In dieser Dissertation wurden das Auftreten und die ökologische Bedeutung Vivianits in Süßwassersedimenten erforscht. Vivianit ist das am weitensten verbreitete reduzierte Eisenphosphatmineral, das sich in Gewässersedimenten bildet. Über die Mechanismen der Vivianitbildung in Sedimenten und die quantitative Rolle des Minerals für die Speicherung von Phosphor ist bisher wenig bekannt. Die neuen Erkenntnisse dieser Arbeit basieren auf der Entwicklung einer neuartigen Methode, die eine direkte Identifikation Vivianits mittels Röntgendiffraktometrie in Sedimenten erlaubte. Es gelang erstmalig, Vivianit in Oberflächensedimenten zu quantifizieren. Die vorliegende Arbeit zeigt, dass Vivianit signifikant, mit 10-40 %, zur Phosphorretention in Süßwassersedimenten beitragen kann. Die Untersuchung der Bildungsbedingungen Vivianits in unterschiedlichen Gewässersedimenten Norddeutschlands zeigte, dass das molare Schwefel zu Eisen Verhältnis des Sediments als ein wichtiger Indikator für die Bedingungen identifiziert, welche die Triebkräfte für die An- und Abwesenheit Vivianits darstellen. Eine Eutrophierung von Gewässern und der damit verbundene Anstieg der Sulfidproduktion kann dabei die Bildung Vivianits beeinträchtigen, und eine Abnahme des Phosphorbindungsvermögens des Sediments zur Folge haben. Die vorliegende Arbeit macht deutlich, dass eine artifizielle Erhöhung des Eisengehaltes des Sediments im Rahmen einer Seenrestaurierung eine Vivianitbildung induzieren kann und so langfristig zu einem erhöhten Phosphorrückhalt führt. Sättigungsberechnungen ergaben, dass ein hinsichtlich Vivianits übersättigtes Porenwasser kein sicheres Indiz für die Anwesenheit des Minerals ist. Die Berechnungen sind nicht in der Lage die kleinskaligen chemischen Bedingungen im Porenraum des Sediments abzubilden. Die Untersuchungen zeigen, dass die Bildung von Vivianit einen wichtigen Prozess der Phosphorbindung in Gewässersedimenten darstellt, der bislang jedoch weitestgehend vernachlässigt wurde. / In this thesis, the occurrence and environmental relevance of vivianite in freshwater sediments were explored. Vivianite is the most common reduced iron phosphate mineral which forms in sedimentary environments. Not much is known about the mechanisms which lead to vivianite formation in surface sediments, and about the quantitative role of vivianite in phosphorus sequestration. The development of a novel sediment preparation technique allowed the direct identification of vivianite by powder X-ray diffraction. Notably, for the first time, vivianite was quantified in surface freshwater sediments. The study examplifies that vivianite can significantly contribute to the phosphorus retention in surface freshwater sediments, accounting for 10-40 % of total sedimentary phosphorus. The exploration of vivianite in different surface freshwater sediments located in northern Germany revealed that the sedimentary sulphur to iron ratio is a valuable indicator for the conditions that are important drivers behind the formation or absence of vivianite. It has been demonstrated that eutrophication and the accompanied increase in sulphide production hampers vivianite formation, leading to a decreased phosphorus binding capacity of sediments through increased sediment sulphidization. The present study also revealed, that an iron addition as a measure of lake restoration can trigger vivianite formation, and significantly increases the long-term phosphorus retention of sediments. Pore water equilibrium calculations demonstrated that supersaturated pore water is not sufficient to predict the occurrence of the mineral in situ. Those calculations often fail to predict the occurrence of vivianite because they do not adequately represent chemical conditions within sediment microenvironments. In summary, the formation of vivianite in aquatic sediments constitutes an important process in phosphorus sequestration which has so far largely been ignored.

