Pathways utilized by heavy metal pollutants in urban stormwater runoff

The research concerned the assessment of the pathways utilized by heavy metal pollutants in urban stormwater runoff. A separately sewered urban residential catchment of approximately 107 hectares in Chelmsley Wood, north-east Birmingham was the subject of the field investigation. The catchment area, almost entirely residential, had no immediate industrial heavy metal input, however, industry was situated to the north of the catchment. The perimeter of the catchment was bounded by the M6 motorway on the northern and eastern sides and was believed to contribute to aerial deposition. Metal inputs to the ground surface were assumed to be confined to normal suburban activities, namely, aerial deposition, vehicular activity and anthropological activities. A programme of field work was undertaken over a 12 month period, from July 1983 to July 1984. Monthly deposition rates were monitored using a network of deposit cannisters and roadside sediment and soil samples were taken. Stormwater samples were obtained for 19 separate events. All samples were analysed for iron, lead, zinc, copper, chromium, nickel and cadmium content. Rainfall was recorded on site with additional meteorological data obtained from local Meteorological Offices. Use was made of a simple conceptual model designed for the catchment to substantiate hypotheses derived from site investigations and literature, to investigate the pathways utilized for the transportation of heavy metals throughout the catchment.

Identification of industrial sources of airborne heavy metal pollution in urban areas

The research examines the deposition of airborne particles which contain heavy metals and investigates the methods that can be used to identify their sources. The research focuses on lead and cadmium because these two metals are of growing public and scientific concern on environmental health grounds. The research consists of three distinct parts. The first is the development and evaluation of a new deposition measurement instrument - the deposit cannister - designed specifically for large-scale surveys in urban areas. The deposit cannister is specifically designed to be cheap, robust, and versatile and therefore to permit comprehensive high-density urban surveys. The siting policy reduces contamination from locally resuspended surface-dust. The second part of the research has involved detailed surveys of heavy metal deposition in Walsall, West Midlands, using the new high-density measurement method. The main survey, conducted over a six-week period in November - December 1982, provided 30-day samples of deposition at 250 different sites. The results have been used to examine the magnitude and spatial variability of deposition rates in the case-study area, and to evaluate the performance of the measurement method. The third part of the research has been to conduct a 'source-identification' exercise. The methods used have been Receptor Models - Factor Analysis and Cluster Analysis - and a predictive source-based deposition model. The results indicate that there are six main source processes contributing to deposition of metals in the Walsall area: coal combustion, vehicle emissions, ironfounding, copper refining and two general industrial/urban processes. |A source-based deposition model has been calibrated using facctorscores for one source factor as the dependent variable, rather than metal deposition rates, thus avoiding problems traditionally encountered in calibrating models in complex multi-source areas. Empirical evidence supports the hypothesised associatlon of this factor with emissions of metals from the ironfoundry industry.

Some aspects of the interaction of humic substances with metal ions

Humic substances are the major organic constituents of soils and sediments. They are heterogeneous, polyfunctional, polydisperse, macromolecular and have no accurately known chemical structure. Their interactions with radionuclides are particularly important since they provide leaching mechanisms from disposal sites. The central theme to this research is the interaction of heavy metal actinide analogues with humic materials. Studies described focus on selected aspects of the characteristics and properties of humic substances. Some novel approaches to experiments and data analysis are pursued. Several humic substances are studied; all but one are humic acids, and those used most extensively were obtained commercially. Some routine characterisation techniques are applied to samples in the first instance. Humic substances are coloured, but their ultra-violet and visible absorption spectra are featureless. Yet, they fluoresce over a wide range of wavelengths. Enhanced fluorescence in the presence of luminescent europium(III) ions is explained by energy transfer from irradiated humic acid to the metal ion in a photophysical model. Nuclear magnetic resonance spectroscopy is applied to the study of humic acids and their complexes with heavy metals. Proton and carbon-13 NMR provides some structural and functionality information; Paramagnetic lanthanide ions affect these spectra. Some heavy metals are studied as NMR nuclei, but measurements are restricted by their sensitivity. A humic acid is fractionated yielding a broad molecular weight distribution. Electrophoretic mobilities and particle radii determined by Laser Doppler Electrophoretic Light Scattering are sensitive to the conditions of the supporting media, and the concentration and particle size distribution of humic substances. In potentiometric titrations of humate dispersions, the organic matter responds slowly and the mineral acid addition is buffered. Proton concentration data is modelled and a mechanism is proposed involving two key stages, both resulting in proton release after some conformational changes.

