Multiple self-aligned iron nanowires by a dual selective chemical vapor deposition process

We have demonstrated a self-aligned process to fabricate organized iron nanowires on a planarized surface with wire dimensions down to 50 nm. Polishing was used to expose an alternating silicon silicon dioxide edge and a dual selective metal deposition process produced the nanowires. The initial selective deposition produced a tungsten layer on the exposed polysilicon regions. The discovery that selective chemical vapor deposition of iron from Fe(CO)(5) precursor on dielectric surfaces over tungsten surfaces is the key factor that enables the self-alignment of the iron nanowires. Dimensions of the wires are determined by the thickness of the thermal oxide. (c) 2007 The Electrochemical Society.

Modeling colloid deposition on a protein layer adsorbed to iron-oxide-coated sand

Our recent study reported that conformation change of granule-associated Bovine Serum Albumin (BSA) may influence the role of the protein controlling colloid deposition in porous media (Flynn et al., 2012). The present study conceptualized the observed phenomena with an ellipsoid morphology model, describing BSA as an ellipsoid taking a side-on or end-on conformation on granular surface, and identified the following processes: (1) at low adsorbed concentrations, BSA exhibited a side-on conformation blocking colloid deposition; (2) at high adsorbed concentrations, BSA adapted to an end-on conformation promoted colloid deposition; and (3) colloid deposition on the BSA layer may progressively generate end-on molecules (sites) by conformation change of side-on BSA, resulting in sustained increasing deposition rates. Generally, the protein layer lowered colloid attenuation by the porous medium, suggesting the overall effect of BSA was inhibitory at the experimental time scale. A mathematical model was developed to interpret the ripening curves. Modeling analysis identified the site generation efficiency of colloid as a control on the ripening rate (declining rate in colloid concentrations), and this efficiency was higher for BSA adsorbed from a more dilute BSA solution. © 2012 Elsevier B.V.

Polycyclic aromatic hydrocarbon (PAH) dispersion and deposition to vegetation and soil following a large scale chemical fire

Polycyclic aromatic hydrocarbons (PAHs) were determined in soil and vegetation following a large scale chemical fire involving 10,000 ton of polypropylene. In comparison with sites outside the plume from the fire, PAH concentrations were elevated in grass shoots (by up to 70-fold) and in soil (by up to 370-fold). The pattern of PAH dispersion under the plume was dependent on the physical-chemical properties of individual PAHs. The lighter, least hydrophobic PAHs were dispersed into the environment at greater distances than heavier, more hydrophobic PAHs. At the most distant sampling point (4.5 km) under the plume, the low molecular weight PAHs were still considerably elevated in vegetation samples compared to control sites. Dispersion appeared to be regulated by the compounds partitioning between the vapour and particulate phase, with dry particulate deposition occurring closer to the fire source than gaseous deposition. For all PAHs, the fire resulted in greater contamination of soils compared to grasses, with the relative ratio of plant/soil contamination decreasing as hydrophobicity increased.

Comparing the influence of two different natural organic matter types on colloid deposition in saturated porous medium

Humic acid and protein are two major organic matter types encountered in natural and polluted environment, respectively. This study employed Triple Pulse Experiments (TPEs) to investigate and compare the influence of Suwannee River Humic Acid (SRHA) (model humic acid) and Bovine Serum Albumin (BSA) (model protein) on colloid deposition in a column packed with saturated iron oxide-coated quartz sand. Study results suggest that adsorbed SRHA may inhibit colloid deposition by occupying colloid sites on the porous medium. Conversely, BSA may promote colloid deposition by a 'filter ripening' mechanism. This study provides insight to understand the complex behavior of colloids in organic matter-presented aquifers and sand filters. © (2012) Trans Tech Publications, Switzerland.

