The Application Of Radioisotopes In The Study Of Estuarine Sedimentary Processes

The spatial and temporal distributions of some radionuclides in effluents originating from the British Nuclear Fuels Ltd (BNFL) reprocessing plant at Windscale, which are released into the Irish Sea, have been studied in sediments at 16 sites in the salt marsh region near Newbiggin on the Esk estuary Cumbria, England. The concentration of non-conservative radionuclides in surface sediments of the area cannot be described by a single parameter, but there is a high correlation with organic C, Cu, Al and the Si : Al ratio with particle size. The preservation of the historical record of the BNFL effluents in the Esk sediments is dependent on the hydrology of the area, as it effects such processes as accretion, erosion and remixing. From the 106Ru and 210Po concentrations and the 137Cs : 134Cs ratio in the sediment profiles with depth, we have identified these processes. Sedimentation rates at sites of accretion vary between 0·5 and 3 cm year−1. However, at some sites they appear to be much higher, approximately 6 cm year−1 in the top 10 cm, but they are not consistent throughout the depth profiles. This may be a true reflection of variable accretion related to sediment type, or one which is influenced by surficial mixing. Some cores showed evidence of continuous accretion but no significant radioactivity was detected at depths below 35–40 cm, indicating an overall sedimentation rate of approximately 1·5 cm year−1 for the 25–30-year period since BNFL effluents first entered the Irish Sea.

Relationships Between Seston Available Food And Feeding-Activity In The Common Mussel Mytilus-Edulis

The feeding and metabolic rates of Mytilus edulis L. of different body sizes were measured in response to changes in particle concentrations ranging from 2 to 350 mg l-1. Rates of oxygen consumption were not significantly affected by changes in seston concentration, whereas clearance rates gradually declined with increasing particle concentration. Pseudofaeces production was initiated at relatively low seston concentrations (<5 mg l-1). Marked seasonal changes were recorded in the composition of suspended particulates (seston) in an estuary in south-west England. Total seston was sampled at frequent intervals throughout an annual cycle and analysed in terms of: particle size-frequency distributions, total dry weight (mg l-1), inorganic content, chlorophyll a, carbohydrate, protein and lipid. The particulate carbohydrate, protein and lipid content provided an estimate of the food content of the seston. The results are discussed in terms of the “food available” to a nonselective suspension feeder, such as M. edulis, during a seasonal cycle. The effect of inorganic silt in suspension was mainly to limit by “dilution” the amount of food material ingested rather than to reduce the amount of material filtered by the mussel. In winter, the food content of the material ingested was 5%, and this increased to 25% during the spring and summer.

Acceptance angle effects on the beam attenuation in the ocean

The beam attenuation serves as a proxy for particulate matter and is a key parameter in visibility algorithms for the aquatic environment. It is well known, however, that the beam attenuation is a function of the acceptance angle of the transmissometer used to measure it. Here we compare eight different transmissometers with four different acceptance angles using four different deployment strategies and sites, and find that their mean attenuation values differ markedly and in a consistent way with instrument acceptance angle: smaller acceptance angles provide higher beam attenuation values. This difference is due to variations in scattered light collected with different acceptance angles and is neither constant nor easy to parameterize. Variability (in space or time) in the ratios of beam attenuations measured by two different instruments correlates, in most cases, with the particle size parameter (as expected from Mie theory), but this correlation is often weak and can be the opposite of expectations based on particle size changes. We recommended careful consideration of acceptance angle in applications of beam transmission data especially when comparing data from different instruments. (C) 2009 Optical Society of America

Global assessment of ocean carbon export by combining satellite observations and food-web models

The export of organic carbon from the surface ocean by sinking particles is an important, yet highly uncertain, component of the global carbon cycle. Here we introduce a mechanistic assessment of the global ocean carbon export using satellite observations, including determinations of net primary production and the slope of the particle size spectrum, to drive a food-web model that estimates the production of sinking zooplankton feces and algal aggregates comprising the sinking particle flux at the base of the euphotic zone. The synthesis of observations and models reveals fundamentally different and ecologically consistent regional-scale patterns in export and export efficiency not found in previous global carbon export assessments. The model reproduces regional-scale particle export field observations and predicts a climatological mean global carbon export from the euphotic zone of ~6 Pg C yr−1. Global export estimates show small variation (typically < 10%) to factor of 2 changes in model parameter values. The model is also robust to the choices of the satellite data products used and enables interannual changes to be quantified. The present synthesis of observations and models provides a path for quantifying the ocean's biological pump.

