Thèse de doctorat--Littérature française, générale et comparée--Strasbourg 2, 2005. Titre de soutenance : Le thème du pays natal dans les oeuvres poétiques de René Char, Aimé Césaire et Tchicaya U Tam'si.

Ce travail de thèse propose d’étudier les œuvres de Supervielle, Saint-John Perse et Char au prisme de la dynamique animale. Il confronte ces textes du XXe siècle à des problématiques plus récentes qui, dans le courant de la « zoopoétique » développée par Anne Simon, considèrent les bêtes littéraires dans leur aspect corporel, organique, mouvant, autant que symbolique. Au-delà de leur dimension métaphorique, les animaux innervent en effet les textes d’une force de création issue de leur qualité d’êtres vivants. Des insectes aux grands mammifères, l’éventail de la relation des bêtes au monde et à l’humain ouvre dans les textes de multiples problématiques sémantiques et stylistiques, appréhendées dans la première partie de ce travail, qui analyse l’influence des existences animales au cœur de l’écriture poétique et de ses rythmes particuliers. La faune apparaît, ainsi que l’approfondit la deuxième partie, comme vectrice d’une pensée élargie de l’environnement. S’appuyant sur des approches anthropologiques, ces analyses font ressortir un traitement particulier des notions de nature ou de paysage, montrant les animaux comme outils de modélisation de l’espace, mais aussi de la pensée. Par le surgissement constant de leur altérité, désirée ou perturbatrice, ils confrontent les poètes aux frontières floues de leur propre individualité. Dans une dernière partie, l’animalité concrète est étudiée en parallèle des facultés qu’a la poésie d’interroger son siècle et une langue élargie au contact des modalités de communication animale. Nous observons que le pistage d’une bête et l’appréhension d’une pensée poétique ressortissent à des herméneutiques proches, entre veille, émerveillement et distance, quittant parfois la rationalité du langage pour explorer les marges de la folie, dans une dynamique de l’oblicité. Est révélée dans ce rapprochement de la bête et du poème une constance de la faille, et une jouissance de l’échappée. / This thesis analyses the works of Supervielle, Saint-John Perse and Char through the prism of animal dynamics. It reads these twentieth-century texts in light of recent criticism, which, in the vein of "zoopoetics" developed by Anne Simon, considers the physical, organic, moving dimensions of literary animals as well as their symbolic significance. Beyond their metaphorical meanings, animals energize the texts with a creative force that stems from their quality as living beings. From insects to large mammals, the range of relationships that animals have to the world and to humans opens up multiple semantic and stylistic problems examined in the first part of this thesis, which analyses the influence of animal existence on poetic writing and poetic rhythm. Based on anthropological approaches, the second part argues that fauna serve as a vehicle for a broader thinking about the environment. This reading illuminates a particular treatment of nature and landscape that uses animals as tools for modelling space as well as thought : through the constant emergence of their desired or disruptive otherness, literary animals confront poets with the blurred boundaries of their own individuality. In the last part, concrete animality is studied alongside poetry’s power to question its own era and its language, which extends to the animalistic modes of communication. The tracking of a beast and the apprehension of a poetic thought emerge from similar hermeneutics, encompassing watchfulness, wonder, and distance, and sometimes leaving the rationality of language to explore the margins of madness in a dynamic of obliquity This kinship between poetry and animality is revealed in the persistence of gaps, and of the pleasures of escape.