High-resolution reconstruction of atmospheric deposition of trace metals and metalloids since AD 1400 recorded by ombrotrophic peat cores in Hautes-Fagnes, Belgium

The objective of our study was to determine the trace metal accumulation rates in the Misten bog, Hautes-Fagnes, Belgium, and assess these in relation to established histories of atmospheric emissions from anthropogenic sources. To address these aims we analyzed trace metals and metalloids (Pb, Cu, Ni, As, Sb, Cr, Co, V, Cd and Zn), as well as Pb isotopes, using XRF, Q-ICP-MS and MC-ICP-MS, respectively in two 40-cm peat sections, spanning the last 600 yr. The temporal increase of metal fluxes from the inception of the Industrial Revolution to the present varies by a factor of 5–50, with peak values found between AD 1930 and 1990. A cluster analysis combined with Pb isotopic composition allows the identification of the main sources of Pb and by inference of the other metals, which indicates that coal consumption and metallurgical activities were the predominant sources of pollution during the last 600 years.

Co-deposition of organic carbon and arsenic in Bengal Delta aquifers.

We present data showing that arsenic (As) was codeposited with organic carbon (OC) in Bengal Delta sediments as As and OC concentrations are highly (p < 0.001) positively correlated in core profiles collected from widely dispersed geographical sites with different sedimentary depositional histories. Analysis of modern day depositional environments revealed that the As/OC correlations observed in cores are due to As retention and high OC inputs in vegetated zones of the deltaic environment. We hypothesize that elevated concentrations of As occur in vegetated wetland sediments due to concentration and retention of arsenate in aerated root zones and animal burrows where copious iron(III) oxides are deposited. On burial of the sediment, degradation of organic carbon from plant and animal biomass detritus provides the reducing conditions to dissolve iron(III) oxides and release arsenite into the porewater. As tubewell abstracted aquifer water is an invaluable resource on which much of Southeast Asia is now dependent, this increased understanding of the processes responsible for As buildup and release will identify, through knowledge of the palaeosedimentary environment, which sediments are at most risk of having high arsenic concentrations in porewater. Our data allow the development of a new unifying hypothesis of how As is mobilized into groundwaters in river flood plains and deltas of Southeast Asia, namely that in these highly biologically productive environments, As and OC are codeposited, and the codeposited OC drives As release from the sediments. We present data showing that arsenic (As) was codeposited with organic carbon (OC) in Bengal Delta sediments as As and OC concentrations are highly (p < 0.001) positively correlated in core profiles collected from widely dispersed geographical sites with different sedimentary depositional histories. Analysis of modern day depositional environments revealed that the As?OC correlations observed in cores are due to As retention and high OC inputs in vegetated zones of the deltaic environment. We hypothesize that elevated concentrations of As occur in vegetated wetland sediments due to concentration and retention of arsenate in aerated root zones and animal burrows where copious iron(III) oxides are deposited. On burial of the sediment, degradation of organic carbon from plant and animal biomass detritus provides the reducing conditions to dissolve iron(III) oxides and release arsenite into the porewater. As tubewell abstracted aquifer water is an invaluable resource on which much of Southeast Asia is now dependent, this increased understanding of the processes responsible for As buildup and release will identify, through knowledge of the palaeosedimentary environment, which sediments are at most risk of having high arsenic concentrations in porewater. Our data allow the development of a new unifying hypothesis of how As is mobilized into groundwaters in river flood plains and deltas of Southeast Asia, namely that in these highly biologically productive environments, As and OC are codeposited, and the codeposited OC drives As release from the sediments.

Ti mesh anodes prepared by electrochemical deposition for the direct methanol fuel cell

An anode structure based on Ti mesh has been developed for the direct methanol fuel cell (DMFC). This new anode was prepared by electrochemical deposition of a ~ 3 µ m PtRu catalyst layer on ~ 50 µ m Ti mesh. It has a thinner structure compared to that of a porous carbon-based conventional anode. The Ti mesh anode shows a performance comparable to, and exceeding that, of the conventional anode in a DMFC operating with 0.25 or 0.5 M methanol solution and atmosphere oxygen at 90 C. However, it shows a lower performance of the cell when higher concentrations of methanol was employed. This may be attributed to its thin and open structure, which could facilitate the transport of methanol from the flow field to the anode catalyst layer and carbon dioxide in the opposite direction. © 2006 International Association for Hydrogen Energy.

