Synthesis of well-dispersed nanoparticles within porous solid structures using surface-tethered surfactants in supercritical CO2

We have developed a new method for the synthesis of Pd nanoparticles with controllable sizes within a silica matrix using solid-supported surfactants in supercritical CO2. XRD, HRTEM and CO chemisorption data show that unformly sized Pd nanoparticles are evenly distributed within the porous silica and are chemically tethered by surfactant molecules [poly(oxyethylene stearyl ether) and fluorinated poly(oxyethylene)]. It is postulated that tiny solid-supported surfactant assemblies act as nano-reactors for the template synthesis of nanoparticles or clusters from the soluble precursors therein.

Numerical study of 2D heat transfer in a scraped surface heat exchanger

A numerical study of fluid mechanics and heat transfer in a scraped surface heat exchanger with non-Newtonian power law fluids is undertaken. Numerical results are generated for 2D steady-state conditions using finite element methods. The effect of blade design and material properties, and especially the independent effects of shear thinning and heat thinning on the flow and heat transfer, are studied. The results show that the gaps at the root of the blades, where the blades are connected to the inner cylinder, remove the stagnation points, reduce the net force on the blades and shift the location of the central stagnation point. The shear thinning property of the fluid reduces the local viscous dissipation close to the singularity corners, i.e. near the tip of the blades, and as a result the local fluid temperature is regulated. The heat thinning effect is greatest for Newtonian fluids where the viscous dissipation and the local temperature are highest at the tip of the blades. Where comparison is possible, very good agreement is found between the numerical results and the available data. Aspects of scraped surface heat exchanger design are assessed in the light of the results. (C) 2003 Elsevier Ltd. All rights reserved.

Effect of heat on rheology, surface hydrophobicity and molecular weight distribution of glutens extracted from flours with different bread-making quality

Gluten was extracted from flours of several different wheat varieties of varying baking quality. Creep compliance was measured at room temperature and tan 6 was measured over a range of temperatures from 25 to 95 degrees C. The extracted glutens were heat-treated for 20 min at 25, 40, 50, 60, 70 and 90 degrees C in a water bath, freeze-dried and ground to a fine powder. Tests were carried out for extractability in sodium dodecyl sulphate, free sulphydryl (SH) groups using Ellman's method, surface hydrophobicity and molecular weight (MW) distribution (MWD) using field-flow fractionation and multi-angle laser light scattering. With increasing temperature, the glutens showed a decrease in extractability, with the most rapid decreases occurring between 70 and 90 degrees C, a major transition in tan 6 at around 60 degrees C and a minor transition at 40 degrees C for most varieties, a decrease in free SH groups and surface hydrophobicity and a shift in the MWD towards higher MW. The poor bread-making variety Riband showed the highest values of tan delta and Newtonian compliance, the lowest content of free SH groups and the largest increase of HMW/LMW with increasing temperature. No significant correlations with baking volume were found between any of the measured parameters. (c) 2007 Elsevier Ltd. All rights reserved.

Arsenicicoccus bolidensis a novel arsenic reducing actinomycete in contaminated sediments near the Adak mine (northern Sweden): impact on water chemistry

Weathering of mine tailings in Adak results in high As concentrations in surface and ground water, sediments, and soil. In spite of the oxic conditions, As-rich surface and ground, water samples indicate As(III) species predominantly (up to 83%). Several microorganisms were isolated from the enrichment cultures that were involved in As cycling. Amongst them was Arsenicicoccus bolidensis - a novel gram-positive, facultatively anaerobic, coccus-shaped actinomycete, which actively reduced As(V) to As(III) in aqueous media. A. bolidensis reduced 0.06-0.20 mM day(-1) As(V). As(V) reduction displays a direct correlation between the initial As(V) concentration, growth rate, and biomass yield. (c) 2006 Elsevier B.V. All rights reserved.