Mineral matter affect various coal properties as well as the yield and composition of products released during thermal processes. This necessitates investigation of the effect of the inherent minerals on the products derived during pyrolysis, as pyrolysis forms the basis of most coal utilisation processes. A real challenge in this research has been quantifying the changes seen and attributing these effects to specific minerals. Thus far it has been deemed impossible to predict product yields based on the mineral composition of the parent coal. Limited research regarding these aspects has been done on South African coal and the characterisation of pyrolysis products in previous studies was usually limited to one product phase. A novel approach was followed in this study and the challenges stated were effectively addressed. A vitrinite-rich South African coal from the Highveld coal field, was prepared to an undersize of 75 μm and divided into two fractions. HCl/HF acid washing reduced the ash yield from 14.0 wt% d.b. to 2.0 wt% d.b. (proximate analysis). Pyrolysis was carried out with the North-West University (NWU) Fischer Assay setup at 520, 750 and 900°C under N2 atmosphere and atmospheric pressure. The effect of acid washing and the addition of minerals on the derived pyrolysis products were evaluated. Acid washing led to lower water and tar yields, whilst the gas yields increased, and the char yields were unaffected. The higher gas yield can be related to increased porosity after mineral removal as revealed by Brunauer-Emmett-Teller (BET) CO2 adsorption surface area analysis of the derived chars. Gas chromatography (GC) analyses of the derived pyrolysis gases indicated that the acid washed coal fraction (AW TWD) derived gas contained higher yields of H2, CH4, CO2, C2H4, C2H6, C3H4, C3H6 and C4s when compared to the gas derived from the raw coal fraction (TWD). The CO yield from the TWD coal was higher at all final pyrolysis temperatures. Differences in gas yields were related to increased tar cracking as well as lower hydrogen transfer and de-hydrogenation of the acid washed chars. Analyses of the tar fraction by means of simulated distillation (Simdis), gas chromatography mass spectrometry (GC-MS) –flame ionization detection (–FID) and size exclusion chromatography with ultraviolet (SEC-UV) analyses, indicated that the AW TWD derived tars were more aromatic in nature, containing more heavier boiling point components, which increased with increasing final pyrolysis temperature. The chars were characterised by proximate, ultimate, X-ray diffraction (XRD), X-ray fluorescence (XRF), diffuse reflectance infrared Fourier-transform (DRIFT) and BET CO2 analyses. Addition of either 5 wt% calcite, dolomite, kaolinite, pyrite or quartz to the acid washed fraction (AW TWD) was done in order to determine the effect of these minerals on the pyrolysis products. These minerals were identified as the most prominent mineral phases in the Highveld coal used in this study, by XRD and quantitative evaluation of minerals by scanning electron microscopy (QEMSCAN) analyses. It was found that mineral activity decreased in the order calcite/dolomite>pyrite>kaolinite>>>quartz. Calcite and dolomite addition led to a decrease in tar yield, whilst the gas yields were increased. Markedly, increased water yields were also observed with the addition of calcite, dolomite and pyrite. Kaolinite addition led to increased tar, char and gas yields at 520°C, whilst the tar yield decreased at 750°C. Pyrite addition led to decreased tar and gas yields. Quartz addition had no noteworthy effect on pyrolysis yields and composition, except for a decrease in char yield at all final pyrolysis temperatures and an increased gas yield at 520°C. Regarding the composition of the pyrolysis products, the various minerals had adverse effects. Calcite and dolomite affected the composition of the gas, tar and char phases most significantly, showing definite catalytic activity. Tar producers should take note as presence of these minerals in the coal feedstock could have a significant effect on the tar yield and composition. Kaolinite and pyrite showed some catalytic activity under specific conditions. Model coal-mineral mixtures confirmed synergism between coal-mineral and mineral-mineral interactions. Although some correlation between the pyrolysis products derived from the model coal-mineral mixtures and that of TWD coal was observed, it was not possible to entirely mimic the behaviour of the coal prior to acid washing. Linear regression models were developed to predict the gas, tar and char yields (d.m.m.f.) with mineral composition and pyrolysis temperature as variables, resulting in R2 coefficients of 0.837, 0.785 and 0.846, respectively. Models for the prediction of H2, CO, CO2 and CH4 yields with mineral composition and pyrolysis temperature as variables resulting in R2 coefficients of 0.917, 0.702, 0.869 and 0.978, respectively. These models will serve as foundation for future work, and prove that it is feasible to develop models to predict pyrolysis yields based on mineral composition. Extending the study to coals of different rank can make the models universally applicable and deliver a valuable contribution in industry. / MIng (Chemical Engineering), North-West University, Potchefstroom Campus, 2015

