Stable isotope ratios in rainwater and water vapor act as a tracers of the hydrological cycle. The data on stable isotopic composition in rainwater and water vapor are limited due to the lack of observational studies across the Indian subcontinent and over the ocean. These present day observations are important database to deduce the paleo-climatic condition from geological archives. In majority of the cases, isotopic records are translated into physical factors with the present background knowledge where relationships with physical variables are well established. In case of tropical region, the primary controlling factor identified behind the stable isotopic variations is the amount of rainfall. However recent observations contradict such relationships challenging the role of amount effect and identified source moisture effect on stable isotope ratios in rainwater at Indian stations. The thesis investigated the amount effect relationship of isotopes at seasonal time scales. The long period observation covering 4 years, where daily time interval rainwater samples collected were used for our study. We used two different station locations; Thiruvananthapuram and Bangalore, where monsoonal rainfall is received for Southwest and Northeast periods. The role of mesoscale and synoptic convection and rainout along the transport pathways were found responsible for the isotopic variance. The role of moisture source regions, rainout over the advection pathways, high rainfall producing systems such as depression and cyclones, and continental recycling of water on rainwater and water isotopes ratios were major findings of the thesis work which are detailed in the chapters. Upon knowing the atmospheric and oceanic condition at the moisture source region based on satellite data and reanalysis data set we modeled our observations using the governing equations of isotope fractionation and well accepted Rayliegh’s distillation model. The observations on rainwater and water vapor isotope ratios in oceanic region are extremely limited due to difficulties in conducting sampling. Water vapor and rainwater observations over the Southern Ocean during the expedition of 2013 and estimation of the moisture recycling across the latitudes over the oceanic regions is a novel work in this thesis.

F. graminearum est l’une des espèces prédominantes en tant que pathogène des céréales en Europe et dans les régions tempérées du monde. Cette moisissure appartient au genre Fusarium qui est l’un des genres qui produit le plus de métabolites secondaires, dont de nombreuses mycotoxines. Cependant, les connaissances sur son génome laissent présager que F. graminearum produit une très grande variété de métabolites qui sont encore inconnus. C’est pourquoi l’objectif de cette thèse a été de caractériser le métabolome de cette moisissure en identifiant de nouveaux métabolites ainsi qu’en étudiant leur toxicité. Pour cela, une méthode analytique combinant la spectrométrie de masse de haute résolution et le marquage des métabolites secondaires avec des isotopes stables a été développée. Celle‐ci à tout d’abord était validée avec le métabolome bien connu d’Aspergillus fumigatus avant d’être appliquée au métabolome de F. graminearum. Cette méthode a permis d’identifier 37 nouveaux métabolites, dont les fusaristatines A, C et D qui on été détectées pour la première fois chez F. graminearum. Le deoxynivalenol (DON) est une mycotoxine majeure produite par F. graminearum, c’est pourquoi sa toxicité a été comparée in vivo sur un modèle porcin à celle d’un mélange de fusariotoxines. Les résultats de cette étude ont montré une toxicité bien différente du mélange par rapport au DON seul, que ce soit par rapport à la performance des animaux ou à leur réponse immunitaire. Ceci suggère que certaines des fusariotoxines présentes dans le mélange auraient des répercutions biologiques et donc que leur toxicité reste encore à être élucidée. De plus, l’importance de la caractérisation de la toxicité du métabolome de F. graminearum a été soulignée par les résultats obtenus dans une seconde étude, qui ont révélés une possible implication du DON dans les maladies inflammatoires chroniques de l’intestin par l’intermédiaire des lymphocytes Th17. / F. graminearum is one of the most predominant cereal pathogen in Europe and temperate regions of the world. It belongs to the genera Fusarium, which is one of the most important in terms of the production of secondary metabolites, among which stand several mycotoxins. However, recent advances on the study of its genome suggest that only a small fraction of the secondary metabolites produced by F. graminearum have been identified so far. Therefore, the main objective of this thesis was to characterize the metabolome of this fungus by identifying new metabolites and by analyzing their toxicity. First, an analytical method combining high resolution mass spectrometry and isotopically labeled secondary metabolites was developed. The method was validated with the well known metabolome of Aspergillus fumigatus before it was applied to F. graminearum. As a result, 37 new metabolites were identified such as fusaristatin A, C and D, which were detected for the first time in the metabolome of F. graminearum. Deoxynivalenol (DON) is one of the major mycotoxins produced by this fungus. Therefore, its toxicity was compared to that of a blend of fusariotoxins in vivo in a pig model. The results of this study showed different effects of the blend compared to DON alone on animal performances and immune response. This suggests that some of the fusariotoxins present in the blend could be biologically active and their toxicity should be further investigated. Toxicity of the metabolome of F. graminearum has also been highlighted by the results of a second study which showed a possible implication of DON on the appearance of inflammatory bowel diseases by the action of Th17 lymphocytes.

