Industrial radioactive barite scale: suppression of radium uptake by introduction of competing ions

Incorporation of radioactive isotopes during the formation of barite mineral scale is a widespread phenomenon occurring within the oil, mining and process industries. In a series of experiments radioactive barite/celestite solid solutions (SSBarite-Celcstite) have been synthesized under controlled conditions by the counter diffusion of Ra-226, Ba2+, Sr24+ and SO42- ions through a porous medium (silica gel), to investigate inhibiting effects in Ra uptake associated with the introduction of a competing ion (Sr2+). From characterization studies, the particle size and the morphology of the crystals appear to be related to the initial [Sr]/[Ba] molar ratio of the starting solution. Typically, systems richer in Sr produce smaller sized crystals and clusters characterized by a lower degree of order. The activity introduced to the system is mainly incorporated in the crystals generated from the barite/celestite solid solution as suggested by the activity profiles of the hydrogel columns analysed by gamma-spectrometry. There is a relationship between the initial [Sr]/[Ba] molar ratio of the starting solution and the activity exhibited by the synthesized crystals. An effective inhibition of the Ra-226 uptake during formation of the crystals (SSBarite-Celestite) was obtained through the introduction of a competing ion (Sr2+): the higher the initial [Sr]/[Ba] molar ratio of the starting solution, the lower the intensity of the activity peak in the crystals. (C) 2003 Published by Elsevier Ltd.

The composition and crystallinity of the near-surface regions of weathered alkali feldspars

Our ability to identify thin non-stoichiometric and amorphous layers beneath mineral surfaces has been tested by undertaking X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) work on alkali feldspars from pH 1 dissolution experiments. The outcomes of this work were used to help interpret XPS and TEM results from alkali feldspars weathered for <10,000 years in soils overlying the Shap Granite (north-west England). The chemistry of effluent solutions indicates that silica-rich layers a few nanometers in thickness formed during the pH I experiments. These layers can be successfully identified by XPS and have lower Al/Si, Na/Si, K/Si and Ca/Si values than the outermost similar to 9 nm of unweathered controls. Development of Al-Si non-stoichiometry is coupled with loss of crystal structure to produce amorphous layers that are identifiable by TEM where >similar to 2.5 nm thick, whereas the crystallinity of albite is retained despite leaching of Na to depths of tens to hundreds on nanometers. Integration of XPS data over the outermost 6-9 nm of naturally weathered Shap feldspars shows that they have stoichiometric Al/Si and K/Si ratios, which is consistent with findings of previous TEM work on the same material that they lack amorphous layers. There is some XPS evidence for loss of K from the outermost couple of nanometers of Shap orthoclase, and the possibility of leaching of Na from albite to greater depths cannot be excluded using the XPS or TEM results. This study demonstrates that the leached layer model, as formulated from laboratory experiments, is inapplicable to the weathering of alkali feldspars within acidic soils, which is an essentially stoichiometric reaction. (C) 2008 Elsevier Ltd. All rights reserved.

Seed longevity - moisture content relationships in hermetic and open storage

In seed storage research, moisture content can be maintained by providing a stable relative humidity (e.g. over saturated salt solutions) or by hermetic storage, but the two approaches provide different gaseous environments which might affect longevity. Seeds of timothy (Phleum pratense L.) and sesame (Sesamum indicum L.) were stored at 45 degrees C or 50 degrees C, respectively, with different moisture contents maintained by hermetic storage in laminated-aluminium-foil packets, or by desiccators above either saturated salt solutions or moistened silica gel. Seeds were withdrawn from storage at intervals from 1 to 28 d for up to 480 d and viability estimated. Within a species, the negative logarithmic relation between seed longevity and moisture content did not differ (P> 0.25, timothy; >0.05, sesame) between storage in desiccators over either moistened silica gel or saturated salt solutions, whereas the relation was much steeper (P< 0.005) in hermetic storage: longevity was similar at high moisture contents, but at low values much greater with hermetic storage. This effect of storage method on seed longevity's sensitivity to moisture content implies that oxygen is relatively more deleterious to seeds at lower than at greater moisture contents and confirms that hermetic storage is preferable for long-term seed storage at low moisture contents.

Prediction of cottonseed longevity

The objective of this work was to determine the viability equation constants for cottonseed and to detect the occurrence and depletion of hardseededness. Three seedlots of Brazilian cultivars IAC-19 and IAC-20 were tested, using 12 moisture content levels, ranging from 2.2 to 21.7% and three storage temperatures, 40, 50 and 65 degrees C. Seed moisture content level was reached from the initial value (around 8.8%) either by rehydration, in a closed container, or by drying in desiccators containing silica gel, both at 20 degrees C. Twelve seed subsamples for each moisture content/temperature treatment were sealed in laminated aluminium-foil packets and stored in incubators at those temperatures, until complete survival curves were obtained. Seed equilibrium relative humidity was recorded. Hardseededness was detected at moisture content levels below 6% and its releasing was achieved either naturally, during storage period, or artificially through seed coat removal. The viability equation quantified the response of seed longevity to storage environment well with K-E = 9.240, C-W = 5.190, C-H = 0.03965 and C-Q = 0.000426. The lower limit estimated for application of this equation at 65 degrees C was 3.6% moisture content.

