Abstract Boreal urban forests are becoming more and more fragmented and, at the same time, are exposed to low-level but long-term nitrogen and sulphur deposition. Natural mid-boreal forests are dominated by few tree and shrub species, while herbs and grasses are rare. Soils in mid-boreal forests are rich in ectomycorrhizal (ECM) fungi, forming a symbiotic relationship with forest trees, which is important for the nutrient cycle especially in nutrient-poor ecosystems. Aims of this thesis were 1) to study differences between mid-boreal urban and rural forests in composition of macrofungi and structure of plant communities, 2) to explore whether responses of Scots pine seedlings to excess N are mediated via soil or via air, and 3) to study if partial removal of vegetation and humus layer alleviates the adverse effects of excess N on plant and fungal communities, and promotes performance and regeneration of Scots pine in urban forests. The growth responses of seedlings and their mycorrhizal colonization were studied in both field and greenhouse experiments. Peroxidase (POD) activity was used as a root stress indicator. Urban forests were poor in number of fruiting ECM fungal species, but rich in herbs and grasses in the field layer, as compared to rural forests. These differences were thought to result from changes in soil properties. ECM fungal colonization in Scots pine roots did not respond significantly to high nitrogen load in soil, but high root POD activity indicated changes in root physiology. ECM macrofungal diversity in urban forests was not markedly increased during a five-year survey after a partial humus removal treatment. On the other hand, fruiting of Cortinarius semisanguineus is a positive response to the treatment. Scots pine seedling emergence was poor due to rapid revegetation at the urban sites, but the treatment promoted both root and shoot growth of planted Scots pine seedlings in urban forests. Decreased root POD activity in Scots pine seedlings in the humus removal treatment possibly indicates lowered root stress. Soil manipulations may result in a risk of nutrient leakage, and a risk of invasion by non-typical plants. Also, small stand size with high recreation pressure causes a risk for tree regeneration in urban forest stands. These risks need to be considered when planning management of urban coniferous forests.

Le secteur industriel du traitement des déchets génère des émissions gazeuses induisant des nuisances odorantes auprès des populations riveraines des installations. Ces effluents gazeux contiennent une grande diversité de composés volatils : oxygénés (acides gras volatils, cétones, aldéhydes, alcools), azotés et soufrés (hydrogène sulfuré (H2S), diméthylsulfure (DMS), diméthyldisulfure (DMDS) et méthanethiol (MT)). Ces effluents gazeux sont traités par un dispositif approprié que sont les bioprocédés. Néanmoins, les seuils de perception des composés odorants et plus particulièrement ceux des composés soufrés, très bas, obligent à atteindre des efficacités d’abattement particulièrement élevées, faute de quoi le résiduel de concentration peut être à l’origine d’un impact notable sur les populations riveraines. L’objectif de cette étude est donc d’améliorer les performances de ces procédés biologiques par la mise en oeuvre de filières de traitement. L’originalité de ce travail est d’évaluer les performances d’épuration d’un mélange de composés soufrés par la mise en oeuvre du couplage de deux procédés biologiques que sont le lit percolateur et le biofiltre.Le premier résultat de ce travail de thèse a consisté à évaluer l’impact du pH sur l’activité de dégradation de composés soufrés en mélange (H2S, DMS et DMDS) en mettant en oeuvre des microcosmes. La valeur du pH de la phase aqueuse a une influence sur l’efficacité d’élimination des DMS et DMDS. Une élimination complète de ces derniers est observée pour une gamme de pH comprise entre 5 et 7. Les performances de ce couplage ont été comparées avec celles observées dans le cas de biofiltres seuls (dupliquats). Après une phase d’acclimatation, un fonctionnement stable est maintenu en conditions opératoires stationnaires. Les potentialités du couplage ont été mises en évidence, les niveaux d’abattement des DMS et DMDS étant supérieurs (de l’ordre de 20%) pour le couplage de bioprocédés. La composante microbiologique a fait l’objet d’une attention particulière en évaluant les densités de deux populations connues pour dégrader ces composés soufrés (Hyphomicrobium et Thiobacillus thioparus) par q-PCR au sein du biofiltre couplé au filtre percolateur et des biofiltres de référence. Les résultats obtenus mettent en évidence la présence de ces deux populations à des taux élevés (104 copies du gène ADNr-16S/ng ADN extrait pour Thiobacillus thioparus et 104-106 copies du gène ADNr-16S/ng ADN extrait pour Hyphomicrobium). La répartition de ces deux populations est similaire dans les deux cas (couplage et biofiltres seuls).Face à des perturbations représentatives de celles observées sur site, la robustesse du couplage a pu être mise en évidence, les niveaux d’efficacité d’avant les chocs sont récupérés dans un délai inférieur ou égal à 72 heures après l’arrêt de la perturbation. Enfin, une application sur site (équarrissage) a