Autocatalytic deposition of composite coatings

The deposition and properties of electroless nickel composite coatings containing graphite, PTFE and chromium were investigated. Solutions were developed for the codeposition of graphite and chromium with electroless nickel. Solutions for the deposition of graphite contained heavy metal ions for stability, with non-ionic and anionic surfactants to provide wetting and dispersion of the particles. Stability for the codeposition of chromium particles was achieved by oxidation of the chromium. Thin oxide layers of 200 nm thick prevented initiation of the electroless reaction onto the chromium. A mechanism for the formation of electroless composite coatings was considered based on the physical adsorption of particles and as a function of the adsorption of charged surfactants and metal cations from solution. The influence of variables such as particle concentration in solution, particle size, temperature, pH, and agitation on the volume percentage of particles codeposited was studied. The volume percentage of graphite codeposited was found to increase with concentration in solution and playing rate. An increase in particle size and agitation reduced the volume percentage codeposited. The hardness of nickel-graphite deposits was found to decrease with graphite content in the as-deposited and heat treated condition. The frictional and wear properties of electroless nickel-graphite were studied and compared to those of electroless nickel-PTFE. The self-lubricating nature of both coatings was found to be dependent on the ratio of coated area to uncoated area, the size and content of lubricating material in the deposit, and the load between contacting surfaces. The mechanism of self-lubrication was considered, concluding that graphite only produced an initial lubricating surface due to the orientation of flakes, unlike PTFE, which produced true self-lubrication throughout the coating life. Heat treatment of electroless nickel chromium deposits at 850oC for 8 and 16 hours produced nickel-iron-chromium alloy deposits with a phosphorus rich surface of high hardness. Coefficients of friction and wear rates were intially moderate for the phosphorus rich layer but increased for the nickel-iron-chromium region of the coating.

Background levels of urban land contamination

The research work reported in this thesis is concerned with the development and application of an urban scale sampling methodology for measuring and assessing background levels of heavy metal soil contamination in large and varied urban areas. The policy context of the work is broadly the environmental health problems posed by contaminated land and their implications for urban development planning. Within this wider policy context, the emphasis in the research has been placed on issues, related to the determination and application of 'guidelines' for assessing the significance of contaminated land for environmental planning. In concentrating on background levels of land contamination, the research responds to the need for additional techniques which address both the problems of measuring soil contamination at the urban scale and which are also capable of providing detailed information for use in the assessment of contaminated sites. Therefore, a key component of the work has been the development of a land-use based sampling framework for generating spatially comprehensive data on heavy metals in soil. The utility of the information output of the sampling method is demonstrated in two alternative ways. Firstly, it has been used to map the existing pattern of typical levels of heavy metals in urban soils. Secondly, it can be used to generate both generalised data in the form of 'reference levels' from which the overall significance of .background contamination may be assessed and detailed data, termed 'normal limit levels' for use in the assessment of site specific investigation data. The fieldwork was conducted in the West Midlands Metropolitan County and surface soil has been sampled and analysed for a measure of plant-available' and 'total' lead cadmium, copper and zinc. The research contrasts with much of the previous work on contaminated land which has generally concentrated on either the detailed investigation of individual sites suspected of being contaminated or the appraisal of land contamination resulting from specific point sources.

Crack closure and residual stress effects in fatigue of a particle-reinforced metal matrix composite

A study of the influence of macroscopic quenching stresses on long fatigue crack growth in an aluminium alloy-SiC composite has been made. Direct comparison between quenched plate, where high residual stresses are present, and quenched and stretched plate, where they have been eliminated, has highlighted their rôle in crack closure. Despite similar strength levels and identical crack growth mechanisms, the stretched composite displays faster crack growth rates over the complete range of ΔK, measured at R = 0.1, with threshold being displaced to a lower nominal ΔK value. Closure levels are dependent upon crack length, but are greater in the unstretched composite, due to the effect of surface compressive stresses acting to close the crack tip. These result in lower values of ΔKeff in the unstretched material, explaining the slower crack growth rates. Effective ΔKth values are measured at 1.7 MPa√m, confirmed by constant Kmax testing. In the absence of residual stress, closure levels of approximately 2.5 MPa√m are measured and this is attributed to a roughness mechanism.