Homologous size-extension of hybrid vanadate capsules – solid state structures, solution stability and surface deposition

The dimensions and cavity sizes of the molecular capsules with the general formula [V₁₀O₁₈L₄]¹⁰⁻ can be controlled modularly through the nature of the bifunctional, rigid organophosphonate ligands L¹ and L² (L¹ = bis(4-phosphonatophenyl)ethyne and L² = bis(4-phosphonatophenyl)butadiyne); the solution stability of the molecular entities as demonstrated by ESI-MS studies permits their assembly on the Au(111) surface on a sub-monolayer scale giving rise to a 2D supramolecular structure that is comparable to the packing arrangements of the capsules in the crystal structures.

Filling the gap: A 60 ky record of mixed carbonate-siliciclastic turbidite deposition from the Great Barrier Reef

Late Pleistocene to Holocene margin sedimentation on the Great Barrier Reef, a mixed carbonatesiliciclastic margin, has been explained by a transgressive shedding model. This model has challenged widely accepted sequence stratigraphic models in terms of the timing and type of sediment (i.e. carbonate vs. siliciclastic) deposited during sea-level oscillations. However, this model documents only hemipelagic sedimentation and the contribution of coarse-grained turbidite deposition, and the role of submarine canyons in this process, remain elusive on this archetypal margin. Here we present a new model of turbidite deposition for the last 60 ky in the north-eastern Australia margin. Using highresolution bathymetry, 58 new and existing radiometric ages, and the composition of 81 turbidites from 15 piston cores, we found that the spatial and temporal variation of turbidites is controlled by the relationship between sea-level change and the variable physiography along the margin. Siliciclastic and mixed carbonate-siliciclastic turbidites were linked to canyons indenting the shelf-break and the welldeveloped shelf-edge reef barriers that stored sediment behind them. Turbidite deposition was sustained while the sea-level position allowed the connection and sediment bypassing through the interreef passages and canyons. Carbonate turbidites dominated in regions with more open conditions at the outer-shelf and where slope-confined canyons dominated or where canyons are generally less abundant. The turn-on and maintenance of carbonate production during sea-level fluctuations also influenced the timing of carbonate turbidite deposition. We show that a fundamental understanding of the variable physiography inherent to mixed carbonate-siliciclastic margins is essential to accurately interpret deep-water, coarse-grained deposition within a sequence stratigraphic context. 

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.

The role of deposition process on pressure dip formation underneath a granular pile

This paper describes an experimental investigation on the pressure dip phenomenon in a conical pile of granular solids. The roles of different deposition processes such as the pouring rate, pouring height and deposition jet size on the pressure dip formation were studied. Test results confirmed that the pressure dip is a robust phenomenon in a pile formed by top deposition. When the deposition jet radius is significantly smaller than the final pile radius (i.e. concentrated deposition), a dip developed in the centre as shown in previous studies. However, when the deposition jet radius is comparable to the final pile radius (i.e. diffuse deposition), the location of the dip moves towards the edge of deposition jet, with a local maximum pressure developed in the centre. For concentrated deposition, an increase in the pouring rate may enhance the depth of the dip and reduce its width, while an increase in the pouring height has only a negligible effect in the studied range. The results suggest the pressure dip is closely related to the initial location, intensity and form of downslope flows. © 2013 Elsevier Inc. All rights reserved.