été conduite sur une période de trois mois et a permis de valider les résultats de laboratoire et de montrer l’adaptabilité d’un tel système face à la variabilité d’un effluent réel. / Waste treatment industries generate gaseous emissions that may induce odor annoyance to the surrounding populations. These gaseous effluents contain a large variety of volatile compounds such as oxygenated (volatile fatty acids, ketones, aldehydes and alcohols), nitrogen and sulphur compounds (hydrogen sulphide (H2S), dimethylsulphide (DMS), dimethyldisulfide (DMDS) and methanethiol (MT). These gaseous emissions are controlled by using an adequate system such as biotechniques. Nevertheless, because of their very low odor thresholds, complete elimination of sulphur compounds has to be assessed, as the residual concentration can induce an odorous impact on neighbourhood populations. The aim of this study is to improve these bioprocesses performances by carrying out an adequate system strategy. The originality of this work is to evaluate the removal efficiency of a mixture of sulphur compounds by implementing a combination of two bioprocesses and more precisely a biotrickling filter and biofilter.The first step of this PhD. work consisted of evaluating the pH impact on the biodegradation activity of a mixture of sulphur compounds (H2S, DMS and DMDS) by using microcosms. The pH has an impact on the removal efficiency of DMS and DMDS. The total removal of these compounds is observed for a pH range between 5 and 7. The performances of the coupling have been compared with those reached by implementing control biofilters (duplicated). After an acclimatization period, stable performances are maintained under constant operating conditions. The efficiency of the coupling have been highlighted, the DMS and DMDS abatement levels are superior (around 20%) for the bioprocesses combination.The microbiological component has been investigated within all biofilters by estimating the densities of two populations involved in the biodegradation of sulphur compounds (Hyphomicrobium and Thiobacillus thioparus), by using qPCR. The obtained results highlighted the presence of both populations at high level (104 copies of DNAr-16S gene/ng extracted DNA for Thiobacillus thioparus and 104-106 copies of DNAr-16S gene/ng extracted DNA for Hyphomicrobium). The repartition of these two bacterial populations is similar in both cases (coupling system and reference biofilters). Under transient shock load conditions, the robustness of the coupling has been revealed. The efficiency levels before the shock load are recovered 48 hours after the perturbation off. Finally, the monitoring of an on- site pilot (rendering facility) has been carried out during three months. The laboratory results have been confirmed and the suitability of such a system has been showed under industrial gas variability.

Abstract The effects of restoration and certain elements, nitrogen, sulphur, calcium and Misch metal, on the hot ductility of austenitic, high-alloyed austenitic and duplex stainless steels have been investigated by means of hot rolling, hot tensile, hot bending and stress relaxation tests. The results of these different testing methods indicated that hot rolling experiments using stepped specimens is the most effective way to investigate the relationship between the softening and cracking phenomena under hot rolling conditions. For as-cast, high-alloyed and duplex stainless steels with a low impurity level, the cracking tendency was observed to increase with increasing pass strain and temperature, being minimal for the small strain of 0.1. No cracking occurred in these steels when rolled in the wrought condition. It could be concluded that the cracking problems are only exhibited by the cast structure with the hot ductility of even partially recrystallised steel being perfectly adequate. However, the recrystallisation kinetics of the high-alloyed austenitic stainless steels, determined by stress relaxation and double-pass rolling tests, were found to be so slow that only partial softening can be expected to occur between roughing passes under normal rolling conditions. In the duplex steel, the restoration is fairly fast so that complete softening can occur within typical interpass times in hot rolling, while certain changes in the phase structure take place as well. Sulphur was found to be an extremely harmful element in duplex stainless steel with regard to their hot ductility so that severe cracking can take place with sulphur content above 30 ppm. However, the effect of sulphur can be eliminated by reducing its content and by calcium or Misch metal treatments that significantly increase the number and decrease the average size of the inclusions. It seems that the desulphurisation capacity of an element is the most important property for assessing its usefulness in reducing the detrimental influence of sulphur. The hot ductility of type 316L stainless steel determined by tensile tests was found to be better for nitrogen content of 0.05 wt-% than 0.02%, while in double-hit tensile tests the hot ductility values were identical. The mechanism whereby nitrogen affects hot ductility remains unclear but a retarding effect on static recrystallisation was observed.