A adubação equilibrada com nitrogênio e enxofre pode alterar a nutrição e produção das gramíneas forrageiras. Mediante as aplicações de combinações de doses de nitrogênio com doses de enxofre, objetivou-se avaliar os efeitos: a) nas frações desses nutrientes no solo e correlacionar com as quantidades acumuladas desses nutrientes pela Brachiaria brizantha cv. Marandu; b) nas variáveis de crescimento, concentração total e formas inorgânicas de nitrogênio e enxofre e relação N:S nas raízes da gramínea forrageira; c) no consumo e eficiência do uso da água pela gramínea; d) nas variáveis estruturais, produção de massa seca e na quantidade acumulada desses nutrientes no capim-marandu e, e) na diagnose nutricional de nitrogênio e enxofre no capim, buscando determinar os níveis críticos para esses nutrientes. Dois experimentos simultâneos foram conduzidos em casa de vegetação, um com e outro sem o capim-marandu, no período de setembro a dezembro de 2008, utilizando um solo classificado como Neossolo Quartzarênico. Cinco doses de nitrogênio (0; 100; 200; 300 e 400 mg dm-3) foram combinadas com cinco doses de enxofre (0; 10; 20; 30 e 40 mg dm-3) em um fatorial 52 fracionado, com quatro repetições. No experimento sem plantas verificou-se o efeito da adubação com doses de nitrogênio e enxofre nas frações desses nutrientes no solo. A adubação com nitrogênio aumentou as frações inorgânicas de nitrato e amônio, nitrogênio total hidrolisável, nitrogênio amoniacal hidrolisável, aminoaçúcar e nitrogênio não identificado. A aplicação de doses de enxofre incrementou enxofre-éster e o enxofre residual do solo. No experimento com plantas observou-se que o fornecimento de doses de nitrogênio com doses de enxofre aumentou a massa seca de raízes, as concentrações de enxofre, nitrato e sulfato nas raízes, enquanto o comprimento e a superfície radicular, concentrações de nitrogênio e de amônio e relação N:S no sistema radicular responderam significativamente às doses de nitrogênio. Ocorreu aumento no consumo e na eficiência do uso da água pelo capim com adubação combinada de doses de nitrogênio com doses de enxofre. Número de folhas, número de perfilhos, área foliar, massa seca da parte aérea e quantidade acumulada de nutrientes pela parte aérea do capim responderam significativamente à adubação nitrogenada no primeiro corte das plantas, mas houve a necessidade de adicionar o enxofre na adubação com nitrogênio para maximizar essas variáveis nos dois crescimentos seguintes do capim. Apenas a adubação com nitrogênio foi significativa no primeiro período de crescimento, enquanto as combinações de doses de nitrogênio com doses de enxofre foram significativas no segundo e terceiro períodos de crescimento para o valor SPAD, concentrações de nitrogênio e enxofre e relação N:S nas folhas diagnósticas do capim. Correlações significativas entre a concentração de nitrogênio nas folhas diagnósticas e o valor SPAD foram observadas para os três períodos de crescimento do capim. A falta de resposta ao enxofre no primeiro período de crescimento da gramínea mostrou a baixa demanda por esse nutriente nessa fase. Os benefícios da adubação nitrogenada foram maximizados pelo suprimento conjunto com enxofre nos dois períodos subseqüentes de crescimento do capim-marandu. / Nitrogen and sulphur balanced fertilization may change mineral nutrition and yield of forage grasses. Based on the supply of combinations of nitrogen and sulphur rates, the objectives were to evaluate the effects: a) in these nutrient fractions in the soil and to correlate this fractions with nitrogen and sulphur content in Brachiaria brizantha; b) the combination of nitrogen rates with sulphur rates on the root growth characteristics, in nitrogen and sulphur, total concentration and inorganic forms and N:S ratio in roots of the forage grass; c) on water consumption and efficient use by Marandu palisadegrass; d) on structural characteristics, aboveground forage yield and nutrient content in the grass and e) on nutritional diagnosis of these nutrients in the forage, trying to obtain the critical levels of these nutrients. Two experiments were carried out at the same time under greenhouse conditions, one with and one without the Marandu palisadegrass from September to December 2008, and the soil was an Entisol. Five nitrogen rates (0; 100; 200; 300 and 400 mg dm-3) were combined with five sulphur rates (0; 10; 20; 30 and 40 mg dm-3) in fractionated 52 factorial, with four replications. In the experiment without plants, the nitrogen and sulphur fertilization changed these nutrients fractions in the soil. Nitrogen fertilization increased inorganic fractions of nitrate and ammonium, hydrolyzable total nitrogen, hydrolyzable ammonium, amino sugars and unidentified nitrogen. Application of sulphur rates increased estersulphur and residual sulphur in the soil. In the experiment with plants, supply of both nitrogen and sulphur increased root dry matter production, total sulphur, nitrate and sulphate-sulphur concentrations, while for total root length and root surface area, total nitrogen and ammonium concentrations and N:S only ratio nitrogen rates had significant responses. Nitrogen and sulphur rates increased the water consumption and efficiency of use by grass. Numbers of leaves, number of tillers, leaf area, shoot dry masss and nitrogen content in the shoots of forage grass showed significant responses to nitrogen fertilization in the first growth period but it was necessary to add sulphur in the fertilization to maximize these variables for following two growth period of the grass. Only nitrogen fertilization was significant in the first growth period, while the combinations of nitrogen and sulphur rates were significant for the SPAD value, concentrations of nitrogen and sulphur and N:S ratio in diagnostic leaves of the grass. Significant correlation was observed for nitrogen concentration in diagnostic leaves and SPAD value the three growth periods. Sulphur demand by Marandu palissadegrass was low in the first growth period, but the nitrogen fertilization benefits were maximized by adding sulphur in the fertilization of this grass.