Mineral matter affect various coal properties as well as the yield and composition of products released during thermal processes. This necessitates investigation of the effect of the inherent minerals on the products derived during pyrolysis, as pyrolysis forms the basis of most coal utilisation processes. A real challenge in this research has been quantifying the changes seen and attributing these effects to specific minerals. Thus far it has been deemed impossible to predict product yields based on the mineral composition of the parent coal. Limited research regarding these aspects has been done on South African coal and the characterisation of pyrolysis products in previous studies was usually limited to one product phase. A novel approach was followed in this study and the challenges stated were effectively addressed. A vitrinite-rich South African coal from the Highveld coal field, was prepared to an undersize of 75 μm and divided into two fractions. HCl/HF acid washing reduced the ash yield from 14.0 wt% d.b. to 2.0 wt% d.b. (proximate analysis). Pyrolysis was carried out with the North-West University (NWU) Fischer Assay setup at 520, 750 and 900°C under N2 atmosphere and atmospheric pressure. The effect of acid washing and the addition of minerals on the derived pyrolysis products were evaluated. Acid washing led to lower water and tar yields, whilst the gas yields increased, and the char yields were unaffected. The higher gas yield can be related to increased porosity after mineral removal as revealed by Brunauer-Emmett-Teller (BET) CO2 adsorption surface area analysis of the derived chars. Gas chromatography (GC) analyses of the derived pyrolysis gases indicated that the acid washed coal fraction (AW TWD) derived gas contained higher yields of H2, CH4, CO2, C2H4, C2H6, C3H4, C3H6 and C4s when compared to the gas derived from the raw coal fraction (TWD). The CO yield from the TWD coal was higher at all final pyrolysis temperatures. Differences in gas yields were related to increased tar cracking as well as lower hydrogen transfer and de-hydrogenation of the acid washed chars. Analyses of the tar fraction by means of simulated distillation (Simdis), gas chromatography mass spectrometry (GC-MS) –flame ionization detection (–FID) and size exclusion chromatography with ultraviolet (SEC-UV) analyses, indicated that the AW TWD derived tars were more aromatic in nature, containing more heavier boiling point components, which increased with increasing final pyrolysis temperature. The chars were characterised by proximate, ultimate, X-ray diffraction (XRD), X-ray fluorescence (XRF), diffuse reflectance infrared Fourier-transform (DRIFT) and BET CO2 analyses. Addition of either 5 wt% calcite, dolomite, kaolinite, pyrite or quartz to the acid washed fraction (AW TWD) was done in order to determine the effect of these minerals on the pyrolysis products. These minerals were identified as the most prominent mineral phases in the Highveld coal used in this study, by XRD and quantitative evaluation of minerals by scanning electron microscopy (QEMSCAN) analyses. It was found that mineral activity decreased in the order calcite/dolomite>pyrite>kaolinite>>>quartz. Calcite and dolomite addition led to a decrease in tar yield, whilst the gas yields were increased. Markedly, increased water yields were also observed with the addition of calcite, dolomite and pyrite. Kaolinite addition led to increased tar, char and gas yields at 520°C, whilst the tar yield decreased at 750°C. Pyrite addition led to decreased tar and gas yields. Quartz addition had no noteworthy effect on pyrolysis yields and composition, except for a decrease in char yield at all final pyrolysis temperatures and an increased gas yield at 520°C. Regarding the composition of the pyrolysis products, the various minerals had adverse effects. Calcite and dolomite affected the composition of the gas, tar and char phases most significantly, showing definite catalytic activity. Tar producers should take note as presence of these minerals in the coal feedstock could have a significant effect on the tar yield and composition. Kaolinite and pyrite showed some catalytic activity under specific conditions. Model coal-mineral mixtures confirmed synergism between coal-mineral and mineral-mineral interactions. Although some correlation between the pyrolysis products derived from the model coal-mineral mixtures and that of TWD coal was observed, it was not possible to entirely mimic the behaviour of the coal prior to acid washing. Linear regression models