Distal Deposition of Tephra from the Eyjafjallajökull 2010 Summit Eruption

The 2010 Eyjafjallajökull lasted 39 days and had 4 different phases, of which the first and third (14–18 April and 5–6 May) were most intense. Most of this period was dominated by winds with a northerly component that carried tephra toward Europe, where it was deposited in a number of locations and was sampled by rain gauges or buckets, surface swabs, sticky-tape samples and air filtering. In the UK, tephra was collected from each of the Phases 1–3 with a combined range of latitudes spanning the length of the country. The modal grain size of tephra in the rain gauge samples was 25 um, but the largest grains were 100 um in diameter and highly vesicular. The mass loading was equivalent to 8–218 shards cm2, which is comparable to tephra layers from much larger past eruptions. Falling tephra was collected on sticky tape in the English Midlands on 19, 20 and 21st April (Phase 2), and was dominated by aggregate clasts (mean diameter 85 um, component grains <10 um). SEM-EDS spectra for aggregate grains contained an extra peak for sulphur, when compared to control samples from the volcano, indicating that they were cemented by sulphur-rich minerals e.g. gypsum (CaSO4⋅H2O). Air quality monitoring stations did not record fluctuations in hourly PM10 concentrations outside the normal range of variability during the eruption, but there was a small increase in 24-hour running mean concentration from 21–24 April (Phase 2). Deposition of tephra from Phase 2 in the UK indicates that transport of tephra from Iceland is possible even for small eruption plumes given suitable wind conditions. The presence of relatively coarse grains adds uncertainty to concentration estimates from air quality sensors, which are most sensitive to grain sizes <10 um. Elsewhere, tephra was collected from roofs and vehicles in the Faroe Islands (mean grain size 40 um, but 100 um common), from rainwater in Bergen in Norway (23–91 um) and in air filters in Budapest, Hungary (2–6 um). A map is presented summarizing these and other recently published examples of distal tephra deposition from the Eyjafjallajökull eruption. It demonstrates that most tephra deposited on mainland Europe was produced in the highly explosive Phase 1 and was carried there in 2–3 days.

INTERPLAY OF CAF2 SUBSTRATE ROUGHENING AND FILM DEPOSITION RATE ON RADIATIVE SCATTERING OF SURFACE-PLASMON POLARITONS FROM AG FILMS

The radiative decay of surface plasmon polaritons has been investigated in an attempt to characterize the surface roughness of Ag films prepared under different conditions. The polaritons were excited by the method of attenuated total reflection of light. The films were deposited on the face of a 60-degrees BK-7 glass prism at a rate that was deliberately fixed in two different ranges (centred on 0.1 and 10 nm s-1) and in some cases a CaF2 underlayer was used to roughen the film surfaces. The intensity of the scattered light emitted from the opposite face of the films was measured as a function of direction for each using the same sensitivity scale and was correlated with the preparation of the film. It was found that on nominally smooth substrates fast-deposited thinner films give out more light and are deduced to have greater short wavelength (300-600 nm) roughness amplitude. There is also evidence for long wavelenth (7 mum) periodic roughness due to the prism substrate itself. On CaF2 roughened surfaces the light output from the films is further increased and the peak intensity is backward directed with respect to the exciting laser beam direction. Here roughness on a lateral scale of 350 nm is responsible. Also, elastic scattering of surface plasmon polaritons at grain boundaries reduces the light output from fast deposited, small grain, films on CaF2 roughened surfaces. Overall, a consistent picture of roughness induced radiative polariton decay emerges for all cases studied.

On the optical properties of bismuth oxide thin films prepared by pulsed laser deposition

The optical properties of bismuth oxide films prepared by pulsed laser deposition (PLD), absorption in the photon energy range 2.50-4.30 eV and optical functions (n, k, epsilon(1), and epsilon(2)) in the domain 3.20-6.50 eV, have been investigated. As-prepared films (d = 0.05-1.50 mum) are characterized by a mixture of polycrystalline and amorphous phases. The fundamental absorption edge is described by direct optical band-to-band transitions with energies 2.90 and 3.83 eV The dispersion of the optical functions provided values of 4.40-6.25 eV for electron energies of respective direct transitions. In the spectral range 400-1000 nm, bismuth oxide films show a normal dispersion, which can be interpreted in the frame of a single oscillator model. (C) 2004 Elsevier B.V. All rights reserved.