A adubação equilibrada com nitrogênio e enxofre pode alterar a nutrição e produção das gramíneas forrageiras. Mediante as aplicações de combinações de doses de nitrogênio com doses de enxofre, objetivou-se avaliar os efeitos: a) nas frações desses nutrientes no solo e correlacionar com as quantidades acumuladas desses nutrientes pela Brachiaria brizantha cv. Marandu; b) nas variáveis de crescimento, concentração total e formas inorgânicas de nitrogênio e enxofre e relação N:S nas raízes da gramínea forrageira; c) no consumo e eficiência do uso da água pela gramínea; d) nas variáveis estruturais, produção de massa seca e na quantidade acumulada desses nutrientes no capim-marandu e, e) na diagnose nutricional de nitrogênio e enxofre no capim, buscando determinar os níveis críticos para esses nutrientes. Dois experimentos simultâneos foram conduzidos em casa de vegetação, um com e outro sem o capim-marandu, no período de setembro a dezembro de 2008, utilizando um solo classificado como Neossolo Quartzarênico. Cinco doses de nitrogênio (0; 100; 200; 300 e 400 mg dm-3) foram combinadas com cinco doses de enxofre (0; 10; 20; 30 e 40 mg dm-3) em um fatorial 52 fracionado, com quatro repetições. No experimento sem plantas verificou-se o efeito da adubação com doses de nitrogênio e enxofre nas frações desses nutrientes no solo. A adubação com nitrogênio aumentou as frações inorgânicas de nitrato e amônio, nitrogênio total hidrolisável, nitrogênio amoniacal hidrolisável, aminoaçúcar e nitrogênio não identificado. A aplicação de doses de enxofre incrementou enxofre-éster e o enxofre residual do solo. No experimento com plantas observou-se que o fornecimento de doses de nitrogênio com doses de enxofre aumentou a massa seca de raízes, as concentrações de enxofre, nitrato e sulfato nas raízes, enquanto o comprimento e a superfície radicular, concentrações de nitrogênio e de amônio e relação N:S no sistema radicular responderam significativamente às doses de nitrogênio. Ocorreu aumento no consumo e na eficiência do uso da água pelo capim com adubação combinada de doses de nitrogênio com doses de enxofre. Número de folhas, número de perfilhos, área foliar, massa seca da parte aérea e quantidade acumulada de nutrientes pela parte aérea do capim responderam significativamente à adubação nitrogenada no primeiro corte das plantas, mas houve a necessidade de adicionar o enxofre na adubação com nitrogênio para maximizar essas variáveis nos dois crescimentos seguintes do capim. Apenas a adubação com nitrogênio foi significativa no primeiro período de crescimento, enquanto as combinações de doses de nitrogênio com doses de enxofre foram significativas no segundo e terceiro períodos de crescimento para o valor SPAD, concentrações de nitrogênio e enxofre e relação N:S nas folhas diagnósticas do capim. Correlações significativas entre a concentração de nitrogênio nas folhas diagnósticas e o valor SPAD foram observadas para os três períodos de crescimento do capim. A falta de resposta ao enxofre no primeiro período de crescimento da gramínea mostrou a baixa demanda por esse nutriente nessa fase. Os benefícios da adubação nitrogenada foram maximizados pelo suprimento conjunto com enxofre nos dois períodos subseqüentes de crescimento do capim-marandu. / Nitrogen and sulphur balanced fertilization may change mineral nutrition and yield of forage grasses. Based on the supply of combinations of nitrogen and sulphur rates, the objectives were to evaluate the effects: a) in these nutrient fractions in the soil and to correlate this fractions with nitrogen and sulphur content in Brachiaria brizantha; b) the combination of nitrogen rates with sulphur rates on the root growth characteristics, in nitrogen and sulphur, total concentration and inorganic forms and N:S ratio in roots of the forage grass; c) on water consumption and efficient use by Marandu palisadegrass; d) on structural characteristics, aboveground forage yield and nutrient content in the grass and e) on nutritional diagnosis of these nutrients in the forage, trying to obtain the critical levels of these nutrients. Two experiments were carried out at the same time under greenhouse conditions, one