Integrated optics for nulling interferometry in the thermal infrared

Modal filtering is based on the capability of single-mode waveguides to transmit only one complex amplitude function to eliminate virtually any perturbation of the interfering wavefronts, thus making very high rejection ratios possible in a nulling interferometer. In the present paper we focus on the progress of Integrated Optics in the thermal infrared [6-20 mu m] range, one of the two candidate technologies for the fabrication of Modal Filters, together with fiber optics. In conclusion of the European Space Agency's (ESA) "Integrated Optics for Darwin" activity, etched layers of clialcogenide material deposited on chalcogenide glass substrates was selected among four candidates as the technology with the best potential to simultaneously meet the filtering efficiency, absolute and spectral transmission, and beam coupling requirements. ESA's new "Integrated Optics" activity started at mid-2007 with the purpose of improving the technology until compliant prototypes can be manufactured and validated, expectedly by the end of 2009. The present paper aims at introducing the project and the components requirements and functions. The selected materials and preliminary designs, as well as the experimental validation logic and test benches are presented. More details are provided on the progress of the main technology: vacuum deposition in the co-evaporation mode and subsequent etching of chalcogenide layers. In addition., preliminary investigations of an alternative technology based on burying a chalcogenide optical fiber core into a chalcogenide substrate are presented. Specific developments of anti-reflective solutions designed for the mitigation of Fresnel losses at the input and output surface of the components are also introduced.

Hydrogen bond-induced pair formation of glycine on the chiral Cu{531} surface

Enantio-specific interactions on intrinsically chiral or chirally modified surfaces can be identified experimentally via comparison of the adsorption geometries of similar nonchiral and chiral molecules. Information about the effects of substrate-related and in interactions on the adsorption geometry of glycine, the only natural nonchiral amino acid, is therefore important for identifying enantio-specific interactions of larger chiral amino acids. We have studied the long- and short-range adsorption geometry and bonding properties of glycine on the intrinsically chiral Cu{531} surface with low-energy electron diffraction, near-edge X-ray absorption One structure spectroscopy, X-ray photoelectron spectroscopy, and temperature-programmed desorption. For coverages between 0.15 and 0.33 ML (saturated chemisorbed layer) and temperatures between 300 and 430 K, glycine molecules adsorb in two different azimuthal orientations, which are associated with adsorption sites on the {110} and {311} microfacets of Cu{531}. Both types of adsorption sites allow a triangular footprint with surface bonds through the two oxygen atoms and the nitrogen atom. The occupation of the two adsorption sites is equal for all coverages, which can be explained by pair formation due to similar site-specific adsorption energies and the possibility of forming hydrogen bonds between molecules on adjacent {110} and {311} sites. This is not the ease for alanine and points toward higher site specificity in the case of alanine, which is eventually responsible for the enantiomeric differences observed for the alanine system.

A new method for evaluating regional air quality forecasts

A Kriging interpolation method is combined with an object-based evaluation measure to assess the ability of the UK Met Office's dispersion and weather prediction models to predict the evolution of a plume of tracer as it was transported across Europe. The object-based evaluation method, SAL, considers aspects of the Structure, Amplitude and Location of the pollutant field. The SAL method is able to quantify errors in the predicted size and shape of the pollutant plume, through the structure component, the over- or under-prediction of the pollutant concentrations, through the amplitude component, and the position of the pollutant plume, through the location component. The quantitative results of the SAL evaluation are similar for both models and close to a subjective visual inspection of the predictions. A negative structure component for both models, throughout the entire 60 hour plume dispersion simulation, indicates that the modelled plumes are too small and/or too peaked compared to the observed plume at all times. The amplitude component for both models is strongly positive at the start of the simulation, indicating that surface concentrations are over-predicted by both models for the first 24 hours, but modelled concentrations are within a factor of 2 of the observations at later times. Finally, for both models, the location component is small for the first 48 hours after the start of the tracer release, indicating that the modelled plumes are situated close to the observed plume early on in the simulation, but this plume location error grows at later times. The SAL methodology has also been used to identify differences in the transport of pollution in the dispersion and weather prediction models. The convection scheme in the weather prediction model is found to transport more pollution vertically out of the boundary layer into the free troposphere than the dispersion model convection scheme resulting in lower pollutant concentrations near the surface and hence a better forecast for this case study.

