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.

The deformation behaviour of the collapsing and destructured soils of the Sana'a area and their response to field treatment

Previous work has indicated the presence of collapsing and structured soils in the surface layers underlying Sana's, the capital of Yemen Republic. This study set out initially to define and, ultimately, to alleviate the problem by investigating the deformation behaviour of these soils through both field and laboratory programmes. The field programme was carried out in Sana'a while the laboratory work consisted of two parts, an initial phase at Sana's University carried out in parallel with the field programme on natural and treated soils and the major phase at Aston University carried out on natural, destructured and selected treated soils. The initial phase of the laboratory programme included classification, permeability, and single (collapsing) and double oedometer tests while the major phase, at Aston, was extended to also include extensive single and double oedometer tests, Scanning Electron Microscopy and Energy Dispersive Spectrum analysis. The mechanical tests were carried out on natural and destructed samples at both the in situ and soaked moisture conditions. The engineering characteristics of the natural intact, field-treated and laboratory destructured soils are reported, including their collapsing potentials which show them to be weakly bonded with nil to severe collapsing susceptibility. Flooding had no beneficial effect, with limited to moderate improvement being achieved by preloading and roller compaction, while major benefits were achieved from deep compaction. From these results a comparison between the soil response to the different treatments and general field remarks were presented. Laboratory destructuring reduced the stiffness of the soils while their compressibility was increasing. Their collapsing and destructuring mechanisms have been examined by studying the changes in structure accompanying these phenomena. Based on the test results for the intact and the laboratory destructured soils, a simplified framework has been developed to represent the collapsing and deformation behaviour at both the partially saturated and soaked states, and comments are given on its general applicability and limitations. It has been used to evaluate all the locations subjected to field treatment. It provided satisfactory results for the deformation behaviour of the soils destructed by field treatment. Finally attention is drawn to the design considerations together with the recommendations for the selection of potential improvement techniques to be used for foundation construction on the particular soils of the Sana's region.

The performance of stabilized and unstabilized minestone in an aqueous environment with emphasis on its erosion resistance

Britain's sea and flood defences are becoming increasingly aged and as a consequence, more fragile and vulnerable. As the government's philosophy on resources shifts against the use of prime quarried and dredged geo-materials, the need to find alternative bulk materials to bolster Britain's prone defences becomes more pressing. One conceivable source for such a material is colliery waste or minestone. Although a plethora of erosion-abrasion studies have been carried out on soils and soil-cements, very little research has been undertaken to determine the resistance of minestone and its cement stabilized form to the effects of water erosion. The thesis reviews the current extent to which soil-cements, minestone and cement stabilized minestone (CSM) have been employed for hydraulic construction projects. A synopsis is also given on the effects of immersion on shales, mudstones and minestone, especially with regard to the phenomena of slaking. A laboratory study was undertaken featuring a selection of minestones from several British coalfields. The stability of minestone and CSM in sea water and distilled water was assessed using slaking tests and immersion monitoring and the bearing on the use of these materials for hydraulic construction is discussed. Following a review of current erosion apparatus, the erosion/abrasion test and rotating cylinder device were chosen and employed to assess the erosion resistance of minestone and CSM. Comparison was made with a sand mix designed to represent a dredged sand, the more traditional, bulk hydraulic construction material. The results of the erosion study suggest that both minestone and CSM were more resistant to erosion and abrasion than equivalently treated sand mixes. The greater resistance of minestone to the agents of erosion and abrasion is attributed to several factors including the size of the particles, a greater degree of cement bonding and the ability of the minestone aggregate to absorb, rather than transmit shock waves produced by impacting abrasive particles. Although minestone is shown to be highly unstable when subjected to cyclic changes in its moisture content, the study suggests that even in an intertidal regime where cyclic immersion does takes place, minestone will retain sufficient moisture within its fabric to prevent slaking from taking place. The slaking study reveals a close relationship between slaking susceptibility and total pore surface area as revealed by porosimetry. The immersion study shows that although the fabric of CSM is rapidly attacked in sea water, a high degree of the disruption is associated with the edges and corners of samples (ie. free surface) while the integrity of the internal fabric remains relatively intact. CSM samples were shown to be resilient when subjected to immersion in distilled water. An overall assessment of minestone and CSM would suggest that with the implementation of judicious selection and appropriate quality control they could be used as alternative materials for flood and sea defences. It is believed, that even in the harsh regime of a marine environment, CSM could be employed for temporary and sacrificial schemes.

Geographical variation in carbon dioxide fluxes from soils in agro-ecosystems and its implications for life-cycle assessment

1. Exchange of carbon dioxide (CO2) from soils can contribute significantly to the global warming potential (GWP) of agro-ecosystems. Due to variations in soil type, climatic onditions and land management practices, exchange of CO2 can differ markedly in different geographical locations. The food industry is developing carbon footprints for their products necessitating integration of CO2 exchange from soils with other CO2 emissions along the food chain. It may be advantageous to grow certain crops in different geographical locations to minimize CO2 emissions from the soil, and this may provide potential to offset other emissions in the food chain, such as transport. 2. Values are derived for the C balance of soils growing horticultural crops in the UK, Spain and Uganda. Net ecosystem production (NEP) is firstly calculated from the difference in net primary production (NPP) and heterotrophic soil respiration (Rh). Both NPP and Rh were estimated from intensive direct field measurements. Secondly, net biome production (NBP) is calculated by subtracting the crop biomass from NEP to give an indication of C balance. The importance of soil exchange is discussed in the light of recent discussions on carbon footprints and within the context of food life-cycle assessment (LCA). 3. The amount of crop relative to the biomass and the Rh prevailing in the different countries were the dominant factors influencing the magnitude of NEP and NBP. The majority of the biomass for lettuce Lactuca sativa and vining peas Pisum sativum, was removed from the field as crop; therefore, NEP and NBP were mainly negative. This was amplified for lettuces grown in Uganda (-16·5 and -17 t C ha-1 year-1 compared to UK and Spain -4·8 to 7·4 and -5·1 to 6·3 t C ha-1 year-1 for NEP and NBP, respectively) where the climate elevated Rh. 4. Synthesis and applications. This study demonstrates the importance of soil emissions in the overall life cycle of vegetables. Variability in such emissions suggests that assigning a single value to food carbon footprints may not be adequate, even within a country. Locations with high heterotrophic soil respiration, such as Spain and Uganda (21·9 and 21·6 t C ha-1 year-1, respectively), could mitigate the negative effects of climate on the C costs of crop production by growth of crops with greater returns of residue to the soil. This would minimize net CO2 emissions from these agricultural ecosystems.