with and one without the Marandu palisadegrass from September to December 2008, and the soil was an Entisol. Five nitrogen rates (0; 100; 200; 300 and 400 mg dm-3) were combined with five sulphur rates (0; 10; 20; 30 and 40 mg dm-3) in fractionated 52 factorial, with four replications. In the experiment without plants, the nitrogen and sulphur fertilization changed these nutrients fractions in the soil. Nitrogen fertilization increased inorganic fractions of nitrate and ammonium, hydrolyzable total nitrogen, hydrolyzable ammonium, amino sugars and unidentified nitrogen. Application of sulphur rates increased estersulphur and residual sulphur in the soil. In the experiment with plants, supply of both nitrogen and sulphur increased root dry matter production, total sulphur, nitrate and sulphate-sulphur concentrations, while for total root length and root surface area, total nitrogen and ammonium concentrations and N:S only ratio nitrogen rates had significant responses. Nitrogen and sulphur rates increased the water consumption and efficiency of use by grass. Numbers of leaves, number of tillers, leaf area, shoot dry masss and nitrogen content in the shoots of forage grass showed significant responses to nitrogen fertilization in the first growth period but it was necessary to add sulphur in the fertilization to maximize these variables for following two growth period of the grass. Only nitrogen fertilization was significant in the first growth period, while the combinations of nitrogen and sulphur rates were significant for the SPAD value, concentrations of nitrogen and sulphur and N:S ratio in diagnostic leaves of the grass. Significant correlation was observed for nitrogen concentration in diagnostic leaves and SPAD value the three growth periods. Sulphur demand by Marandu palissadegrass was low in the first growth period, but the nitrogen fertilization benefits were maximized by adding sulphur in the fertilization of this grass.

INTRODUÇÃO: Metionina (Met), cisteína (Cys), homocisteína (Hcy) e taurina (Tau) são os quatro aminoácidos sulfurados (AAS), mas apenas a Met e Cys são incorporadas em proteínas. Os três principais produtos doS AAS, glutationa, (GSH), Hcy e Tau influenciam, principalmente, as respostas inflamatória e imune. A Tau e GSH diminuem a inflamação, enquanto que a Hcy apresenta efeito oposto. Os pacientes HIV+ apresentam baixos níveis de GSH e outros nutrientes antioxidantes, mostrando relação direta entre Cys (e GSH) com células CD4+. Não se conhece o mecanismo pelo qual as mudanças na ingestão dos AAS influenciam este fenômeno. Paralelamente, as relações entre Hcy, doenças inflamatórias e alterações in vitro no comportamento das células imunes levantou ressalvas sobre a suplementação de dietas com AAS. OBJETIVOS : investigar as vias dos AAS em pacientes HIV+ nas condições de jejum e pós-sobrecarga de Met frente à dieta habitual (OH) isolada ou acompanhada da suplementação de Cys (NAC) ou glutamina (Gln). MÉTODOS : 12 pacientes HIV+ (6 M e 6 F, de 25 a 36 anos), sob tratamento anti-retroviral pelo esquema tríplice, sem infecções secundárias e 20 controles saudáveis (10M e 10F, 23-28 anos) foram randomicamente distribuídos para suplementação com NAC (N-acetilcisteína, 1g/d) ou Gln (20 g/d) em estudo cruzado com 7 dias de dieta separados por uma semana de washout (Wo com DH). Amostras de sangue após jejum noturno de 10 a 12 horas foram coletadas antes (MO) e após (M1) cada regime dietético. A seguir, os indivíduos ingeriram metionina (100 mg/kg), com coletas de sangue após 2 e 4 horas para a determinação da área abaixo da curva (AAC). No MO, ambos os grupos foram avaliados quanto à antropometria (IMC, kg/m2), funções glomerular (uréia, creatinina) e hepatocelular (γ-GT), estados nutricional (albumina, cálcio, ácido fólico e vitamina 812) e antioxidante (ácido úrico, GSH, GSSG, Hcy), glicose, lipídios (triacilgliceróis e frações de colesterol) e AAS, serina (Ser), glicina (Gly), glutamato (Glu) e Gln. O grupo HIV também foi caracterizado pela carga viral e contagem de CD4+ e CD8+. As comparações estatísticas entre os grupos e entre as dietas mostraram homogeneidade para IMC, albumina, cálcio, vitamina 