L’Archéen, de 4 à 2,5 Ga, est la période qui a connu les plus grands bouleversements géologiques et biologiques de l’histoire de la Terre : formation des continents, transition d’une tectonique à composante verticale vers une tectonique des plaques horizontale, apparition de la vie, … Le but de cette thèse est d’étudier les conditions environnementales de la Terre à l’Archéen, par l’analyse des compositions isotopiques de métaux de transition (Fe, Zn) de roches provenant principalement de la province d’Isua au Groenland (3,8 Ga). Après avoir adapté le protocole de séparation du Fe, Cu, Zn à des échantillons riches en Fe, nous avons acquis les données par spectrométrie de masse à source plasma et à multicollection MC-ICPMS. Nous nous sommes d’abord intéressés au processus de serpentinisation de la croûte océanique, réaction produisant à la fois des nutriments pour la vie (CH 4 , H 2 ) et des minéraux catalyseurs (mackinawite) de la formation abiotique d’acides aminés, molécules du vivant. L’affleurement d’Isua comporte une unité ophiolitique présentant les serpentinites les plus anciennes (3.81-3.70 Ga) : leur analyse permet d’appréhender la réaction de serpentinisation à l’Archéen. Les résultats obtenus pour la composition isotopique du zinc dans ces roches et dans des serpentinites modernes ont permis d’établir une correspondance entre le processus de serpentinisation à Isua et la mise en place de volcans de boues de serpentinites à l’aplomb de la fosse des Mariannes. Nous avons ainsi pu identifier Isua comme une zone d’arrière-arc de subduction océanique, lieu d’une serpentinisation produisant des fluides de température variable (100-300°C) et de pH alcalin (9-12). Nous montrons que cette configuration atypique réunissant serpentinisation, fluides alcalins et édifices volcaniques est favorable à l’émergence du vivant. Nous avons ensuite analysé de nombreux échantillons de formations de fer rubané (BIFs), sédiments propres à l’Archéen et au début du Protérozoïque. L’évolution de la composition isotopique du zinc de ces échantillons au cours du temps a permis d’établir une chronologie de l'émersion des continents.Nos résultats sont en faveur d’une émersion débutant il y a 2,9 Ga. Enfin, nos données nous informent sur la colonisation des continents émergés par la vie à 2,6 Ga et sur la pédogenèse de sols archéens comportant un horizon organique. / During the Archean (4 to 2.5 Ga ago), the Earth experienced the biggest changes in terms of geological and biological settings – continental growth, transition from sagduction towards purely horizontal plate tectonics, emergence of life, … The purpose of the present study is to better understand the archean earth environment by measuring the isotopic composition of transition metals – Zn, Fe – of archean rocks. Most of the samples belong to the Isua supracrustal belt, in Greenland, dated 3.8 Ga. The chemical extraction protocol of Fe, Cu, Zn was adapted to our Fe-rich samples and isotopic analyses were conducted by multicollection inductively coupled plasma mass spectrometry. The serpentinization of the oceanic crust produces fuels for life (CH 4 , H 2 ) and mackinawite, which catalyses formation of complex organic compounds. Serpentinization may thus provide a suitable environment for the emergence of the first biomolecules. We analysed the oldest known serpentinites from Isua (3.81-3.70 Ga) to comprehend the archean serpentinization process. The isotopic compositions of zinc reported in this samples and in modern serpentinites attest to a strong similarity between Isua and the Mariana serpentinite mud volcanoes. We identified Isua as an oceanic forearc environment permeated by high-pH (9-12) hydrothermal solutions at medium temperature (100-300°C). We show that such an environment could have fostered the emergence of early life. We also analyzed several banded iron formations (BIF), which are sediments limited to the Archean and Proterozoic. The temporal evolution of these samples' isotopic composition shows a close relationship with the continental freeboard. Our results support the continental emersion starting 2.9 Ga ago. Besides, we identified the life colonization of continents at 2.6 Ga together with pedogenesis of archean soils with an organic horizon.

