface characteristics. Such changes can be more than simply aesthetic, creating surface/subsurface heterogeneity in stone at the block scale, promoting stress gradients to be set up as surface response to, for example, temperature fluctuations, can diverge from subsurface response. This paper reports preliminary experiments investigating the potential of biofilms and iron precipitation as surface-modifiers on stone, exploring the idea of block-scale surface-to-depth heterogeneity, and investigating how physical alteration in the surface and near-surface zone can have implications for subsurface response and potentially for long-term decay patterns. Salt weathering simulations on fresh and surface-modified stone suggest that even subtle surface modification can have significant implications for moisture uptake and retention, salt concentration and distribution from surface to depth, over the period of the experimental run. The accumulation of salt may increase the retention of moisture, by modifying vapour pressure differentials and the rate of evaporation.
Temperature fluctuation experiments suggest that the presence of a biofilm can have an impact on energy transfer processes that occur at the stone surface (for example, buffering against temperature fluctuation), affecting surface-to-depth stress gradients. Ultimately, fresh and surface-modified blocks mask different kinds of system, which respond to inputs differently because of different storage mechanisms, encouraging divergent behaviour between fresh and surface modified stone over time.

Relativistic radiatively damped R -matrix calculations of the electron-impact excitation of helium-like iron and krypton

Electron-impact excitation data for He-like ions are of significant importance for diagnostic applications to both laboratory and astrophysical plasmas. Here we report on the first fully relativistic R -matrix calculations with radiation damping for the He-like ions Fe 24+ and Kr 34+ . Effective collision strengths for these two ions have been determined with and without damping over a wide temperature range for all transitions between the 49 levels through n = 5. We find that damping has a pronounced effect on the effective collision strengths for excitation to some of the low-lying levels, but its effect on excitation to the vast majority of levels is small. At the energy of a resonance peak, we also investigate the effect of radiation damping on the angular distribution of scattered electrons. Finally, we compare our results for Fe 24+ with an earlier intermediate coupling frame transformation R -matrix calculation with radiation damping by Whiteford et al ( J. Phys. B: At. Mol. Opt. Phys. 34 3179) and find good agreement, especially for excitation to the lower levels.