On the structure of Langmuir turbulence

The Stokes drift induced by surface waves distorts turbulence in the wind-driven mixed layer of the ocean, leading to the development of streamwise vortices, or Langmuir circulations, on a wide range of scales. We investigate the structure of the resulting Langmuir turbulence, and contrast it with the structure of shear turbulence, using rapid distortion theory (RDT) and kinematic simulation of turbulence. Firstly, these linear models show clearly why elongated streamwise vortices are produced in Langmuir turbulence, when Stokes drift tilts and stretches vertical vorticity into horizontal vorticity, whereas elongated streaky structures in streamwise velocity fluctuations (u) are produced in shear turbulence, because there is a cancellation in the streamwise vorticity equation and instead it is vertical vorticity that is amplified. Secondly, we develop scaling arguments, illustrated by analysing data from LES, that indicate that Langmuir turbulence is generated when the deformation of the turbulence by mean shear is much weaker than the deformation by the Stokes drift. These scalings motivate a quantitative RDT model of Langmuir turbulence that accounts for deformation of turbulence by Stokes drift and blocking by the air–sea interface that is shown to yield profiles of the velocity variances in good agreement with LES. The physical picture that emerges, at least in the LES, is as follows. Early in the life cycle of a Langmuir eddy initial turbulent disturbances of vertical vorticity are amplified algebraically by the Stokes drift into elongated streamwise vortices, the Langmuir eddies. The turbulence is thus in a near two-component state, with suppressed and . Near the surface, over a depth of order the integral length scale of the turbulence, the vertical velocity (w) is brought to zero by blocking of the air–sea interface. Since the turbulence is nearly two-component, this vertical energy is transferred into the spanwise fluctuations, considerably enhancing at the interface. After a time of order half the eddy decorrelation time the nonlinear processes, such as distortion by the strain field of the surrounding eddies, arrest the deformation and the Langmuir eddy decays. Presumably, Langmuir turbulence then consists of a statistically steady state of such Langmuir eddies. The analysis then provides a dynamical connection between the flow structures in LES of Langmuir turbulence and the dominant balance between Stokes production and dissipation in the turbulent kinetic energy budget, found by previous authors.

Enantiospecific adsorption of alanine on the chiral Cu{531} surface

We have studied enantiospecific differences in the adsorption of (S)- and (R)-alanine on Cu{531}R using low-energy electron diffraction (LEED), X-ray photoelectron spectroscopy, and near edge X-ray absorption fine structure (NEXAFS) spectroscopy. At saturation coverage, alanine adsorbs as alaninate forming a p(1 4) superstructure. LEED shows a significantly higher degree of long-range order for the S than for the R enantiomer. Also carbon K-edge NEXAFS spectra show differences between (S)- and (R)-alanine in the variations of the ð resonance when the linear polarization vector is rotated within the surface plane. This indicates differences in the local adsorption geometries of the molecules, most likely caused by the interaction between the methyl group and the metal surface and/or intermolecular hydrogen bonds. Comparison with model calculations and additional information from LEED and photoelectron spectroscopy suggest that both enantiomers of alaninate adsorb in two different orientations associated with triangular adsorption sites on {110} and {311} microfacets of the Cu{531} surface. The experimental data are ambiguous as to the exact difference between the local geometries of the two enantiomers. In one of two models that fit the data equally well, significantly more (R)-alaninate molecules are adsorbed on {110} sites than on {311} sites whereas for (S)-alaninate the numbers are equal. The enantiospecific differences found in these experiments are much more pronounced than those reported from other ultrahigh vacuum techniques applied to similar systems.