Orientador: Roberto Perez Xavier / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Geociências / Made available in DSpace on 2018-08-24T11:02:32Z (GMT). No. of bitstreams: 1 AcevedoSerrato_AnderssonAlirio_M.pdf: 3771845 bytes, checksum: af79a7b62ce99b19ea8f0dedd231322e (MD5) Previous issue date: 2014 / Resumo: O depósito aurífero de Juruena, localiza-se no setor oeste da Província Aurífera de Alta Floresta, sul do Cráton Amazônico, onde se hospeda em rochas graníticas da Suíte Intrusiva Paranaíta (1819 - 1793 Ma). Foram reconhecidos cinco tipos de alteração hidrotermal no depósito, organizado cronologicamente do evento mais precoce à mais jovem: (1) alteração potássica com veios de quartzo-sulfetos e quartzo+clorita+fluorita+sulfetos; (2) alteração sericitica com veios de quartzo+molibdenita±pirita com halo de feldspato K e veios de quartzo+calcita+clorita com halo de sericita ; (3) carbonatação com veios de calcita-fluorita-sulfetos; (4) silicificação, pervasiva e em veios; e (5) alteração propilítica com veios de epídoto e calcita. A mineralização encontra-se hospedada nos eventos 1 e 3, onde aparece principalmente como inclusões ou preenchendo fraturas em pirita e também relacionado com fases minerais ricas em Te-Bi-Ag. Estudos da paragênese do minério combinados com analises de microssonda, indicam sucessivos eventos de formação de piritas, definidos em quatro gerações: pirita euedral porosa (py1), desenvolvida nos veios iniciais da alteração potássica; pirita de granulação grossa, arredondada a subhedral, não porosa (py2), representante da segunda geração de pirita com cristais ocorrendo distribuídos na alteração potássica e sericitica; pirita anedral, muito porosa, com abundantes inclusões de silicatos, sendo esta fase dominante na alteração sericitica (py3). Pirita sobrecrescida nos cristais da geração mais jovem (py3) representante por tanto da ultima geração. Ressalta-se ainda que as gerações de py2 e py3 contém inclusões de ouro livre e ouro-teluretos. A geoquímica de elementos traço em pirita, revela que pirita de estágios mais precoces (py1) geralmente são mais pobres em ouro (Au < 0.02wt%) quando comparada à pirita de fases mais tardia (py2 e py3) que pode mostrar valores de Au de até 0.035 wt%. As análises também sugerem que o ouro deve ocorrer como nano- micropartículas na pirita e não como parte de sua estrutura cristalina. O cobre apresenta comportamento oposto, com contrações mais baixas em pirita tardia (Cu < 0.04wt%). Uma amostra de molibdenita associada à paragênese do minério aurífero forneceu uma idade modelo Re-Os de 1805 ± 7 Ma. Levando em consideração o erro, esta idade se sobrepõe parcialmente às idades U-Pb SHRIMP em zircão de 1790 ± 6.4 Ma,(com um nível de confiança de 95%, MSWD = 4.8, n =15) e de 1792 ± 5.8 (com um nível de confiança de 95%, MSWD = 0.32, n =17) obtidas, respectivamente em biotita monzogranito (principal hospedeira da mineralização) e em micromonzogranito representante da ultima fase granítica no depósito. Essa sobreposição sugere uma possível relação genética entre o magmatismo félsicos de idade correlata ao da Suíte Intrusiva Paranaíta e a mineralização aurífera. Dados de inclusões fluidas indicam que fluidos aquo-carbônicos com salinidades entre 0.6 e 11.3 wt% NaCl equiv. e temperaturas no intervalo de 341 ¿ 456 oC foram responsáveis pelos estágios iniciais da mineralização aurífera conteúdos na alteração potássica. Durante a evolução os fluidos ricos em CO2 decrescem, dando lugar para um regime de fluidos aquosos de salinidade elevada (31.4 e 36 wt% NaCl equiv.) com temperaturas entre 239 e 349 oC , representado por inclusões fluidas saturadas em sais. Fluidos essencialmente aquosos mais frios (155 ¿ 285 oC ) e de baixa salinidade representa os estágios finais do sistema hidrotermal. Valores calculados de ?18O para os fluidos hidrotermais oscilam entre 6.9 e 0.5 ¿ indicando uma fonte predominantemente magmática, com adição de pequenas quantidades de aguas meteóricas nos veio mais tardios da alteração