Dans le cadre des études portant sur l’impact de l’aviation sur le changement climatique, les traînées de condensation font partie des phénomènes présentant le plus d’incertitudes quant à leur rôle. Dans ce contexte, l’étude vise à mieux décrire les caractéristiques physico-chimiques du panache dans le champ proche d’un avion, celles-ci pouvant conditionner les propriétés des traînées de condensation formées.Pour cela, des simulations spatiales tridimensionnelles de type RANS ont été réalisées à l’aide du code CEDRE de l’ONERA, prenant en compte les processus microphysiques, les réactions chimiques, et l’écoulement aérodynamique autour et dans le sillage d'une configuration réaliste d'un avion de transport civil. Les modèles microphysiques intégrés permettent de décrire les processus d’activation des particules de suie et les processus de condensation et d’évaporation d’eau à leur surface.Une phase de validation du code a été menée pour chacun des processus pris en compte, montrant un bon accord avec les données de la littérature. Des études de sensibilité ont également été conduites afin d’évaluer l’impact des paramètres atmosphériques et des caractéristiques des effluents sur les propriétés des cristaux de glace formés. L’augmentation de la teneur en soufre du carburant entraîne un accroissement de l’activité des suies et aboutit à une distance d’apparition plus courte et une opacité plus élevée des traînées de condensation. Lorsque la quantité d’eau émise est suffisante, l’augmentation du nombre de suies éjectées entraîne un accroissement de la concentration de glace, résultant en un fort accroissement de l’opacité et de la superficie de la traînée de condensation. / In the framework of the impact of aviation on climate change studies, the involvement of contrails is identified as one of the most uncertain components. In this context, this study aims to better describe the physico-chemical properties of the plume in the near-field of an aircraft, for they could be critical to contrails properties.To this end, RANS spatial simulations have been performed using the code CEDRE of ONERA, taking into account the microphysical processes, chemical reactions, and the air flow around and in the wake of a realistic civil transport aircraft. Microphysical models have been implemented in order to describe the soot activation processes and the condensation and evaporation of water upon their surface.A validation phase of the code has been carried out for each of the processes taken into account, showing good agreements with data from the literature. Sensitivity studies have also been performed in order to assess the impact of atmospheric parameters and exhaust characteristics on formed contrails properties. The increase of the fuel sulphur content leads to increased soot activation that results in a shorter contrail onset and increased contrail opacity. If the amount of emitted water is sufficient, the increase of the number of ejected soot particles causes an increase of ice concentration that results in an important increase of contrail opacity and surface area.