Development of novel brush-type chiral stationary phases based on terpenoid selectors: HPLC evaluation and theoretical investigation of enantioselective binding interactions

The terpenoid chiral selectors dehydroabietic acid, 12,14-dinitrodehydroabietic acid and friedelin have been covalently linked to silica gel yielding three chiral stationary phases CSP 1, CSP 2 and CSP 3, respectively. The enantiodiscriminating capability of each one of these phases was evaluated by HPLC with four families of chiral aromatic compounds composed of alcohols, amines, phenylalanine and tryptophan amino acid derivatives and beta-lactams. The CSP 3 phase, containing a selector with a large friedelane backbone is particularly suitable for resolving free alcohols and their derivatives bearing fluorine substituents, while CSP 2 with a dehydroabietic architecture is the only phase that efficiently discriminates 1, 1'-binaphthol atropisomers. CSP 3 also gives efficient resolution of the free amines. All three phases resolve well the racemates of N-trifluoracetyl and N-3,5-dinitrobenzoyl phenylalanine amino acid ester derivatives. Good enantioseparation of beta-lactams and N-benzoyl tryptophan amino acid derivatives was achieved on CSP 1. In order to understand the structural factors that govern the chiral molecular recognition ability of these phases, molecular dynamics simulations were carried out in the gas phase with binary diastereomeric complexes formed by the selectors of CSP 1 and CSP 2 and several amino acid derivatives. Decomposition of molecular mechanics energies shows that van der Waals interactions dominate the formation of the diastereomeric transient complexes while the electrostatic binding interactions are primarily responsible for the enantioselective binding of the (R)- and (S)-analytes. Analysis of the hydrogen bonds shows that electrostatic interactions are mainly associated with the formation of N-(HO)-O-...=C enantio selective hydrogen bonds between the amide binding sites from the selectors and the carbonyl groups of the analytes. The role of mobile phase polarity, a mixture of n-hexane and propan-2-ol in different ratios, was also evaluated through molecular dynamics simulations in explicit solvent. (c) 2006 Elsevier Ltd. All rights reserved.

Enhanced second order non-linear optical properties of silica sol-gel thin films through photo-induced poling

Sol-gel derived inorganic materials are of interest as hosts for non-linear optically active guest molecules and they offer particular advantages in the field of non-linear optics. Orientationally ordered glasses have been prepared using a sol-gel system based on tetramethoxysilane, methyltrimethoxysilane and a non-linear optical chromophore Disperse Red 1. The novel technique of photo-induced poling was used to generate enhanced levels of polar order. The level of enhancement is strongly dependent on the extent of gelation and an optimum preparation time of ∼100 h led to an enhancement factor of ∼5. Films prepared in this manner exhibited a high stability of the polar order.

Ultra-thin porous silica coated silver-platinum alloy nano-particle as a new catalyst precursor

Templated sol-gel encapsulation of surfactant-stabilised micelles containing metal precursor(s) with ultra-thin porous silica coating allows solvent extraction of organic based stabiliser from the composites in colloidal state hence a new method of preparing supported alloy catalysts using the inorganic silica-stabilised nano-sized, homogenously mixed, silver - platinum (Ag-Pt) colloidal particles is reported.

Silica templating of a self-assembling peptide amphiphile that forms nanotapes

The peptide amphiphile C16-KTTKS templates silica polymerization, enabling the production of silica nanotape structures, imaged via electron microscopy (TEM and SEM). X-ray scattering shows that the nanotapes comprise stacked layers, as for the parent peptide amphiphile, but with a substantially increased layer spacing resulting from silica polymerization.

The biometeorology of high-altitude insect layers.

Flight at high altitude is part of a migration strategy that maximises insect population displacement. This thesis represents the first substantial analysis of insect migration and layering in Europe. Vertical-looking entomological radar has revealed specific characteristics of high-altitude flight: in particular layering (where a large proportion of the migrating insects are concentrated in a narrow altitude band). The meteorological mechanisms underpinning the formation of these layers are the focus of this thesis. Aerial netting samples and radar data revealed four distinct periods of high-altitude insect migration: dawn, daytime, dusk, and night-time. The most frequently observed nocturnal profiles during the summertime were layers. It is hypothesised that nocturnal layers initiate at a critical altitude (200–500 m above ground level) and time (20:00–22:00 hours UTC). Case study analysis, statistical analysis, and a Lagrangian trajectory model showed that nocturnal insect layers probably result from the insects’ response to meteorological conditions. Temperature was the variable most correlated with nocturnal insect layer presence and intensity because insects are poikilothermic, and temperatures experienced during high-altitude migration in temperate climates are expected to be marginal for many insects’ flight. Hierarchical effects were detected such that other variables—specifically wind speed—were only correlated with insect layer presence and intensity once temperatures were warm. The trajectory model developed comprised: (i) insect flight characteristics; (ii) turbulent winds (which cause vertical spread of the layer); and (iii) mean wind speed, which normally leads to horizontal displacements of hundreds of kilometres in a single migratory flight. This thesis has revealed that there is considerable migratory activity over the UK in the summer months, and a range of fascinating phenomena can be observed (including layers). The UK has moved from one of the least studied to perhaps the best studied environments of aerial insect migration and layering in the world.