were developed to predict the gas, tar and char yields (d.m.m.f.) with mineral composition and pyrolysis temperature as variables, resulting in R2 coefficients of 0.837, 0.785 and 0.846, respectively. Models for the prediction of H2, CO, CO2 and CH4 yields with mineral composition and pyrolysis temperature as variables resulting in R2 coefficients of 0.917, 0.702, 0.869 and 0.978, respectively. These models will serve as foundation for future work, and prove that it is feasible to develop models to predict pyrolysis yields based on mineral composition. Extending the study to coals of different rank can make the models universally applicable and deliver a valuable contribution in industry. / MIng (Chemical Engineering), North-West University, Potchefstroom Campus, 2015

The Mae Tao watershed, northwestern Thailand, has become contaminated with cadmium (Cd) from the zinc mining activities area in the nearby Thanon-Thongchai mountains. Consumption of Cd-contaminated rice has led to documented human health impacts. The aim of this study was to clarify transfer pathways from creek and canal waters to the paddy field soils near Baan Mae Tao Mai village and to determine the relationship between Cd forms in the soil and uptake by rice plants. Soils, irrigation canal sediments and water samples were collected during the dry season and at the onset of the rainy season. Rice samples were collected at harvesting time and samples of soil fertiliser were also obtained. Water samples were filtered, ultrafiltered and analysed by ICP-MS whilst sub-samples of dried, ground soils and sediments were first subjected to micro-wave assisted acid digestion (modified US EPA method 3052). XPRD and SEM-EDX methods were used for mineralogical characterisation and selective chemical extractions have assisted in the characterisation of solid phase Cd associations. Transfer mainly occurred in association with particulate matter during flooding and channel dredging and, in contrast with many other studies, most of the soil Cd was associated with exchangeable and carbonate-bound fractions. Moreover, there was a significant positive relationship between soil total Cd and rice grain Cd (R2=0.715), but a stronger relationship between both the Tessier-exchangeable soil Cd and the BCR-exchangeable soil Cd and rice grain Cd (R2=0.895 and 0.861, respectively). Stable Isotope Exchange (gives isotopically exchangeable Cd - E value) is generally considered to provide a better measure of bioavailability. The results of this study showed that SIE gave values which significantly positive correlated with the Tessier exchangeable fraction. Biochar has a porous structure and acidic functional groups on its surface which give it a high capacity to affect heavy metal adsorption when added to soils. Biochar samples were produced from rice husk (RHC) and miscanthus (MC) since these are cheap and readily available materials in Thailand. Indeed rice husk char is already used for rice seed germination by local farmers. Evaluation of the chemical and physical properties of the chars showed that the lower temperature (350°C) chars had greater proportions of oxygen-containing functional groups than those produced at 700°C. Moreover the low temperature RHC had the greater cation exchange capacity than the MC produced at the same temperature. In abiotic feasibility tests, it was shown that RHC was more effective than MC at lowering soil available Cd. The former reduced the E values for the medium-Cd soils by 4.7% and 16.0% when 1% and 5% RHC, was added, respectively. From pot experiments, in medium-Cd soils, 1% and 5% RHC amendment showed the potential to decrease Cd uptake by rice roots. However, further work involving addition of a greater proportion of biochar with a higher number of replicates is needed to reach more robust conclusions.

Thesis (MScEng (Process Engineering))--University of Stellenbosch, 2010. / ENGLISH ABSTRACT: The world’s depleting fossil fuels and increasing greenhouse gas emissions have given rise to much research into renewable and cleaner energy. Biomass is unique in providing the only renewable source of fixed carbon. Agricultural residues such as Sugarcane Bagasse (SB) are feedstocks for ‘second generation fuels’ which means they do not compete with production of food crops. In South Africa approximately 6 million tons of raw SB is produced annually, most of which is combusted onsite for steam generation. In light of the current interest in bio-fuels and the poor utilization of SB as energy product in the sugar industry, alternative energy recovery processes should be investigated. This study looks into the thermochemical upgrading of SB by means of pyrolysis. Biomass pyrolysis is defined as the thermo-chemical decomposition of organic materials in the absence of oxygen or other reactants. Slow Pyrolysis (SP), Vacuum Pyrolysis (VP), and Fast Pyrolysis (FP) are studied in this thesis. Varying amounts of