Bimetallic effects in the liquid phase hydrogenation of 2-butanone

A series of bimetallic Ru-containing monometallic and bimetallic catalysts were prepared and tested for their activity for the hydrogenation of 2-butanone to 2-butanol at 30 °C and 3 bar H2. RuPt bimetallic catalysts were the most active for the reaction, with a ratio of 5 wt% Ru:1 wt% Pt on activated carbon (AC) found to be optimum. The activity of this bimetallic catalyst was more than double that of the sum of the activities of the monometallic Ru and Pt catalysts, providing evidence of a “bimetallic” effect. Structural analysis of the bimetallic catalysts revealed that they consisted of clusters of particles of the order of 1–2 nm. Extended X-ray absorption fine structure analysis showed that there were two types of particle on the surface of the bimetallic RuPt catalyst, specifically monometallic Ru and bimetallic RuPt particles. For the bimetallic particles, it was possible to fit the data with a model in which a Ru core of 1.1 nm is enclosed by two Pt-rich layers, the outer layer containing only 13 at% Ru. Pretreatment of the monometallic and bimetallic catalysts in hydrogen had a significant effect on the activity. Both the bimetallic and monometallic Ru-based catalysts showed a trend of decreasing activity with increasing temperature of prereduction in hydrogen. This loss of activity was almost fully reversible by exposure of the catalysts to air after reduction. The changing activity with exposure to different gas phase environments could not be attributed to changes in particle size or surface composition. It is proposed that the introduction of hydrogen results in a gradual smoothing of the surface and loss of defect sites; this process being reversible on introduction of air. These defect sites are particularly important for the dissociative adsorption of hydrogen, potentially the rate-determining step in this reaction.

Organisational controls, typologies and time scales of paraglacial gravel-dominated coastal systems

The fundamental controls on the initiation and development of gravel-dominated deposits (beaches and barriers) on paraglacial coasts are particle size and shape, sediment supply, storm wave activity (primarily runup), relative sea-level (RSL) change, and terrestrial basement structure (primarily as it affects accommodation space). This paper examines the stochastic basis for barrier organisation as shown by variation in gravel barrier architecture. We recognise punctuated self-organisation of barrier development that is disrupted by short phases of barrier instability. The latter results from positive feedback causing barrier breakdown when sediment supply is exhausted. We examine published typologies for gravel barriers and advocate a consolidated perspective using rate of RSL change and sediment supply. We also consider the temporal variation in controls on barrier development. These are examined in terms of a simple behavioural model (BARCH) for prograding gravel barrier architecture and its sensitivity to such controls. The nature of macroscale (102–103 years) gravel barrier development, including inherited characteristics that influence barrier genesis, as well as forcing from changing RSL, sediment supply, headland control and barrier inertia, is examined in the context of long-surviving barriers along the southern England coastline.

Reuse of construction waste: performance under repeated loading

The use of recycled aggregates has increased greatly over the last decade owing to enhanced environmental sensitivities. The level of performance required by such materials is dependent upon the applications for which they are used. Many recycled construction wastes have adequate shear strength in relation to various geotechnical applications. However, a possible drawback of these materials is the risk of crushing during repeated loading. The work reported in this paper examined two waste materials: crushed concrete and building debris, both regarded as construction wastes. Tests were also performed on traditionally used crushed rock, in this case basalt. The materials were subjected to repeated loading in a large direct shear apparatus. The amount of crushing was quantified by performing particle size analysis of the tested material. The results have shown that both recycled construction wastes were susceptible to particle crushing. The amount of crushing was influenced by both the vertical pressure and the number of loading cycles. This leads to a marked decrease in peak friction angle

Development of sampling methods for Raman analysis of solid dosage forms of therapeutic and illicit drugs