An investigation of the mechanics of wire drawing with the superposition of an oscillatory drawing stress

A number of investigators have studied the application of oscillatory energy to a metal undergoing plastic deformation. Their results have shown that oscillatory stresses reduce both the stress required to initiate plastic deformation and the friction forces between the tool and workpiece. The first two sections in this thesis discuss historically and technically the devolopment of the use of oscillatory energy techniques to aid metal forming with particular reference to wire drawing. The remainder of the thesis discusses the research undertaken to study the effect of applying longitudinal oscillations to wire drawing. Oscillations were supplied from an electric hydraulic vibrator at frequencies in the range 25 to 500 c/s., and drawing tests were performed at drawing speeds up to 50 ft/m. on a 2000 lbf. bull-block. Equipment was designed to measure the drawing force, drawing torque, amplitude of die and drum oscillation and drawing speed. Reasons are given for selecting mild steel, pure and hard aluminium, stainless steel and hard copper as the materials to be drawn, and the experimental procedure and calibration of measuring equipment arc described. Results show that when oscillatory stresses are applied at frequencies within the range investigated : (a) There is no reduction in the maximum drawing load. (b) Using sodium stearate lubricant there is a negligible reduction in the coefficient of friction between the die and wire. (c) Pure aluminium does not absorb sufficient oscillatory energy to ease the movement of dislocations. (d) Hard aluminium is not softened by oscillatory energy accelerating the diffusion process. (e) Hard copper is not cyclically softened. A vibration analysis of the bull-block and wire showed that oscillatory drawiing in this frequency range, is a mechanical process of straining; and unstraining the drawn wire, and is dependent upon the stiffness of the material being drawn and the drawing machine. Directions which further work should take are suggested.

Synthesis and characterisation of pillared clay catalysts for hydro-cracking of heavy liquid fuels

A range of chromia pillared montmorillonite and tin oxide pillared laponite clay catalysts, as well as new pillared clay materials such as cerium and europium oxide pillared montmorillonites were synthesised. Methods included both conventional ion exchange techniques and microwave enhanced methods to improve performance and/or reduce preparation time. These catalytic materials were characterised in detail both before and after use in order to study the effect of the preparation parameters (starting material, preparation method, pillaring species, hydroxyl to metal ratio etc.) and the hydro cracking procedure on their properties. This led to a better understanding of the nature of their structure and catalytic operation. These catalysts were evaluated with regards to their performance in hydrocracking coal derived liquids in a conventional microbomb reactor (carried out at Imperial College). Nearly all catalysts displayed better conversions when reused. The chromia pillared montmorillonite CM3 and the tin oxide pillared laponite SL2a showed the best "conversions". The intercalation of chromium in the form of chromia (Cr203) in the interlayer clearly increased conversion. This was attributed to the redox activity of the chromia pillar. However, this increase was not proportional to the increase in chromium content or basal spacing. In the case of tin oxide pillared laponite, the catalytic activity might have been a result of better access to the acid sites due to the delaminated nature of laponite, whose activity was promoted by the presence of tin oxide. The manipulation of the structural properties of the catalysts via pillaring did not seem to have any effect on the catalysts' activity. This was probably due to the collapse of the pillars under hydrocracking conditions as indicated by the similar basal spacing of the catalysts after use. However, the type of the pillaring species had a significant effect on conversion. Whereas pillaring with chromium and tin oxides increased the conversion exhibited by the parent clays, pillaring with cerium and europium oxides appeared to have a detrimental effect. The relatively good performance of the parent clays was attributed to their acid sites, coupled with their macropores which are able to accommodate the very high molecular mass of coal derived liquids. A microwave reactor operating at moderate conditions was modified for hydro cracking coal derived liquids and tested with the conventional catalyst NiMo on alumina. It was thought that microwave irradiation could enable conversion to occur at milder conditions than those conventionally used, coupled with a more effective use of hydrogen. The latter could lead to lower operating costs making the process cost effective. However, in practice excessive coke deposition took place leading to negative total conversion. This was probably due to a very low hydrogen pressure, unable to have any hydro cracking effect even under microwave irradiation. The decomposition of bio-oil under microwave irradiation was studied, aiming to identify the extent to which the properties of bio-oil change as a function of time, temperature, mode of heating, presence of char and catalyst. This information would be helpful not only for upgrading bio-oil to transport fuels, but also for any potential fuel application. During this study the rate constants of bio-oil's decomposition were calculated assuming first order kinetics.