sericitica. Os valores ?34S para os sulfetos (-7.1 até +1.5 ¿), são consistente com a precipitação a partir de uma fonte magmática oxidada. Um importante zoneamento foi reconhecido: valores menores de ?34Ssulfetos (-7.1 até -4.5 ¿) tendem a se associar aos veios representativos do estágio precoce da mineralização aurífera, enquanto que valores mais elevados de ?34Ssulfetos (-0.5 até +1.5 ¿) correspondem ao sulfetos contidos na carbonatação, o ultimo evento estudado. Este zoneamento é o resultado da interação fluido-rocha que muda as condições de oxidação-redução ao longo da evolução do fluido magmático-hidrotermal no depósito. Baseados nos dados de campo, petrográficos, de inclusões fluidas, isotópicos e na geoquímica de elementos traço é possível definir que o depósito aurífero de Juruena se trata de um sistema magmático-hidrotermal, com fluidos ricos em CO2 que evoluem para fluidos aquosos. O minério foi depositado diretamente dos fluidos hidrotermais durante diferentes e repetidos pulsos hidrotermais de composição variável. Os processos de formação do depósito aurífero de Juruena são similares aos depósitos do tipo ouro-pórfiro. / Abstract: The Juruena deposit belongs to a large group of intrusion-hosted gold deposits of the Alta Floresta Gold Province in the southern portion of the Amazonian Craton. This gold deposit is hosted by granitic rocks of Paranaita Intrusive Suite (1819 to 1793 Ma) which is crosscut by different sets of mafic intrusions. The hydrothermal alteration can be divided into five stages, from early to late: (1) potassic alteration, with quartz+sulfides and quartz+chlorite+fluorite+sulfides veins (2) sericitic alteration with quartz+molybdenite±pyrite veins with K-feldspar halo and quartz+calcite+chlorite veins with sericitic halo; (3) carbonatization with calcite+fluorite+sulfides veins; (4) silicification, pervasive and in veins; and (5) propylitic alteration with epidote and calcite veins. The mineralization is hosted in stages 1 and 3, where it occurs mostly as particles or filling fractures in the pyrite crystals and related with Te-Bi-Ag phases. Paragenetic studies of the mineralization combined with microprobe analysis indicated successive stages of pyrite formation defined in four generations: euhedral porous form the earliest generation, developed in the earliest veins from potassic alteration (py1). Coarser grained pyrite is a rounded to subhedral nonporous generation distributed in potassic and sericitic alterations (py2). Anhedral very porous generation contains abundant inclusions of silicates and is the dominant generation on the sericitic alteration (py3). Py2 and py3 contain inclusions of native gold and gold tellurides. The fourth generation (py4) overgrows the earlier py3. The geochemistry of trace elements in pyrite reveal that the earliest generation (py1) is particularly depleted in Au (Au ? 0.02 wt%) in comparison with other pyrite generations (py2 and py3) that showed results up to 0.35 wt% Au. Microprobe analysis also suggests that gold occurs mostly as nano- micro-size particles in the pyrite, and not as part of its crystal structure. Copper presents opposite behavior, with the lowest concentration on the richest gold pyrites (Cu ? 0.04 wt%.). A sample of molybdenite coexisting with Au-bearing pyrite from stage 2, revealed a Re-Os model age of 1805 ± 7 Ma. Taking into account the uncertainties, this age could overlaps with the U/Pb SHRIMP obtained in zircon from granitic rocks of the Paranaíta Intrusive Suite at 1790 ± 6.4 Ma (95% confidence level, MSDW= 4.8, n = 15) and 1792 ± 5.8Ma (95% confidence level, MSDW = 0.32, n = 17). This poses a genetic relationships between the felsic magmatism attributed to this granitic suite and the emplacement of the gold mineralization at the Juruena deposit, which can be defined as the result of a magmatic-hydrothermal system. Fluid inclusions microthermometric data obtained in veins of quartz constrain the formation of the early mineralizing events in the range of 341 and 