The results of a study aimed at determining the most important experimental parameters for automated, quantitative analysis of solid dosage form pharmaceuticals (seized and model 'ecstasy' tablets) are reported. Data obtained with a macro-Raman spectrometer were complemented by micro-Raman measurements, which gave information on particle size and provided excellent data for developing statistical models of the sampling errors associated with collecting data as a series of grid points on the tablets' surface. Spectra recorded at single points on the surface of seized MDMA-caffeine-lactose tablets with a Raman microscope (lambda(ex) = 785 nm, 3 mum diameter spot) were typically dominated by one or other of the three components, consistent with Raman mapping data which showed the drug and caffeine microcrystals were ca 40 mum in diameter. Spectra collected with a microscope from eight points on a 200 mum grid were combined and in the resultant spectra the average value of the Raman band intensity ratio used to quantify the MDMA: caffeine ratio, mu(r), was 1.19 with an unacceptably high standard deviation, sigma(r), of 1.20. In contrast, with a conventional macro-Raman system (150 mum spot diameter), combined eight grid point data gave mu(r) = 1.47 with sigma(r) = 0.16. A simple statistical model which could be used to predict sigma(r) under the various conditions used was developed. The model showed that the decrease in sigma(r) on moving to a 150 mum spot was too large to be due entirely to the increased spot diameter but was consistent with the increased sampling volume that arose from a combination of the larger spot size and depth of focus in the macroscopic system. With the macro-Raman system, combining 64 grid points (0.5 mm spacing and 1-2 s accumulation per point) to give a single averaged spectrum for a tablet was found to be a practical balance between minimizing sampling errors and keeping overhead times at an acceptable level. The effectiveness of this sampling strategy was also tested by quantitative analysis of a set of model ecstasy tablets prepared from MDEA-sorbitol (0-30% by mass MDEA). A simple univariate calibration model of averaged 64 point data had R-2 = 0.998 and an r.m.s. standard error of prediction of 1.1% whereas data obtained by sampling just four points on the same tablet showed deviations from the calibration of up to 5%.

A review of the effect of the addition of hydrogen in the selective catalytic reduction of NOx with hydrocarbons on silver catalysts

Research is progressing fast in the field of the hydrogen assisted hydrocarbon selective catalytic reduction (HC-SCR) over Ag-based catalysts: this paper is a review of the work to date in this area. The addition of hydrogen to the HC-SCR reaction feed over Ag/Al2O3 results in a remarkable improvement in NO (x) conversion using a variety of different hydrocarbon feeds. There is some debate concerning the role that hydrogen has to play in the reaction mechanism and its effect on the form of Ag present during the reaction. Many of the studies use in situ UV-Vis spectroscopy to monitor the form of Ag in the catalyst and appear to indicate that the addition of hydrogen promotes the formation of small Ag clusters which are highly reactive for NO (x) conversion. However, some authors have expressed concern about the use of this technique for these materials and further work is required to address these issues before this technique can be used to give an accurate assessment of the state of Ag during the SCR reaction. A study using in situ EXAFS to probe the H-2 assisted octane-SCR reaction has shown that small Ag particles (containing on average 3 silver atoms) are formed during the SCR reaction but that the addition of H-2 to the feed does not result in any further change in the Ag particle size. This points to the direct involvement of H-2 in the reaction mechanism. Clearly the addition of hydrogen results in a large increase in the number and variety of adsorbed species on the surface of the catalyst during the reaction. Some authors have suggested that conversion of cyanide to isocyanate is the rate-determining step and that hydrogen promotes this conversion. Others have suggested that hydrogen reduces nitrates to more reactive nitrite species which can then activate the hydrocarbon; activation of the hydrocarbon to form acetates has been proposed as the key step. It is probable that all these promotional effects can take place and that it very much depends on the reaction temperature and feed conditions as to which one is most important.

Effects of environment and an introduced invertebrate species on the structure of benthic macroinvertebrate species at the catchment level