A local integrated pulp and paper Kraft mill had come under pressure from the local communities and mill personnel to reduce the odours that were perceived to be generated at the Farm Dams and irrigation farm situated adjacent to the mill. The typical odours associated with Kraft mills are due to the generation of four reduced sulphur compounds such as hydrogen sulphide (H2S), methyl-mercaptan (CH3SH), dimethyl-sulphide (CH3)2S and dimethyl-disulphide (CH3)2S2. These compounds are collectively referred to as Total Reduced Sulphur (TRS) components which are generated as a direct result of the Kraft pulping and chemical recovery process. These components can either be in the gaseous or aqueous phase depending on the characteristics of the effluent. Gaseous and aqueous TRS profiling of the mill indicated that hydrogen sulphide (H2S) was the main odour component generated and emitted from the Clarifiers and the Treated Effluent Transfer Sump (TETS) at the effluent treatment plant. The hydrogen sulphide (H2S) emission levels were affected by process upsets, sludge removal frequencies, chemical composition of the effluent, Sulphate Reducing Bacteria (SRB) activity, pH and temperature fluctuations. Treatment options such as pH control using slaked lime, dosing of biocides, addition of biomodifiers and/or a sulphate reduction inhibitor were investigated. The use of slaked lime, Ca(OH) 2, for pH control was not practical due to continuous pH fluctuations, increasing the pH would increase the scaling tendencies of the effluent and would also affect the soil cation-anion exchange properties of the irrigated farm land. The use of non-oxidising biocides was effective in reducing SRB activity between 99.2% and 99.8% at dosages between 4 mg/l and 25 mg/l. However, the use of biocides was not considered as a long term treatment option due to the various disadvantages such as the stability of the biocides at fluctuating pH and temperatures, half-life, environmental accumulation, toxicity and costs. The aqueous H2S level was reduced by 79% using different combinations of biomodifiers (nitrates, nitrites, molybdenum). Increasing the dosages of the biomodifiers (> 500mg/l) would be required to increase the reduction of H2S levels by more than 79%. The increased dosages would significantly increase the cost of the treatment programme. The accumulation of nitrates, nitrites and molybdenum could affect the soil texture, cation-anion exchange capacity, permeability, Sodium Absorption Ratio (SAR) and nutrient availability. A more environmentally friendly and cost effective treatment was found using sodium nitrate (biomodifier) together with AQ (sulphate reduction inhibitor). The continuous dosing of 50 mg/l sodium nitrate together with 4 mg/l AQ would be effective in reducing the average aqueous H2S levels (40 mg/l) by at least 92%. This treatment would also be compatible with aeration or oxidation procedures to further increase the removal of H2S to achieve an aqueous H2S level of <1 mg/l. Aeration or oxidation would also increase the dissolved oxygen and COD levels, increase the inhibition of SRB activity and oxidise any reduced sulphur. The dosing of sodium nitrate and AQ to control the generation of H2S is not patented in South Africa. It can, therefore, be used to treat the Kraft mill effluent without violating any intellectual property rights in South Africa. / Dissertation (MSc(Applied Science))--University of Pretoria, 2008. / Chemical Engineering / unrestricted

Abstract The combustion of fuels in motor vehicles is one of the most significant causes of air emissions. The use of oxidation catalysts in exhaust gas emission treatment can reduce hydrocarbons (HCs) and carbon monoxide (CO) emissions by more than 90%. Fuels and engine lubricants contain impurities like sulphur (S) and phosphorus (P), which can have a significant effect on the activity and durability of oxidation catalysts. This thesis aims at increasing the current knowledge of the deactivation phenomena caused by sulphur and phosphorus in diesel and natural/bio gas oxidation catalysts. Accelerated laboratory scale sulphur, phosphorus and thermal treatments in gas-phase conditions were carried out for alumina (Al2O3) based platinum (Pt) and platinum-palladium (PtPd) metallic monolith diesel and natural gas oxidation catalysts. In addition, a vehicle-aged natural gas oxidation catalyst and an engine-bench-aged diesel oxidation catalyst were studied and used as a reference for the laboratory-scale-aged catalysts. BET-BJH, FESEM, TEM, XPS and DRIFT were used as characterization techniques to determine changes on the catalysts. The effect of accelerated deactivation treatments on the catalyst activity was determined using laboratory scale measurements in CO, HC and nitric oxide (NO) oxidation. Sulphur and phosphorus were found to cause morphological and chemical changes on the studied catalysts. Sulphur was found to be adsorbed vertically throughout the entire catalyst support from the catalyst surface to the metallic monolith, while phosphorus accumulated