456 oC from a low to moderate-salinity (0.6 and 11.3 wt% NaCl equiv.) H2O-CO2-NaCl fluid. At late stages of gold mineralization, fluid gradually become CO2-poor and higher salinities (31.4 to 36 wt% NaCl equiv.), represented by NaCl-bearing fluid inclusions. More diluted (0.4 to 13.7 wt% Nacl equiv.) and cooler (185 to 285 oC) aqueous fluid inclusions dominate the latest stages of the magmatic-hydrothermal system. Calculated ?18Ofluid values range from 6.9 to 0.5 ¿ indicating that ore fluids of essentially magmatic origin in the earlier mineralizing stages undergoes mixing with meteoric waters in the late stages. Sulfides from early veins display ?34SSulfide values in the range of -7.1 to -4.5 ¿, whereas more enriched ?34SSulfide values varying from -0.5 to +1.5 ¿ are obtained in sulfides from the late veins sets. The more negative ?34SSulfide values may reflect sulfides precipitation from oxidized magmatic fluids in the early ore stages, whereas higher ?34SSulfide values be attained in later stages as a result of water-rock interactions, fluid mixing and change of the redox conditions. Based on field, petrography, fluid inclusions, isotopic evidence and geochemistry of trace elements in pyrites, is possible to define that Juruena gold deposits is a magmatic-hydrothermal system, with hot CO2-fluid rich that evolve to lower temperature, aqueous fluids. The gold was precipitated directly from the hydrothermal solution during different pulses. The formation processes of the Juruena gold deposit are most similar with a typical small Au-porphyry system formed in the Paleoproterozoic / Mestrado / Geologia e Recursos Naturais / Mestre em Geociências

Esta pesquisa aborda, a partir de uma perspectiva bioarqueológica comparativa, a problemática das mudanças nos padrões de subsistência associados à intensificação da agricultura e suas implicações no processo de complexificação social na costa dos Andes Centrais. Para tanto, se examinaram indicadores de patologia oral, estresse nutricional e isótopos estáveis, e outros dados paleodietéticos e arqueológicos de 09 populações pré-históricas da costa dos Andes Centrais datadas para o período Formativo (~3000-1 a.C.). Os resultados mostram que as dietas a predomínio de carboidratos são muito antigas na região, inclusive nos sítios litorâneos e que o processo de complexificação ocorreu em presença da agricultura como base econômica. As formações teocráticas do 3ro e 2do milênios a.C. floresceram baseadas na agricultura de tubérculos, leguminosas, árvores frutíferas e milho em menor quantidade (abaixo de 20%), apelando a técnicas agrícolas adaptadas às características de aridez dos vales da bacia do Pacífico. Uma drástica mudança na dieta costeira andina ocorreu entre 500-1 a.C., quando o milho passa ser o principal produto de subsistência ao nível regional em concomitância com o aparecimento de governos seculares. / From a comparative bioarchaeological perspective this research addresses the issue of changes in subsistence patterns associated with the intensification of agriculture on the coast of the Central Andes and their implications to the social complexity process. Markers of oral pathology and nutritional stress were examined, along with stable isotopes, and other paleodietetic and archaeological data of 09 prehistoric coastal populations dated to the Formative period (~3000-1 BC). The results show that the predominance of rich carbohydrate diets is very old in the region, also on shoreline settlements, and the process of complexity was based in agriculture as an economic basis. The theocratic societies of 3rd and 2nd millennium BC flourished based on agriculture of tubers, legumes, fruit trees and corn in smaller quantities (below 20%), using farming techniques highly adapted to the aridity of the Pacific basin valleys. A drastic change in the Andean coastal diet occurred between 500-1 BC, when the corn became the main regional staple concomitant to the appearance of secular governments

No description available.