812, Hcy, HDL-colesterol, uréia e creatinina. Os pacientes apresentaram valores maiores de glicose, triacilgliceróis, γ-GT, LDL-colesterol e GSSG paralelalemente às menores concentrações de ácido úrico, GSH e todos os AAS, exceto Hcy. A sobrecarga de metionina igualou (pelos valores de delta) os grupos para Met, Hcy, Tau e Gln. As suplementações de NAC e Gln levaram o grupo HIV+ a concentrações maiores de GSH (NAC > Gln), atuando diferentemente em seus precursores: G/y (Gln > NAC) e Cys (NAC > Gln) e resultando em consumo similar de Ser e produção de Tau. Ambas as dietas reduziram GSSG/GSH (NAC > Gln) e apenas NAC aumentou (6 x) a Hcy. Esta última foi piorada pela sobrecarga de Mel. Assim, HIV+ resulta em deficiências múltiplas de vitaminas e aminoácidos levando a menores níveis de GSH e GSSG/GSH mais elevada. Os principais problemas de menor formação de Cys e menor incorporação de Cys em GSH foram resolvidos dando-se Met, NAC e Gln aos pacientes, ainda permanecendo a desvantagem do aumento da Hcy com Met ou suplementação de NAC. / BACKGROUNO: Methionine (Met), cysteine (Cys), homocysteine (Hcy), and, taurine (Tau) are the 4 sulfur-containing amino acids (SAA), but only Met and Cys are incorporated into proteins. The 3 major products of SAA, glutathione (GSH), Hcy and Tau influence, mainly, inflammatory and of immune responses. Tau and GSH ameliorate inflammation whereas Hcy has the opposite effect. HIV+ patients present low levelis of GSH and other antioxidants nutrients, showing a direct relationship between Cys (and GSH) with CD4+/ cells. How changes in SAA intake influence this phenomenon is unknown and the relationships among Hcy, inflammatory diseases, and in vitro alterations in immune cell behavior create a cautionary note about supplementation of diets with SAA. OBJECTIVE: To investigate SAA pathways in HIV+ patients on fast and Met-overload (Met-DL) states after taken diet habitual without (HD) or with supplements of Cys (NAC) or glutamine (Gln). METHOOS: 12 HIV+ (6M and 6F, 25-36 yrs old) patients under HAART without secondary infections and 20 healthy (10M and 10F, 23-28 yrs old) controls were randomly assigned to either NAC (N-acetylcysteine, 1g/d) or Gln (20g/d) diets, in a 7-day diet crossover design, separated by a 7-day washout (with HD) period. Blood samples were drawn after overnight fast before (MO) and after each dietary treatments (M1) for the resting measurements. Immediately after blood sampling ali subjects started the Met-DL by ingesting at once 100 mg Met/kg BW and having the blood draw after 2 and 4 hours for the area under the curve (AUC) determination. At MO both groups were assessed for anthropometry (BMI, kg/m2), glomerular (plasma urea and creatinina) and hepatocellular (plasma γGT activity) funetions, nutritional (albumin, calcium, folic acid and vitamin B12) and antioxidant (uric acid, GSH, GSSG, Hey) states, glucose, lipids (triglycerides and cholesterol fractions) and SAA, serine (Ser), glyeine (Gly), glutamate (Glu) and Gln. The HIV+ group was characterized also by viral load, CD4+ and CD8+ counts. The statistical comparisons between groups and among diets showed group homogeneity for 8MI, albumin, calcium, vitamin B12, Hey, HDL-cholesterol, urea and creatinine. The patients presented higher values of glucose, triglycerides, γ-GT, LDL-cholesterol, and GSSG along with lower concentrations of uric acid, GSH and all but Hcy amino acids. The Met-OL equalized (Δ values) the groups for Met, Hcy, Tau and Gln. NAC and Gln diets led the HIV+ group to a higher concentrations of GSH (NAC > Gln) by acting differently on its precursors: Gly (Gln > NAC) and Cys (NAC > Gln), resulting similar consumption of Ser and production of Tau. Both diets reduced GSSG/GSH (NAC > Gln) and only NAC increased (6 x) Hey. The later was worsened by Met-OL. Thus HIV+ results in multiple deficiencies of vitamins and amino acids leading to lower levels of GSH and higher GSSG/GSH ration. The main problems of lower formation of Cys and low ineorporation of Cys and Gly into GSH were greatly solved by giving Met, NAC and Gln to the patients, hence remaining the drawback of increasing Hcy with Met or NAC supplements.

