Adsorption, orientation and thermal decomposition of copper(II) hexafluoroacetylacetonate on rutile TiO2(110)

We have investigated the adsorption and thermal decomposition of copper hexafluoroacetylacetonate (Cu-11(hfaC)(2)) on single crystal rutile TiO2(110). Low energy electron diffraction shows that room temperature saturation coverage of the Cu-II(hfac)(2) adsorbate forms an ordered (2 x 1) over-layer. X-ray and ultra-violet photoemission spectroscopy of the saturated surface were recorded as the sample was annealed in a sequential manner to reveal decomposition pathways. The results show that the molecule dissociatively adsorbs by detachment of one of the two ligands to form hfac and Cu-1(hfac) which chemisorb to the substrate at 298 K. These ligands only begin to decompose once the surface temperature exceeds 473 K where Cu core level shifts indicate metallisation. This reduction from Cu(I) to Cu(0) takes place in the absence of an external reducing agent and without disproportionation and is accompanied by the onset of decomposition of the hfac ligands. Finally, C K-edge near edge X-ray absorption fine structure experiments indicate that both the ligands adsorb aligned in the < 001 > direction and we propose a model in which the hfac ligands adsorb on the 5-fold coordinated Ti atoms and the Cu-1(hfac) moiety attaches to the bridging O atoms in a square planar geometry. The calculated tilt angle for these combined geometries is approximately 10 degrees to the surface normal.

Layer-by-layer electrostatic entrapment of protein molecules on superparamagnetic nanoparticle: new strategy to enhance adsorption capacity and maintain biological activity

There is a recent interest to use inorganic-based magnetic nanoparticles as a vehicle to carry biomolecules for various biophysical applications, but direct attachment of the molecules is known to alter their conformation leading to attenuation in activity. In addition, surface immobilization has been limited to monolayer coverage. It is shown that alternate depositions of negatively charged protein molecules, typically bovine serum albumin (BSA) with a positively charged aminocarbohydrate template such as glycol chitosan (GC) on magnetic iron oxide nanoparticle surface as a colloid, are carried out under pH 7.4. Circular dichroism (CD) clearly reveals that the secondary structure of the entrapped BSA sequential depositions in this manner remains totally unaltered which is in sharp contrast to previous attempts. Probing the binding properties of the entrapped BSA using small molecules (Site I and Site II drug compounds) confirms for the first time the full retention of its biological activity as compared with native BSA, which also implies the ready accessibility of the entrapped protein molecules through the porous overlayers. This work clearly suggests a new method to immobilize and store protein molecules beyond monolayer adsorption on a magnetic nanoparticle surface without much structural alteration. This may find applications in magnetic recoverable enzymes or protein delivery.

Transport and distribution of lindane and simazine in a riverine environment: measurements in bed sediments and modelling

Aquatic sediments often remove hydrophobic contaminants from fresh waters. The subsequent distribution and concentration of contaminants in bed sediments determines their effect on benthic organisms and the risk of re-entry into the water and/or leaching to groundwater. This study examines the transport of simazine and lindane in aquatic bed sediments with the aim of understanding the processes that determine their depth distribution. Experiments in flume channels (water flow of 10 cm s(-1)) determined the persistence of the compounds in the absence of sediment with (a) de-ionised water and (b) a solution that had been in contact with river sediment. In further experiments with river bed sediments in light and dark conditions, measurements were made of the concentration of the compounds in the overlying water and the development of bacterial/algal biofilms and bioturbation activity. At the end of the experiments, concentrations in sediments and associated pore waters were determined in sections of the sediment at 1 mm resolution down to 5 mm and then at 10 mm resolution to 50 mm depth and these distributions analysed using a sorption-diffusion-degradation model. The fine resolution in the depth profile permitted the detection of a maximum in the concentration of the compounds in the pore water near the surface, whereas concentrations in the sediment increased to a maximum at the surface itself. Experimental distribution coefficients determined from the pore water and sediment concentrations indicated a gradient with depth that was partly explained by an increase in organic matter content and specific surface area of the solids near the interface. The modelling showed that degradation of lindane within the sediment was necessary to explain the concentration profiles, with the optimum agreement between the measured and theoretical profiles obtained with differential degradation in the oxic and anoxic zones. The compounds penetrated to a depth of 40-50 rum over a period of 42 days. (C) 2004 Society of Chemical Industry.