Mechanical properties of sheet metal under forming conditions

In the bulge test, a sheet metal specimen is clamped over a circular hole in a die and formed into a bulge by the hydraulic pressure on one side of the specirnen. As the unsupported part of the specimen is deformed in this way, its area is increased, in other words, the material is generally stretched and its thickness generally decreased. The stresses causing this stretching action are the membrane stresses in the shell generated by the hydraulic pressure, in the same way as the rubber in a toy balloon is stretched by the membrane stresses caused by the air inside it. The bulge test is a widely used sheet metal test, to determine the "formability" of sheet materials. Research on this forming process (2)-(15)* has hitherto been almost exclusively confined to predicting the behaviour of the bulged specimen through the constitutive equations (stresses and strains in relation to displacements and shapes) and empirical work hardening characteristics of the material as determined in the tension test. In the present study the approach is reversed; the stresses and strains in the specimen are measured and determined from the geometry of the deformed shell. Thus, the bulge test can be used for determining the stress-strain relationship in the material under actual conditions in sheet metal forming processes. When sheet materials are formed by fluid pressure, the work-piece assumes an approximately spherical shape, The exact nature and magnitude of the deviation from the perfect sphere can be defined and measured by an index called prolateness. The distribution of prolateness throughout the workpiece at any particular stage of the forming process is of fundamental significance, because it determines the variation of the stress ratio on which the mode of deformation depends. It is found. that, before the process becomes unstable in sheet metal, the workpiece is exactly spherical only at the pole and at an annular ring. Between the pole and this annular ring the workpiece is more pointed than a sphere, and outside this ring, it is flatter than a sphere. In the forming of sheet materials, the stresses and hence the incremental strains, are closely related to the curvatures of the workpiece. This relationship between geometry and state of stress can be formulated quantitatively through prolateness. The determination of the magnitudes of prolateness, however, requires special techniques. The success of the experimental work is due to the technique of measuring the profile inclination of the meridional section very accurately. A travelling microscope, workshop protractor and surface plate are used for measurements of circumferential and meridional tangential strains. The curvatures can be calculated from geometry. If, however, the shape of the workpiece is expressed in terms of the current radial (r) and axial ( L) coordinates, it is very difficult to calculate the curvatures within an adequate degree of accuracy, owing to the double differentiation involved. In this project, a first differentiation is, in effect, by-passed by measuring the profile inclination directly and the second differentiation is performed in a round-about way, as explained in later chapters. The variations of the stresses in the workpiece thus observed have not, to the knowledge of the author, been reported experimentally. The static strength of shells to withstand fluid pressure and their buckling strength under concentrated loads, both depend on the distribution of the thickness. Thickness distribution can be controlled to a limited extent by changing the work hardening characteristics of the work material and by imposing constraints. A technique is provided in this thesis for determining accurately the stress distribution, on which the strains associated with thinning depend. Whether a problem of controlled thickness distribution is tackled by theory, or by experiments, or by both combined, the analysis in this thesis supplies the theoretical framework and some useful experimental techniques for the research applied to particular problems. The improvement of formability by allowing draw-in can also be analysed with the same theoretical and experimental techniques. Results on stress-strain relationships are usually represented by single stress-strain curves plotted either between one stress and one strain (as in the tension or compression tests) or between the effective stress and effective strain, as in tests on tubular specimens under combined tension, torsion and internal pressure. In this study, the triaxial stresses and strains are plotted simultaneously in triangular coordinates. Thus, both stress and strain are represented by vectors and the relationship between them by the relationship between two vector functions. From the results so obtained, conclusions are drawn on both the behaviour and the properties of the material in the bulge test. The stress ratios are generally equal to the strain-rate ratios (stress vectors collinear with incremental strain vectors) and the work-hardening characteristics, which apply only to the particular strain paths are deduced. Plastic instability of the material is generally considered to have been reached when the oil pressure has attained its maximum value so that further deformation occurs under a constant or lower pressure. It is found that the instability regime of deformation has already occurred long before the maximum pressure is attained. Thus, a new concept of instability is proposed, and for this criterion, instability can occur for any type of pressure growth curves.

Nanoindentation measurement of surface residual stresses in particle-reinforced metal matrix composites

The surface residual stresses in SiC particle-reinforced Al matrix composites are measured using a recently developed nanoindentation technique. The tensile biaxial residual stress in Al is found to increase with the particle concentration. The stress magnitudes are in reasonable agreement with those from numerical modeling.