on the surface region of the precious metal containing catalysts. Both, sulphur and phosphorus, slightly increased the average size of the precious metal particles size and are adsorbed onto the alumina by chemical bonds. In addition, a partial transformation from PdO to Pd and a change in the shape of the precious metal particles due to phosphorus were detected. Due to the detected structural and chemical changes on the catalysts, sulphur and phosphorus treatments reduced the catalytic activity of the studied diesel and natural-gas-oxidation catalysts. Correspondence between real and simulated ageing was found and thus the used accelerated laboratory scale aging method can be stated to be a good tool to simulate sulphur and phosphorus exposure. / Tiivistelmä Moottoriajoneuvot ovat merkittäviä ilmapäästöjen aiheuttajia. Hapetuskatalyyttejä käyttämällä hiilimonoksidi- ja hiilivetypäästöistä pystytään poistamaan yli 90 %. Polttoaineet ja voiteluaineet sisältävät epäpuhtauksia kuten rikkiä ja fosforia, jotka voivat merkittävästi heikentää hapetuskatalyyttien aktiivisuutta ja kestävyyttä. Väitöskirjan tavoitteena on tuottaa uutta tietoa rikin ja fosforin aiheuttamasta diesel- ja maakaasukatalyyttien deaktivoitumisesta. Metalliseen monoliittiin tuettuja alumiinioksidipohjaisia platina- ja palladiumkatalyytteja ikäytetiin tekemällä niille rikki-, fosfori- ja lämpökäsittelyjä. Maantieikäytettyä maakaasuhapetuskatalyyttiä ja moottoripenkki-ikäytettyä dieselhapetuskatalyyttiä käytettiin laboratorioikäytettyjen katalyyttien referensseinä. Ikäytyskäsittelyjen aiheuttamat muutokset analysoitiin BET-BJH-, FESEM-, TEM-, XPS- ja DRIFT-menetelmillä. Käsittelyjen vaikutus katalyyttien hiilimonoksidin, hiilivetyjen ja typenoksidien hapetusaktiivisuuteen tutkittiin laboratoriomittakaavan aktiivisuuslaitteella. Rikki ja fosfori aiheuttivat rakenteellisia ja kemiallisia muutoksia tutkittuihin katalyytteihin. Rikki adsorboitui koko tukiaineeseen (tukiaineen pinnalta pohjalle), kun taas fosfori adsorboitui vain pinnan alueelle. Sekä rikki että fosfori kasvattivat jalometallipartikkeleiden kokoa sekä muodostivat alumiinioksidin kanssa yhdisteitä. Lisäksi fosforikäsittelyjen havaittiin osittain pelkistävän PdO:n Pd:ksi ja muuttavan jalometallipartikkelien muotoa. Havaitut rikin ja fosforin aiheuttamat rakenteelliset sekä kemialliset muutokset laskivat diesel- ja maakaasukatalyyttien hapetusaktiivisuutta. Laboratorioikäytyksillä havaittiin olevan hyvä korrelaatio todellisissa olosuhteissa tehtyjen ikäytysten kanssa ja tästä syystä työssä käytetyn laboratoriomittakaavan ikäytysmenetelmän voidaan todeta olevan hyvä työkalu simuloimaan rikin ja fosforin aiheuttamaa deaktivoitumista.

Les émissions odorantes constituent un enjeu environnemental dont l'importance n'a cessé de croître dans les zones urbaines et industrielles. Les émissions anthropogéniques de composés soufrés contribuent à une concentration locale excédant fortement le seuil de perception. Afin de satisfaire des contraintes règlementaires de plus en plus strictes, les procédés biologiques dont la biofiltration sont une alternative intéressante car respectueuse de l'environnement et de moindre coût. Les seuils de perception des composés soufrés, très bas (µg. m-3), obligent à atteindre des efficacités d'abattement particulièrement élevées, le résiduel de concentration pouvant être à l'origine d'un impact notable sur les populations riveraines. L'étude a donc consisté à améliorer les performances des biofiltres concernant l'élimination des composés soufrés i) en ajustant certains paramètres opératoires clefs tels que le sens de circulation de l'effluent gazeux, le pH et l'ensemencement du matériau support, ii) en considérant le dimensionnement des biofiltres mis en œuvre (unités pilotes de laboratoire et semi-industrielles) et iii) la complexité du gaz à traiter (mono-polluant et mélange de composés à traiter). / Odorous emissions are a serious concern whose importance became higher in urban and industrial areas. Anthropogenic emissions of sulphur compounds lead to local concentration that exceeds strongly the odour threshold of human nose. In order to fulfil legal requirements that have become stricter in recent years, biological processes and biofiltration more accurately are an interesting alternative as biofilters provide an expanding variety of opportunities for economical and environmentally friendly solutions for many waste gas emissions. The odour thresholds of sulphur compounds are very low (µg.m3 air) and then require that biofilters provide high removal efficiency as the residual concentration can induce an odorous impact on neighbourhood populations.Hence, the study consisted in improving biofilters performances concerning sulphur compounds treatment i) by upgrading important operating parameters such as air flow distribution, pH and inoculation of packing material, ii) by considering biofilters design (laboratory and semi-industrial pilot units) and iii) the gaseous effluent complexity (only one pollutant and mixture of different compounds).