The effects of crop load and berry exposure on the composition of Marlborough Sauvignon blanc grapes and wine from the Brancott vineyard, Blenheim, were explored. Commercially grown, 2-cane and 4-cane Sauvignon blanc vines were used with a row orientation of north-south. Two exposure treatments were imposed in the following manner: complete leaf removal was undertaken in the fruit zone and 50% shade cloth was erected to give a uniform shading treatment to half the trial vines. Weekly thirty-berry and whole bunch samples were taken from each of the 32 plots with the exception of the veraison period when two samples per week were taken. Vine vigour was assessed using pruning and leaf area per vine data. Harvest occurred on different dates for 2-cane and 4-cane pruned vines so that fruit attained from both treatments had similar °Brix. Fruit was processed at the Lincoln University winery. Must analysis and wine analysis were undertaken. As expected, 4-cane vines had almost double the yield of 2-cane vines. Higher crop load significantly reduced leaf area per shoot and shoot thickness. Lower leaf area to fruit ratio for 4-cane berries resulted in delayed onset of veraison and slowed the rate of sugar accumulation. Crop load, which limited leaf area to fruit ratio, appeared to be the dominant factor in determining timing of grape physiological ripeness as expressed by °Brix over other factors such as fruit exposure. Malic acid, tartaric acid, IPMP (iso-propylmethoxypyrazine) and IBMP (iso-butyl-methoxypyrazine) were lower at equivalent °Brix in 4-cane compared with 2-cane berries. Significantly higher concentrations of quercetin were found in exposed compared to shaded berries. Must analysis showed a significant influence of crop load on berry titratable acidity and pH, reflecting berry ripening results. Exposure significantly increased the concentrations of nitrogenous compounds in 4-cane must yet showed no influence on 2-cane must. After wine processing lower malic acid concentrations in wines made from 100% exposed fruit became evident in lower wine titratable acidity but showed no influence on wine pH. Bentonite addition to wines had a small but statistically significant influence on wine by reducing pH, titratable acidity and alcohol. Bound sulphur concentrations were significantly higher in 4-cane versus 2-cane wines. At harvest, methoxypyrazine levels in grapes and wines were very low; IBMP concentrations where significantly lower than those normally found in Sauvignon blanc wines from Marlborough. This was attributed to the absence of basal leaves from the shoots of ripening berries. The results suggest that leaf area to fruit ratio is a powerful determinant of grape and wine quality.

The study undertaken was carried out in the montane tussock grassland region which in the South Island comprises some six million acres. Field trials were established at Mt Somers, Mid Canterbury. This study attempts to elucidate some of the factors connected with the sulphur nutrition of grasses. For the particular trial area it was hoped to determine four key aspects ; 1. Whether the response of the grass to nitrogen is governed by the sulphur level available. 2. A determination of what level of nitrogen was likely to be provided by clover fixation and transferred to the grass component under improved grassland conditions in the area. 3. What the optimum level of sulphur for the association is, allowing adequate sulphur for maximum possible nitrogen fixation as well as for utilization by the grass of the nitrogen transferred. 4. The effects of nitrogen and sulphur on plant chemical composition and any possible relationships between plant and soil as infuenced by these factors. Following a review of literature, a summary of experimental work is presented, with results, discussion and conclusions.