char and bio-oil are produced by the different processes, which both provide advantages to the sugar industry. Char can be combusted or gasified as an energy-dense fuel, used as bio-char fertilizer, or upgraded to activated carbon. High quality bio-oil can be combusted or gasified as a liquid energy-dense fuel, can be used as a chemical feedstock, and shows potential for upgrading to transport fuel quality. FP is the most modern of the pyrolysis technologies and is focused on oil production. In order to investigate this process a 1 kg/h FP unit was designed, constructed and commissioned. The new unit was tested and compared to two different FP processes at Forschungszentrum Karlsruhe (FZK) in Germany. As a means of investigating the devolatilization behaviour of SB a Thermogravimetric Analysis (TGA) study was conducted. To investigate the quality of products that can be obtained an experimental study was done on SP, VP, and FP. Three distinct mass loss stages were identified from TGA. The first stage, 25 to 110°C, is due to evaporation of moisture. Pyrolitic devolatilization was shown to start at 230°C. The final stage occurs at temperatures above 370°C and is associated with the cracking of heavier bonds and char formation. The optimal decomposition temperatures for hemicellulose and cellulose were identified as 290°C and 345°C, respectively. Lignin was found to decompose over the entire temperature range without a distinct peak. These results were confirmed by a previous study on TGA of bagasse. SP and VP of bagasse were studied in the same reactor to allow for accurate comparison. Both these processes were conducted at low heating rates (20°C/min) and were therefore focused on char production. Slow pyrolysis produced the highest char yield, and char calorific value. Vacuum pyrolysis produced the highest BET surface area chars (>300 m2/g) and bio-oil that contained significantly less water compared to SP bio-oil. The short vapour residence time in the VP process improved the quality of liquids. The mechanism for pore formation is improved at low pressure, thereby producing higher surface area chars. A trade-off exists between the yield of char and the quality thereof. FP at Stellenbosch University produced liquid yields up to 65 ± 3 wt% at the established optimal temperature of 500°C. The properties of the bio-oil from the newly designed unit compared well to bio-oil from the units at FZK. The char properties showed some variation for the different FP processes. At the optimal FP conditions 20 wt% extra bio-oil is produced compared to SP and VP. The FP bio-oil contained 20 wt% water and the calorific value was estimated at 18 ± 1 MJ/kg. The energy per volume of FP bio-oil was estimated to be at least 11 times more than dry SB. FP was found to be the most effective process for producing a single product with over 60% of the original biomass energy. The optimal productions of either high quality bio-oil or high surface area char were found to be application dependent. / AFRIKAANSE OPSOMMING: As gevolg van die uitputting van fossielbrandstofreserwes, en die toenemende vrystelling van kweekhuisgasse word daar tans wêreldwyd baie navorsing op hernubare en skoner energie gedoen. Biomassa is uniek as die enigste bron van hernubare vaste koolstof. Landbouafval soos Suikerriet Bagasse (SB) is grondstowwe vir ‘tweede generasie bio-brandstowwe’ wat nie die mark van voedselgewasse direk affekteer nie. In Suid Afrika word jaarliks ongeveer 6 miljoen ton SB geproduseer, waarvan die meeste by die suikermeulens verbrand word om stoom te genereer. Weens die huidige belangstelling in bio-brandstowwe en ondoeltreffende benutting van SB as energieproduk in die suikerindustrie moet alternatiewe energie-onginningsprosesse ondersoek word. Hierdie studie is op die termo-chemiese verwerking van SB deur middel van pirolise gefokus. Biomassa pirolise word gedefinieer as die termo-chemiese afbreking van organiese bio-materiaal in die afwesigheid van suurstof en ander reagense. Stadige Pirolise (SP), Vakuum Pirolise (VP), en Vinnige Pirolise word in hierdie tesis ondersoek. Die drie prosesse produseer veskillende hoeveelhede houtskool en bio-olie wat albei voordele bied vir die suikerindustrie. Houtskool kan as ‘n vaste energie-digte brandstof verbrand of vergas word, as bio-houtskoolkompos gebruik word, of kan verder tot geaktiveerde koolstof geprosesseer word. Hoë kwaliteit bio-olie kan verbrand of vergas word, kan as bron vir chemikalië gebruik word, en toon potensiaal om in die toekoms opgegradeer te kan word tot vervoerbrandstof kwaliteit. Vinnige pirolise is die mees moderne pirolise tegnologie en is op bio-olie produksie gefokus. Om die laasgenoemde proses te toets is ‘n 1 kg/h vinnige pirolise eenheid ontwerp, opgerig en in werking gestel. Die nuwe pirolise eenheid is getoets en vegelyk met twee verskillende vinnige pirolise eenhede by Forschungszentrum Karlsruhe (FZK) in Duitsland. Termo-Gravimetriese