Sulphur stable isotope ratios are useful tracers in geological and environmental studies. They can for example be used to trace the origin of atmospheric sulphate aerosols, because anthropogenic sulphate and natural sulphate have distinguishable δ34S-values (δ34S value of approximately +0 to +8 ‰ for anthropogenic and approximately +12 to +19 ‰ for natural). This is useful for climate modelling research, due to the net cooling effect of aerosol sulphate. In the present study a Nu Plasma II (Nu Instruments) multi collector inductively coupled plasma mass spectrometer (MC-ICP-MS) method for measuring stable sulphur isotope ratios in low sulphur content samples, such as sulphate aerosols, was developed. The method was then applied to a sulphate aerosol sample collected in the Maldives.Most of the measurements were performed at high resolution, due to the interferences on 33S. Heated spray chamber coupled to a desolvating membrane, Aridus II (Cetac), increased the sensitivity and reduced interferences notably compared to wet plasma mode. Aridus II gave more stable measurements than DSN-100 (Nu Instruments). Determinations of δ34S for IAEA S1, S3, and S4 were accurate and the determined δ34S-value of the CIT #39 seawater standard (21.05 ± 0.36 ‰, 2SD, n=42) was comparable with published data. In general, Si internal standardization correction increased precision ~2.5 times compared to non-corrected values. The δ34S-value for the sulphate aerosol sample was determined to 3.82 ±0.41 ‰ (2SD, n=40). Repeatability of ~62 nmol introduced sulphur (2 μg/mL) was generally 0.15 ‰ (2SD, n=5) for the SW and 0.19 ‰ (2SD, n=5) for the sulphate aerosol sample. Comparable results for the SW (20.61±0.09 ‰, 2SD, n=4) and sulphate aersosol sample (3.77 ± 0.08 ‰, 2SD, n=8) were obtained with the method applied to Neptune Plus (Thermo Fischer Scientific) MC-ICP-MS in a different laboratory. The determined aerosol sulphate δ34S-value indicated that the sampled sulphate aerosol originated from anthropogenic sources.

The thesis deals wiring design of automated analyzer ACS 820 for carbon and sulfur. Describes individually all parts and their functionality. Evaluates applicable control components. Thesis discuss design of safety circuit, that will secure safe use of instrument. Part of the thesis is realisation of electrical design and completing the control box.

This thesis is focused on the possibilities of the utilization of the fludized fly ash in ceramic technology, especially in the field of brick manufacturing and ceramic tiles. There were used fly ashes from thermal power plants in Hodonín, Ledvice and Tisová. Fluidized fly ash can be used for manufacturing of building materials. There hasn’t been done extensive research in this area. One of the problem is sulphur dioxide leakage during burning. The work describes the behaviour of fluidized ash during firing. The attention is focused on air pollution of sulphur dioxide. The production of SO2 is controlled so that the aim of the work is to find a way how to avoid leaking. It was proved that addition of sodium ions causes the formation of minerals hauyne and nosean during firing. Also is described the behaviour of the fly ash-soil mixtures. The anhydrite decomposition temperature is lower than in pure fly ash. In the end is fluidized ash applied for the production of dry pressed ceramic tiles. This ash can be used in ceramic technology. However, despite the interesting results there are number of problems that need to be solved.