Graduation date: 2005

The main aim was to investigate the provenance of Viking age antler material findings of moose and red deer from Sigtuna and from three sites on the island of Gotland in the Baltic sea. This was done by analysis of the stable isotopes of carbon, nitrogen and sulphur. Thre were never any living population of these mammals on Gotland during the Viking age. δ34S-values of sulphur from this study was compared with earlier research and by studying maps of the Swedish bedrock. The δ34S-values were more like the δ34S-value for bedrock other than European granite. These bedrocks are found in the south-east of Sweden along the coast towards Gotland. The provenance of the Sigtuna antlers could be three different areas and the material from Gotnald could come from two differente regions. A student-t test between Fröjel and Sigtuna showed no significant correlation between the two populations. A comparison within the Sigtuna material showed a possible difference between two different dated phases. This could mean that an import of antlers from other areas was made when antlers in the Sigtuna region was less available.

Der Einfluss der Modifikation der technologisch relevanten GaAs(100) Oberfläche durch Chalkogene, i.e. Selen, Schwefel und Tellur, wird in dieser Arbeit untersucht. Es wird ein Modell vorgestellt, das die Eigenschaften der modifizierten Oberfläche beschreibt. In einem zweiten Schritt werden die so modifizierten Oberflächen mit Metallen unterschiedlicher Reaktivität und verschiedenen Elektronegativitäten bedampft. Die Bandbreite dieser Eigenschaften wird durch die Metalle Indium und Silber, das Alkalimetall Natrium, das Erdalkalimetall Magnesium und das Halbmetall Antimon abgebildet. Die Untersuchung des Einflusses der Chalkogene auf die chemischen Eigenschaften und die Barrierenhöhe der Metall/GaAs(100) Grenzfläche bilden einen weiteren Schwerpunkt. Die Änderung der Barrierenhöhe wird dabei mit Hilfe des Modells metallinduzierter Bandlückenzustände (metal induced gap states) erklärt. Als experimentelle Techniken werden Photoemissionsspektroskopie, Raman Spektroskopie und Strom-Spannungsmessungen verwendet. / The influence of a modification of the technological relevant GaAs(100) surface by chalcogens, i.e. selenium, sulphur and tellurium, is evaluated in this work. A model is proposed, which describes the properties of the modified surface. In a second step metals of different reactivity and electronegativity have been evaporated onto these modified surfaces. Among these materials were the metals indium and silver, the alkali metal sodium, the earth alkali metal magnesium and the half metal antimony. The investigation of the influence of chalcogens on the chemical properties and the barrier height of the metal/GaAs(100) interface is another point of interest. The change in barrier height is explained by the model of metal induced gap states (MIGS). Photoemission spectroscopy, Raman spectroscopy and current-voltage-measurement have been used as experimental techniques.

Ce mémoire décrit et analyse différents types de systèmes d'échange de droits d'émission utilisés dans le cadre de politiques de gestion de la pollution atmosphérique. L'objectif premier est de répertorier des enjeux juridiques étant liés à l'efficacité de ces systèmes. Dans un premier temps, nous nous attardons à la structure et aux mécanismes internes des systèmes d'échange de droits d'émission. Tout d'abord, nous soulignons le fondement théorique de ce type de système. Nous évaluons par la suite la structure et certains litiges liés au système d'échange américain dans le cadre des émissions de dioxyde de soufre. Dans un deuxième temps, nous continuons la description de systèmes en nous attardant plus spécifiquement aux interactions entre les systèmes d'échange de droits d'émission et les autres politiques et règlementations environnementales (incluant d'autres systèmes d'échange d'émission) visant la même problématique environnementale. / The present essay describes and analyses different types of emissions trading schemes as an instrument in air quality and environmental policy. The objective is to index legal stakes or risks relating to the efficiency of emissions trading schemes. ln the first part, we evaluate the structure and the design of emissions trading schemes. The knowledge of the economic theory transcending those schemes is necessary to understand ail the structural mechanisms. After this evaluation, this essay proposes an analysis of the U.S. sulphur dioxide program based on the U.S. Clean Air Act and sorne of the litigations that occurred in the application of the said program. ln part two, we are describing the structure and the design of emissions trading schemes with the specific goal of underlining the interactions between different types of environmental policies or regulations and emissions trading schemes when they are ail used for the same environmental problem. / "Mémoire présenté à la Faculté des études supérieures en vue de l'obtention du grade de Maîtrise en droit (LL.M.) option recherche". Ce mémoire a été accepté à l'unanimité et classé parmi les 15% des mémoires de la discipline. Commentaires du jury ; "Le jury souligne la difficulté du sujet et l'importance des enjeux économiques, politiques et juridiques. Le candidat a bien déblayé le sujet et a su structurer son analyse de manière intéressante".