High stress monitoring of prestressing tendons in nuclear concrete vessels using fibre-optic sensors

Maintaining the structural health of prestressed concrete nuclear containments is a key element in ensuring nuclear reactors are capable of meeting their safety requirements. This paper discusses the attachment, fabrication and characterisation of optical fibre strain sensors suitable for the prestress monitoring of irradiated steel prestressing tendons. The all-metal fabrication and welding process allowed the instrumented strand to simultaneously monitor and apply stresses up to 1300 MPa (80% of steel's ultimate tensile strength). There were no adverse effects to the strand's mechanical properties or integrity. After sensor relaxation through cyclic stress treatment, strain transfer between the optical fibre sensors and the strand remained at 69%. The fibre strain sensors could also withstand the non-axial forces induced as the strand was deflected around a 4.5 m bend radius. Further development of this technology has the potential to augment current prestress monitoring practices, allowing distributed measurements of short- and long-term prestress losses in nuclear prestressed-concrete vessels. © 2014 Elsevier B.V.

Effect of thermal residual stresses on fatigue crack opening and propagation behavior in an Al/SiCp metal matrix composite

The effects of a thermal residual stress field on fatigue crack growth in a silicon carbide particle-reinforced aluminum alloy have been measured. Stress fields were introduced into plates of material by means of a quench from a solution heat-treatment temperature. Measurements using neutron diffraction have shown that this introduces an approximately parabolic stress field into the plates, varying from compressive at the surfaces to tensile in the center. Long fatigue cracks were grown in specimens cut from as-quenched plates and in specimens which were given a stress-relieving overaging heat treatment prior to testing. Crack closure levels for these cracks were determined as a function of the position of the crack tip in the residual stress field, and these are shown to differ between as-quenched and stress-relieved samples. By monitoring the compliance of the specimens during fatigue cycling, the degree to which the residual stresses close the crack has been evaluated. © 1995 The Minerals, Metals & Material Society.

Fatigue crack growth behaviour in molten-metal processed SiC particle-reinforced aluminium alloys

Fatigue crack initiation and subsequent short crack growth behaviour of 2014-5wt%SiC aluminium alloy composites has been examined in 4-point bend loading using smooth bar specimens. The growth rates of long fatigue cracks have also been measured at different stress ratios using pre-cracked specimens. The distributions of SiC particles and of coarse constituent particles in the matrix (which arise as a result of the molten-metal processing and relatively slow cooling rate) have been investigated. Preferential crack initiation sites were found to be SiC-matrix interfaces, SiC particles associated with constituent particles and the coarse constituent particles themselves. For microstructurally short cracks the dispersed SiC particles also act as temporary crack arresters. In the long crack growth tests, higher fatigue crack growth rates were obtained than for monolithic alloys. This effect is attributed to the contribution of void formation, due to the decohesion of SiC particles, to the fatigue crack growth process in the composite. Above crack depths of about 200 μm 'short' crack growth rates were in good agreement with the long crack data, showing a Pris exponent, m = 4 in both cases. For the long crack and short crack growth tests little effect of specimen orientation and grain size was observed on fatigue crack growth rates, but, specimen orientation affected the toughness. No effect of stress ratio in the range R = 0.2-0.5 was seen for long crack data in the Paris region.

The antioxidant potential of modified quercetins and quercetin-metal complexes

Quercetin is a naturally occurring polyphenol compound present in grapes, red wine, tea, apples and some vegetables. Like other flavonoids, it has been found to have antioxidant activity in studies in vitro, although there is still much debate about the bioavailability of flavonoids in the diet and their in vivo antioxidant activity. In general, it is thought that the antioxidant efficiency of polyphenols increases with increasing hydroxylation of the rings, but there have been few studies of other substitutions. We have prepared several derivatives of quercetin, to test the effect of modification on their antioxidant potential. Sodium salts of quercetin-5-sulfonate and quercetin-5,8-sulfonate, and transition metal complexes of quercetin-5-sulfonate were analysed for their total antioxidant potential using the FRAP assay, and compared to unmodified quercetin. It was found that quercetin-5-sulfonate complexes with Zn, Cu(II), Fe(II) and Mg were all significantly better antioxidants than quercetin, quercetin-5-sulfonate was comparable to quercetin, whereas the sodium salt of quercetin-5,8-sulfonate had a decreased total antioxidant potential. Kinetic studies of the FRAP reaction showed no significant differences between quercitin and any of the derivatives. The reaction of all the quercetins in the FRAP assay was found to be slower to reach completion than ascorbate, and appeared to have biphasic characteristics. These results suggest that transition metal ions may facilitate the transfer of electrons from the polyphenol ring system to the oxidant, while substitution with S03 is electron-withdrawing and destabilizes the ring system. This is important both for understanding the antioxidant ability of flavonoids, and for the design of novel antioxidant compounds. Further work is being carried out to assess the ability of the quercetin complexes to protect cultured cells from oxidative stress.