Model car-exhaust catalyst studied by TPD and TP-RAIRS: Surface reactions of NO on clean and O-covered Ir{100}

The adsorption of NO on Ir{100} has been studied as a function of NO coverage and temperature using temperature programmed reflection absorption infrared spectroscopy (TP-RAIRS), low energy electron diffraction (LEED) and temperature programmed desorption (TPD). After saturating the clean (1 x 5)-reconstructed surface with NO at 95 K. two N-2, desorption peaks are observed upon heating. The first N-2 peak at 346 K results from the decomposition of bridge-bonded NO, and the second at 475 K from the decomposition of atop-bonded NO molecules. NO decomposition is proposed to be the rate limiting step for both N-2 desorption states. For high NO coverages on the (1 x 5) surface, the narrow width of the first N-2 desorption peak is indicative of an autocatalytic process for which the parallel formation of N2O appears to be the crucial step. When NO is adsorbed on the metastable unreconstructed (1 x 1) phase of clean Ir{100} N-2 desorption starts at lower temperatures, indicating that this surface modification is more reactive. When a high coverage of oxygen, near 0.5 ML, is pre-adsorbed on the surface, the decomposition of NO is inhibited and mainly desorption of intact NO is observed.

The surface geometries of the medium and high coverage carbon monoxide structures c(2 × 4)–(2CO) and p(root7- x root7)R19°–(4CO) structure

The surface geometries of the p (root7- x root7)R19degrees-(4CO) and c(2 x 4)-(2CO) layers on Ni {111} and the clean Ni {111} surface were determined by low energy electron diffraction structure analysis. For the clean surface small but significant contractions of d(12) and d(23) (both 2.02 Angstrom) were found with respect to the bulk interlayer distance (2.03 Angstrom). In the c(2 x 4)-(2CO) structure these distances are expanded, with values of d(12) = 2.08 Angstrom and d(23) = 2.06 Angstrom and buckling of 0.08 and 0.02 Angstrom, respectively, in the first and second layer. CO resides near hcp and fcc hollow sites with relatively large lateral shifts away from the ideal positions leading to unequal C-Ni bond lengths between 1.76 and 1.99 Angstrom. For the p(root7- x root7-)R19'-(4CO) layer two best fit geometries were found, which agree in most of their atomic positions, except for one out of four CO molecules, which is either near atop or between bridge and atop. The remaining three molecules reside near hcp and fcc sites, again with large lateral deviations from their ideal positions. The average C Ni bond length for these molecules is, however, the same as for CO on hollow sites at low coverage. The average CNi bond length at hollow sites, the interlayer distances, and buckling in the first Ni layer are similar to the c(2 x 4)(2CO) geometry, only the buckling in the second layer (0.08 Angstrom) is significantly larger. Lateral and vertical shifts of the Ni atoms in the first layer lead to unsymmetric environments for the CO molecules, which can be regarded as an imprint of the chiral p(root7- x root7-)R19degrees lattice geometry onto the substrate.

Spectrally-invariant behavior of zenith radiance around cloud edges simulated by radiative transfer

In a previous paper, we discovered a surprising spectrally-invariant relationship in shortwave spectrometer observations taken by the Atmospheric Radiation Measurement (ARM) program. The relationship suggests that the shortwave spectrum near cloud edges can be determined by a linear combination of zenith radiance spectra of the cloudy and clear regions. Here, using radiative transfer simulations, we study the sensitivity of this relationship to the properties of aerosols and clouds, to the underlying surface type, and to the finite field-of-view (FOV) of the spectrometer. Overall, the relationship is mostly sensitive to cloud properties and has little sensitivity to other factors. At visible wavelengths, the relationship primarily depends on cloud optical depth regardless of cloud phase function, thermodynamic phase and drop size. At water-absorbing wavelengths, the slope of the relationship depends primarily on cloud optical depth; the intercept, by contrast, depends primarily on cloud absorbing and scattering properties, suggesting a new retrieval method for cloud drop effective radius. These results suggest that the spectrally-invariant relationship can be used to infer cloud properties near cloud edges even with insufficient or no knowledge about spectral surface albedo and aerosol properties.