Biotic interactions such as predation and competition can influence aquatic communities at small spatial scales, but they are expected to be overridden by environmental factors at large scales. The continuing threat to freshwater biodiversity of biological invasions indicates that biotic factors do, however, have important structuring roles. In Irish rivers, the native amphipod Gammarus duebeni celticus has become locally extinct, ostensibly through differential predation by the more aggressive and introduced G. pulex. This mechanism explains impacts of G. pulex at within-river spatial scales on native macroinvertebrate community diversity, including declines in ephemeropterans, plecopterans, dipterans and oligochaetes. To determine if these patterns are predictable at larger spatial scales, we assessed patterns in native macroinvertebrate communities across river sites of the Erne catchment in 1998 and 1999, in conjunction with the distribution of G. pulex and G. d. celticus. In both years, G. pulex dominated invaded sites, whereas G. d. celticus occurred at low abundance in uninvaded sites. In both years, invaded sites had lower diversity and fewer pollution sensitive invertebrate species than un-invaded sites. Community ordination in 1998 showed that invaded sites had higher conductivity, smaller substrate particle size and comprised a lower proportion of pollution sensitive taxa including Ephemeroptera and Plecoptera. In contrast, in 1999, conductivity was the only variable explaining site ordination along axis 1, but was unable to separate sites with respect to invasion status. A second explanatory axis separated sites with respect to invasion status, with invaded sites having fewer taxa, including lower abundance of ephemeropterans, dipterans and plecopterans. Laboratory experiments examined the potential role of differential predation between the two Gammarus species in explaining these taxon specific patterns in the field. Survival of the ephemeropterans, Ephemerella ignita and Ecdyonurus venosus and the isopod, Asellus aquaticus, was lower when interacting with G. pulex than with G. d. celticus. This study indicates that G. putex may alter invertebrate community structure at scales beyond those detected within individual rivers. However, effects may be influenced by gradients in physico-chemistry, which may be temporal or depend on catchment characteristics. Invasions by amphipods have increased globally, thus comprehensive assessments of their impacts and of other aquatic invaders, may only be apparent when studies are conducted at a range of spatio-temporal scales.

Activation of waste MDF sawdust charcoal and its reactive dye adsorption characteristics

This paper reports an experimental investigation of converting waste medium density fibreboard (MDF) sawdust into chars and activated carbon using chemical activation and thermal carbonisation processes. The MDF sawdust generated during the production of architectural mouldings was characterised and found to have unique properties in terms of fine particle size and high particle density. It also has a high content of urea formaldehyde resin used as a binder in the manufacturing of MDF board. Direct thermal carbonisation and chemical activation of the sawdust by metal impregnation and acid (phosphoric acid) treatment prior to pyrolysis treatment were carried out. The surface morphology of the raw dust, its chars and activated carbon were examined using scanning electron microscopy (SEM). Adsorptive properties and total pore volume of the materials were also analysed using the BET nitrogen adsorption method. Liquid adsorption of a reactive dye (Levafix Brilliant red E-4BA) by the derived sawdust carbon was investigated in batch isothermal adsorption process and the results compared to adsorption on to a commercial activated carbon (Filtrasorb F400). The MDF sawdust carbon exhibited in general a very low adsorption capacity towards the reactive dye, and physical characterisation of the carbon revealed that the conventional chemical activation and thermal carbonisation process were ineffective in developing a microporous structure in the dust particles. The small size of the powdery dust, the high particle density, and the presence of the urea formaldehyde resin all contributed to the difficulty of developing a proper porous structure during the thermal and chemical activation process. Finally, activation of the dust material in a consolidated form (cylindrical pellet) only achieved very limited improvement in the dye adsorption capacity. This original study, reporting some unexpected outcomes, may serve as a stepping-stone for future investigations of recycle and reuse of the waste MDF sawdust which is becoming an increasing environmental and cost liability. (C) 2004 Elsevier Ltd. All rights reserved.

Characterisation of fluidised bed granulation processes using in situ Raman spectroscopy