Analise (TGA) is gedoen om die ontvlugtigingskenmerke van SB te bestudeer. Eksperimentele werk is verrig om die kwaliteit van produkte van SP, VP, vinnige pirolise te vergelyk. Drie duidelike massaverlies fases van TGA is geïdentifiseer. Die eerste fase (25 – 110°C) is as gevolg van die verdamping van vog. Pirolitiese ontvlugtiging het begin by 230°C. Die finale fase (> 370°C) is met die kraking van swaar verbindings en die vorming van houtskool geassosieer. Die optimale afbrekingstemperatuur vir hemisellulose en sellulose is as 290°C en 345°C, respektiewelik, geïdentifiseer. Daar is gevind dat lignien stadig oor die twede en derde fases afgebreek word sonder ‘n duidelike optimale afbrekingstemperatuur. Die resultate is deur vorige navorsing op TGA van SB bevestig. SP en VP van bagasse is in dieselfde reaktor bestudeer, om ‘n akkurate vergelyking moontlik te maak. Beide prosesse was by lae verhittingstempo’s (20°C/min) ondersoek, wat gevolglik op houtskoolformasie gefokus is. SP het die hoogste houtskoolopbrengs, met die hoogste verbrandingsenergie, geproduseer. VP het hootskool met die hoogste BET oppervlakarea geproduseer, en die bio-olie was weens ‘n dramatiese afname in waterinhoud van beter gehalte. Die meganisme vir die vorming van ‘n poreuse struktuur word deur lae atmosferiese druk verbeter. Daar bestaan ‘n inverse verband tussen die kwantiteit en kwaliteit van die houtskool. Vinnige pirolise by die Universiteit van Stellenbosch het ‘n bio-olie opbrengs van 65 ± 3 massa% by ‘n vooraf vasgestelde optimale temperatuur van 500°C geproduseer. Die eienskappe van bio-olie wat deur die nuwe vinnige pirolise eenheid geproduseer is het goed ooreengestem met die bio-olie afkomstig van FZK se pirolise eenhede. Die houtskool eienskappe van die drie pirolise eenhede het enkele verskille getoon. By optimale toestande vir vinnige pirolise word daar 20 massa% meer bio-olie as by SP en VP geproduseer. Vinnige pirolise bio-olie het ‘n waterinhoud van 20 massa% en ‘n verbrandingswarmte van 18 ± 1 MJ/kg. Daar is gevind dat ten opsigte van droë SB die energie per enheidsvolume van bio-olie ongeveer 11 keer meer is. Vinnige pirolise is die mees doeltreffende proses vir die vervaardiging van ‘n produk wat meer as 60% van die oorspronklike biomassa energie bevat. Daar is gevind dat die optimale hoeveelhede van hoë kwaliteit bio-olie en hoë oppervlakarea houtskool doelafhanklik is.

Although the general principles of biomass gasification are broadly understood, at a larger scale of operation (e.g. > 200 kg/h) there is a lack of confidence in the translation of the basic scientific concepts into a financially viable operation that satisfies regulatory requirements. Looking in particular at the operation of a down-draft type of gasifier, a number of challenges were identified and studied in greater detail. Gasification experiments were performed on wood and straw pellets in a small scale, 21 mm i.d. quartz-tube reactor. These provided useful insight into what was occurring inside the gasifier, and the complexity and roles of the various reaction zones. In order to perform on-line gas analysis measurements in real time, a method was developed which enabled a quadrupole mass spectrometer (QMS) to be used. This was tested in a laboratory environment, and then used on a commercial pilot-plant gasifier (150 to 250 kg/h). This enabled the composition of the gas to be monitored while the plant was started up, and then operated at various levels of gas flow through the plant. In general the concentrations measured during a stable operation were as follows: CO = 16.0 vol.%, H2 = 11.9 vol.%, CO2 = 15.8 vol.%, N2 = 54.1 vol.%, CH4 = 1.9 vol.%, O2 = 0.3 vol.%. Measurements of O2 concentrations in the gas stream on start-up provide useful information on conditions when a flammable atmosphere could exist in the lines/vessels. To help with the development of suitable gas clean-up strategies, the presence of two key sulphur species, H2S and carbonyl sulphide (COS), was studied in more detail. Experimental measurements were taken on the laboratory reactor (e.g. H2S = 286 ppmv, COS = 28 ppmv for gasification of refuse-derived fuel (RDF) pellets), and the commercial pilot-scale gasifier (e.g. H2S = 332 ppmv, COS = 12 ppmv). This data was also compared with theoretical thermodynamic predictions. The steam gasification of char was also studied in a laboratory 9.5 mm i.d. reactor, and kinetic expressions were determined for RDF-derived char. It was shown that high concentrations of H2 (20 vol.%) and CO (15 vol.%) can be achieved, and the temperature at which reactions were initiated was > 700 ºC, and significant at 900 ºC. Interestingly, the RDF-derived char (at carbon conversion from 10 to 70 %) appears to be more reactive than other biochars reported in the literature. However, at high conversion (> 50 %), its apparent reactivity decreases with carbon conversion, behaving in a similar manner to coal chars.