Evaluation of a Lagrangian box model using field measurements from EASE (Eastern Atlantic Summer Experiment) 1996

The Cambridge Tropospheric Trajectory model of Chemistry and Transport (CiTTyCAT), a Lagrangian chemistry model, has been evaluated using atmospheric chemical measurements collected during the East Atlantic Summer Experiment 1996 (EASE '96). This field campaign was part of the UK Natural Environment Research Council's (NERC) Atmospheric Chemistry Studies in the Oceanic Environment (ACSOE) programme, conducted at Mace Head, Republic of Ireland, during July and August 1996. The model includes a description of gas-phase tropospheric chemistry, and simple parameterisations for surface deposition, mixing from the free troposphere and emissions. The model generally compares well with the measurements and is used to study the production and loss of O3 under a variety of conditions. The mean difference between the hourly O3 concentrations calculated by the model and those measured is 0.6 ppbv with a standard deviation of 8.7 ppbv. Three specific air-flow regimes were identified during the campaign – westerly, anticyclonic (easterly) and south westerly. The westerly flow is typical of background conditions for Mace Head. However, on some occasions there was evidence of long-range transport of pollutants from North America. In periods of anticyclonic flow, air parcels had collected emissions of NOx and VOCs immediately before arriving at Mace Head, leading to O3 production. The level of calculated O3 depends critically on the precise details of the trajectory, and hence on the emissions into the air parcel. In several periods of south westerly flow, low concentrations of O3 were measured which were consistent with deposition and photochemical destruction inside the tropical marine boundary layer.

De-agrarianization, re-agrarianization and local economic development: re-orientating livelihoods in African artisanal mining communities

This article contributes to the debate on livelihood diversification in rural sub-Saharan Africa, focusing specifically on the growing economic importance of artisanal and small-scale mining (ASM) in the region. The precipitous decline in the value of many export crops and the removal of subsidies on crucial inputs such as fertilizers have made smallholder production unviable, forcing many farmers to ‘branch out’ into non-farm activities to supplement their incomes. One of the more popular destinations for poor farmers is the low-tech ASM sector which, because of its low barriers to entry, has absorbed millions of rural Africans over the past two decades, the majority of whom are engaged in the extraction of near-surface mineral deposits located on concessions that have been demarcated to multinational corporations. The efforts made hitherto to control this illegal mining activity, both through force and regulation, however, have had little effect, forcing many of the region’s governments and private sector partners to ‘re-think’ their approaches. One strategy that has gained considerable attention throughout the region is intensified support for agrarian-orientated activities, many of which, despite the problems plaguing smallholder agricultural sector and challenges with making it more economically sustainable, are being lauded as appropriate ‘alternative’ sources of employment to artisanal mining. After examining where artisanal mining fits into the de-agrarianization ‘puzzle’ in sub-Saharan Africa, the article critiques the efficacy of ‘re-agrarianization’ as a strategy for addressing the region’s illegal mining problem. A case study of Ghana is used to shed further light on these issues.

Magnetic discontinuities in the near-earth solar wind: evidence of in-transit turbulence or remnants of coronal structure?

Fluctuations in the solar wind plasma and magnetic field are well described by the sum of two power law distributions. It has been postulated that these distributions are the result of two independent processes: turbulence, which contributes mainly to the smaller fluctuations, and crossing the boundaries of flux tubes of coronal origin, which dominates the larger variations. In this study we explore the correspondence between changes in the magnetic field with changes in other solar wind properties. Changes in density and temperature may result from either turbulence or coronal structures, whereas changes in composition, such as the alpha-to-proton ratio are unlikely to arise from in-transit effects. Observations spanning the entire ACE dataset are compared with a null hypothesis of no correlation between magnetic field discontinuities and changes in other solar wind parameters. Evidence for coronal structuring is weaker than for in-transit turbulence, with only ∼ 25% of large magnetic field discontinuities associated with a significant change in the alpha-to-proton ratio, compared to ∼ 40% for significant density and temperature changes. However, note that a lack of detectable alpha-to-proton signature is not sufficient to discount a structure as having a solar origin.