Previous work by the authors Walker et al. [2007b. Fluidised bed characterisation using Raman spectroscopy: applications to pharmaceutical processing. Chemical Engineering Science 62, 3832–3838] illustrated that Raman spectroscopy could be used to provide 3-D maps of the concentration and chemical structure of particles in motion in a fluidised bed, within a relatively short (120 s) time window. Moreover, we reported that the technique, as outlined, has the potential to give detailed in-situ information on how the structure and composition of granules/powders within the fluidised bed (dryer or granulator) vary with the position and evolve with time. In this study we extended the original work by shortening the time window of the Raman spectroscopic analysis to 10 s, which has allowed the in-situ real-time characterisation of a fluidised bed granulation process. Here we show an important new use of the technique which allows in-situ measurement of the composition of the material within the fluidised bed in three spatial dimensions and as a function of time. This is achieved by recording Raman spectra using a probe positioned within the fluidised bed on a long-travel x–y–z stage. In these experiments the absolute Raman intensity is used to provide a direct measure of the amount of any given material in the probed volume, i.e. a particle density. Particle density profiles have been calculated over the granulation time and show how the volume of the fluidised bed decreases with an increase mean granule size. The Raman spectroscopy analysis indicated that nucleation/coalescence in this co-melt fluidised hot melt granulation system occurred over a relatively short time frame (t<30 s). The Raman spectroscopic technique demonstrated accurate correlation with independent granulation experiments which provided particle size distribution analysis. The similarity of the data indicates that the Raman spectra accurately represent solids ratios within the bed, and thus the techniques quantitative capabilities for future use in the pharmaceutical industry.

Adsorption of basic dyes from aqueous solution onto activated carbons

The aim of this research is to compare the adsorption capacity of different types of activated carbons produced by steam activation in small laboratory scale and large industrial scale processes. Equilibrium behaviour of the activated carbons was investigated by performing batch adsorption experiments using bottle-point method. Basic dyes (methylene blue (MB), basic red (BR) and basic yellow (BY)) were used as adsorbates and the maximum adsorptive capacity was determined. Adsorption isotherm models, Langmuir, Freundlich and Redlich-Peterson were used to simulate the equilibrium data at different experimental parameters (pH and adsorbent particle size). It was found that PAC2 (activated carbon produced from New Zealand coal using steam activation) has the highest adsorptive capacity towards MB dye (588 mg/g) followed by F400 (476 mg/g) and PAC 1 (380 mg/g). BR and BY showed higher adsorptive affinity towards PAC2 and F400 than MB. Under comparable conditions, adsorption capacity of basic dyes, MB, BR and BY onto PAC 1, PAC2 and F400 increased in the order: MB <BR <BY. Redlich-Peterson model was found to describe the experimental data over the entire range of concentration under investigation. All the systems show favourable adsorption of the basic dyes with 0 <R-L <I (C) 2007 Elsevier B.V. All rights reserved.

Nucleation and growth in fluidised hot melt granulation

Fluidised hot melt granulation (FHMG) is a novel technology for granulation process in pharmaceutical industry, which has distinct advantages over other commercial techniques. The aim of this research was to investigate granulation and the effect of process parameters that may affect FHMG process. In this work, ballotini beads were used as the model particles and Lutrol (R) F 68 Poloxamer 188 was used as meltable solid binder. In order to determine the granulation and nucleation mechanism in this co-melt FHMG system, several parameters were investigated, such as binder content, particle size of binder and particle size and hydrophobicity of ballotini. These parameters were correlated to granule size distribution, mean granule size and granule shape. Furthermore, these experimental investigations were designed so that the coalescence model could be applied to the co-melt FHMG system. The analysis indicated that the non-inertial regime extends over a relatively short time period of

Liquid marble formation using hydrophobic powders

This work aims to investigate and quantitatively measure “liquid marble” phenomena using hydrophobic powders (granules). The hydrophobic powders based on a copper substrate were prepared by a silver deposition technique of particle sizes 9 µm, 20 µm and 320 µm and of contact angle with water approaching 160°. The hydrophobic powder poly-methylmethacralate (PMMA) particle size 42 µm and contact angle of 120° was also used to determine the effect of powder density on liquid marble stability. The experimental investigations indicated that for successful formation of liquid marbles a number of variables in addition to hydrophobicity need to be considered, namely: powder density; powder particle size; powder shape; liquid marble formation technique. It was found that liquid marbles were formed using all four powders to varying extents, with a low powder particle size forming more stable liquid marbles. In a series of gravimetric tests, adhered powder mass on liquid marbles was found to be directly proportional to the water droplet surface area. A more complete coverage of the water drops were found with PMMA powder than the hydrophobic granules. Moreover, a further procedure was developed to increase the mechanical strength of the liquid marble, by polymerising methylmethacrylate (MMA) on the surface of a PMMA powder – liquid marble, with the aim of maintaining water within a more robust PMMA – liquid marble shell. This technique may prove to be a novel way of encapsulating drug compounds, such as gentamicin sulphate, for PMMA bone cement.