As carbon dissolution rates have been determined for a few chars only, a systematic and comprehensive study was undertaken in this project on the dissolution behaviour of carbon from non-graphitic materials into liquid iron. In addition to measuring the kinetics of carbon dissolution from a number of coal chars into liquid iron as a function of parent coal and coal ash composition, the influence of chemical reactions between solute/solid carbon and ash oxides was also investigated. These studies were supplemented with investigations on one metallurgical coke for the sake of comparison. The wettability of coal chars and coke with liquid iron at 1550 degrees C was measured as a function of time. Being essentially non-wetting, only a marginal improvement in contact angles was observed with time. The accumulation of alumina at the interface was detected for all materials and was seen to increase with time in all cases. Calcium and sulphur also appeared to preferentially accumulate at the interface, concentrating at levels in excess of those expected from the ash composition alone. Despite the high levels of silica in the ash initially, very little silica was detected in the interfacial region, implying ongoing silica reduction reactions. A small amount of silicon was however detected in the iron droplets, indicating silica reduction with solute carbon. It was identified that the reduction reactions can also consume solute carbon in the liquid iron. As this is occurring simultaneously with carbon dissolution into liquid iron, the interdependency of silica reduction and carbon dissolution could potentially limit the observed carbon dissolution rate. A theoretical model was developed for estimating the interfacial contact area between chars and liquid iron. Wettability was found to have a very significant effect on the area of contact. A two-step behaviour was observed in the carbon dissolution of two chars and coke. Slow rates of carbon dissolution in stage II were attributed to very high levels of interfacial blockage by reaction products leading to much reduced areas of contact between carbonaceous material and liquid iron. The first order dissolution rate constants for four chars/coke and the observed trend in first order dissolution rate constants were calculated. These dissolution results compare well with the previously measured dissolution rate constants. The trends in dissolution can be adequately explained on the basis of carbon structure, silica reduction, sulphur concentration in the metal and ash impurities.

In this thesis I have investigated the effects of invading top and intermediate consumers in a size-structured fish community, using a combination of field studies, a lake invasion experiment and smaller scale pond and aquaria experiments. The lake invasion experiment was based on introductions of an intermediate consumer, ninespine stickleback (Pungitius pungitius L.), in to allopatric populations of an omnivorous top predator, Arctic char (Salvelinus alpinus L.). The invasion experiment was performed in two tundra lakes and in two birch forest lakes to investigate the effect of climate on the invasion success. I found that the effect of sticklebacks on char was size dependent. Small char suffered reduced growth from resource competition with sticklebacks whereas the maximum size of adult char increased from the addition of a larger prey resource, stickleback. The negative effect of sticklebacks on the growth of small char suggests that sticklebacks may be a better resource competitor than char, which was also supported by the pond and aquaria experiments. The pond experiments also suggested that char were more efficient cannibals than interspecific predators on sticklebacks. Cannibalism in char may limit the recruitment of char and decrease both their predatory and competitive effect on coexisting species and thereby also promote the coexistence of char and sticklebacks. The successful invasion by sticklebacks and their subsequent increases in density suggest that the absence of sticklebacks in char lakes in this region is not caused by biotic interactions with char. Instead, it may be suggested that co-occurrence of sticklebacks and char in the region is limited by dispersal. The char – stickleback system resembles an intraguild predation system with char as the top consumer and stickleback as the intermediate consumer. The effects of the stickleback invasion is also contrasted with a field study of a northern pike (Esox lucius L.) invasion into a system with coexisting char and stickleback, where pike can be viewed as the top consumer and char as the intermediate consumer both feeding on sticklebacks. In this case pike excluded char. The identity of the invading species and the relative strength of the predatory and competitive interactions in the two contrasting systems are discussed in relation to coexistence in intraguild predation systems. I found that the identity of the invading species is of crucial importance for the response at the ecosystem level, and that the inherent size dependency of competitive and predatory interactions in fish communities is important for attaining a mechanistical understanding of the effects of invasive species in lake ecosystems.

No description available.