Diffusion of the synthetic pyrethroid permethrin into bed-sediments

Bed-sediments are a sink for many micro-organic contaminants in aquatic environments. The impact of toxic contaminants on benthic fauna often depends on their spatial distribution, and the fate of the parent compounds and their metabolites. The distribution of a synthetic pyrethroid, permethrin, a compound known to be toxic to aquatic invertebrates, was studied using river bed-sediments in lotic flume channels. trans/cis-Permethrin diagnostic ratios were used to quantify the photoisomerization of the trans isomer in water. Rates were affected by the presence of sediment particles and colloids when compared to distilled water alone. Two experiments in dark/light conditions with replicate channels were undertaken using natural sediment, previously contaminated with permethrin, to examine the effect of the growth of an algal biofilm at the sediment-water interface on diffusive fluxes of permethrin into the sediment. After 42 days, the bulk water was removed, allowing a fine sectioning of the sediment bed (i.e., every mm down to 5 mm and then 5-10 mm, then every 10 mm down to 50 mm). Permethrin was detected in all cases down to a depth of 5-10 mm, in agreement with estimates by the Millington and Quirk model, and measurements of concentrations in pore water produced a distribution coefficient (K-d) for each section, High K-d's were observed for the top layers, mainly as a result of high organic matter and specific surface area. Concentrations in the algal biofilm measured at the end of the experiment under light conditions, and increases in concentration in the top 1 mm of the sediment, demonstrated that algal/bacterial biofilm material was responsible for high K-d's at the sediment surface, and for the retardation of permethrin diffusion. This specific partition of permethrin to fine sediment particles and algae may enhance its threat to benthic invertebrates. In addition,the analysis of trans/cis-permethrin isomer ratios in sediment showed greater losses of trans-permethrin in the experiment under light conditions, which may have also resulted from enhanced biological activity at the sediment surface.

Geomorphological Map of Ribbed Moraines on the Dubawnt Lake Palaeo-Ice Stream Bed: A Signature of Ice Stream Shut-down?

The beds of active ice streams in Greenland and Antarctica are largely inaccessible, hindering a full understanding of the processes that initiate, sustain and inhibit fast ice flow in ice sheets. Detailed mapping of the glacial geomorphology of palaeo-ice stream tracks is, therefore, a valuable tool for exploring the basal processes that control their behaviour. In this paper we present a map that shows detailed glacial geomorphology from a part of the Dubawnt Lake Palaeo-Ice Stream bed on the north-western Canadian Shield (Northwest Territories), which operated at the end of the last glacial cycle. The map (centred on 63 degrees 55 '' 42'N, 102 degrees 29 '' 11'W, approximate scale 1:90,000) was compiled from digital Landsat Enhanced Thematic Mapper Plus satellite imagery and digital and hard-copy stereo-aerial photographs. The ice stream bed is dominated by parallel mega-scale glacial lineations (MGSL), whose lengths exceed several kilometres but the map also reveals that they have, in places, been superimposed with transverse ridges known as ribbed moraines. The ribbed moraines lie on top of the MSGL and appear to have segmented the individual lineaments. This indicates that formation of the ribbed moraines post-date the formation of the MSGL. The presence of ribbed moraine in the onset zone of another palaeo-ice stream has been linked to oscillations between cold and warm-based ice and/or a patchwork of cold-based areas which led to acceleration and deceleration of ice velocity. Our hypothesis is that the ribbed moraines on the Dubawnt Lake Ice Stream bed are a manifestation of the process that led to ice stream shut-down and may be associated with the process of basal freeze-on. The precise formation of ribbed moraines, however, remains open to debate and field observation of their structure will provide valuable data for formal testing of models of their formation.

Adsorption of water vapor by bare soil in an olive grove in southern Spain

Data for water vapor adsorption and evaporation are presented for a bare soil (sandy loam, clay content 15%) in a southern Spanish olive grove. Water losses and gains were measured using eight high-precision minilysimeters, placed around an olive tree, which had been irrigated until the soil reached field capacity (similar to 0.22 m(3) m(-3)). They were subsequently left to dry for 10 days. A pair of lysimeters was situated at each of the main points of the compass (N, E, S, W), at a distance of 1 m (the inner set of lysimeters; ILS) and 2 m (the outer set of lysimeters; OLS), respectively, from the tree trunk. Distinct periods of moisture loss (evaporation) and moisture gain (vapor adsorption) could be distinguished for each day. Vapor adsorption often started just after noon and generally lasted until the (early) evening. Values of up to 0.7 mm of adsorbed water per day were measured. Adsorption was generally largest for the OLS (up to 100% more on a daily basis), and increased during the dry down. This was mainly the result of lower OLS surface soil moisture contents (period-average absolute difference similar to 0.005 m(3) m(-3)), as illustrated using various analyses employing a set of micrometeorological equations describing the exchange of water vapor between bare soil and the atmosphere. These analyses also showed that the amount of water vapor adsorbed by soils is very sensitive to changes in atmospheric forcing and surface variables. The use of empirical equations to estimate vapor adsorption is therefore not recommended.

Multi-mode approximations to wave scattering by an uneven bed

Approximations to the scattering of linear surface gravity waves on water of varying quiescent depth are Investigated by means of a variational approach. Previous authors have used wave modes associated with the constant depth case to approximate the velocity potential, leading to a system of coupled differential equations. Here it is shown that a transformation of the dependent variables results in a much simplified differential equation system which in turn leads to a new multi-mode 'mild-slope' approximation. Further, the effect of adding a bed mode is examined and clarified. A systematic analytic method is presented for evaluating inner products that arise and numerical experiments for two-dimensional scattering are used to examine the performance of the new approximations.