Layers of nocturnal insect migrants at high-altitude: the influence of atmospheric conditions on their formation

1 Radar studies of nocturnal insect migration have often found that the migrants tend to form well-defined horizontal layers at a particular altitude. 2 In previous short-term studies, nocturnal layers were usually observed to occur at the same altitude as certain meteorological features, most notably at the altitudes of temperature inversions or nocturnal wind jets. 3 Statistical analyses are presented of four years’ data that compared the presence, sharpness and duration of nocturnal layer profiles (observed using continuously-operating entomological radar) with meteorological variables at typical layer altitudes over the UK. 4 Analysis of these large datasets demonstrated that temperature was the foremost meteorological factor persistently associated with the presence and formation of longer-lasting and sharper layers of migrating insects over southern UK.

The influence of the atmospheric boundary layer on nocturnal layers of noctuids and other moths migrating over southern Britain

Insects migrating at high altitude over southern Britain have been continuously monitored by automatically-operating, vertical-looking radars over a period of several years. During some occasions in the summer months, the migrants were observed to form well-defined layer concentrations, typically at heights of 200-400 m, in the stable night-time atmosphere. Under these conditions, insects are likely to have control over their vertical movements and are selecting flight heights which are favourable for long-range migration. We therefore investigated the factors influencing the formation of these insect layers by comparing radar measurements of the vertical distribution of insect density with meteorological profiles generated by the UK Met. Office’s Unified Model (UM). Radar-derived measurements of mass and displacement speed, along with data from Rothamsted Insect Survey light traps provided information on the identity of the migrants. We present here three case studies where noctuid and pyralid moths contributed substantially to the observed layers. The major meteorological factors influencing the layer concentrations appeared to be: (a) the altitude of the warmest air, (b) heights corresponding to temperature preferences or thresholds for sustained migration and (c), on nights when air temperatures are relatively high, wind-speed maxima associated with the nocturnal jet. Back-trajectories indicated that layer duration may have been determined by the distance to the coast. Overall, the unique combination of meteorological data from the UM and insect data from entomological radar described here show considerable promise for systematic studies of high-altitude insect layering.

Evidence for global circuit current flow through water droplet layers

Abstract Foggy air and clear air have appreciably different electrical conductivities. The conductivity gradient at horizontal droplet boundaries causes droplet charging, as a result of vertical current flow in the global atmospheric electrical circuit. The charging is poorly known, as both the current flow through atmospheric water droplet layers and the air conductivity are poorly characterised experimentally. Surface measurements during three days of continuous fog using new instrument techniques show that a shallow (of order 100 m deep) fog layer still permits the vertical conduction current to pass. Further, the conductivity in the fog is estimated to be approximately 20% lower than in clear air. Assuming a fog transition thickness of one metre, this implies a vertical conductivity gradient of order 10 fS m−2 at the boundary. The actual vertical conductivity gradient at a cloud boundary would probably be greater, due to the presence of larger droplets in clouds compared to fog, and cleaner, more conductive clear air aloft.

Ex Vivo Construction of an Artificial Ocular Surface by Combination of Corneal Limbal Epithelial Cells and a Compressed Collagen Scaffold Containing Keratocytes

We have investigated the use of a laminin coated compressed collagen gel containing corneal fibroblasts (keratocytes) as a novel scaffold to support the growth of corneal limbal epithelial stem cells. The growth of limbal epithelial cells was compared between compressed collagen gel and a clinically proven conventional substrate, denuded amniotic membrane. Following compression of the collagen gel, encapsulated keratocytes remained viable and scanning electron microscopy showed that fibres within the compressed gel were dense, homogeneous and similar in structure to those within denuded amniotic membrane. Limbal epithelial cells were successfully expanded upon the compressed collagen resulting in stratified layers of cells containing desmosome and hemidesmosome structures. The resulting corneal constructs of both the groups shared a high degree of transparency, cell morphology and cell stratification. Similar protein expression profiles for cytokeratin 3 and cytokeratin 14 and no significant difference in cytokeratin 12 mRNA expression levels by real time PCR were also observed. This study provides the first line of evidence that a laminin coated compressed collagen gel containing keratocytes can adequately support limbal epithelial cell expansion, stratification and differentiation to a degree that is comparable to the leading conventional scaffold, denuded amniotic membrane.