Die Erkundung und Charakterisierung der unterirdischen Einzugsgebiete gehören zu den zentralen Aufgabengebieten der hydrogeologischen Praxis. Die Erfassung und Ausnutzung von Schwankungen in den chemisch-physikalischen Eigenschaften der Grundwässer bildet dabei einen Grundpfeiler zahlreicher Studien. Ausgelöst werden diese Variationen u.a. durch den Zustrom von Niederschlagswässern in die Grundwassersysteme. Dies kann sowohl infolge des natürlichen Versickerungsprozesses geschehen oder aber technischen Ursprungs sein (z.B. künstliche Grundwasseranreicherung). Niederschlagswässer unterscheiden sich - als Endprodukt des natürlichen meteorologi-schen Destillationsprozesses - bezüglich ihrer Salinität (Mineralgehalt) und ihrer Isotopie zumeist deutlich von natürlichen Grund- und Oberflächenwässern. Die meisten Monitoring- und Erkundungskonzepte, welche derartige Unterschiede ausnutzen, beinhalten daher oft eine Kombination mehrerer Analyseverfahren, wie z.B. die Identifizierung des isotopischen Fingerabdruckes mittels Stabilisotopenanalytik sowie die Bestimmung der Salinität über z.B. Konduktometrie oder Ionenanalysen. Niederschlagswässer, Grundwässer sowie das poröse Medium selbst sind jedoch Materialien natürlichen Ursprungs und daher physikochemisch betrachtet eher komplexe Systemkomponenten. Ein perfekt konservatives Migrationsverhalten ohne Beeinflussungen ist daher nicht zu erwarten; ebenso wenig ist davon auszugehen, dass die messtechnische Erfassung stets einwandfrei verläuft. Vor diesem Hintergrund setzt sich diese Dissertationsschrift kritisch mit dem Einfluss von Messunsicherheiten und Signalmodifikationen auf die Qualität der Nachverfolgung dieser Wässer auseinander. Hierfür wird das Niederschlagswasser als de-facto künstlicher Grundwassertracer behandelt und bezüglich der Anforderungen an diese Tracer-Gruppe bewertet. In mehreren Experimenten und Modellsimulationen auf Labor- und Feldskala wird zudem gezeigt, welche speziellen Anforderungen bei der Nutzung von Regenwässern und Schneeschmelzen als Tracer bestehen. Die Untersuchungsergebnisse verdeutlichen zum einen, dass die technischen Limitationen der Stabilisotopenanalytik bei der Auswertung von Versuchen mit natürlichen Niederschlags-wässern zwingend zu berücksichtigen sind, da sich die begrenzten isotopischen Unterschiede i.d.R. nur um wenige Vielfache vom Hintergrundrauschen der Messung unterscheiden. Dies hat erhebliche Auswirkungen auf die Eineindeutigkeit der invers ermittelten Parameter. Des Weiteren ist zu beachten, dass die stabilen Isotope, obwohl durch ein nahezu inertes Verhalten geprägt, dennoch physikalisch bedingten Transferprozessen unterliegen, welche wiederum von Experimentalbedingungen wie z.B. der Temperatur beeinflusst werden. Außerdem wird offenbart, dass die Migration der sehr gering mineralisierten und chemisch folglich untersättigten Wässer im porösen Medium von chemischen Umwandlungsprozessen (u.a. Mineralreaktionen, Ionenaustausch) z.T. erheblicher Intensität begleitet wird. Diese Reaktionen führen u.a. zur Modifikation des Proxy-Parameters ‚elektrische Leitfähigkeit‘.:Erklärung (mit Auflistung der Veröffentlichungen) Kurzzusammenfassung / Abstract (English) Thesen der Dissertation Danksagung und Förderinformationen Inhaltsverzeichnis Abbildungsverzeichnis Tabellenverzeichnis Abkürzungs- und Symbolverzeichnis 1 Einleitung / Hintergrund 1.1 Motivation dieser Arbeit 1.2 Forschungsfragen im Kontext des Projektes „Regen als Grundwassertracer“ 1.3 Struktur dieser Arbeit 1.4 Hinweis zum kumulativen Charakter dieser Arbeit 2 Theorie I - Markierungsversuche und Parameterermittlung im wassergesättigten, porösen Medium 2.1 Beschreibung von Lockersedimenten als poröse Medien 2.2 Hydrogeologische Markierungsversuche 2.3 Parameterermittlung anhand von Observationsdaten aus Markierungsversuchen 3 Theorie II - Die stabilen Isotope des Wassermoleküls und ihre Nutzung 3.1 Definitionen, Konventionen und Unsicherheiten 3.2 Wassermoleküle in der Hydrosphäre 3.3 Anwendungen in der Hydrogeologie 4 Methodik 4.1 Vorwort zur Methodik / Übersicht zu den Untersuchunge 4.2 Bestimmung der Stabilisotopensignaturen mittels IRMS 4.3 Konduktometrie zur Bestimmung des EC-Wertes 4.4 Verfahren zur Bestimmung weiterer Messgrößen und Parameter 4.5 Versuchsaufbauten auf Laborskala 4.6 Feldstandorte 4.7 Modellsysteme / Modellcodes 4.8 Weitere Hinweise zu den Untersuchunge 5 Variabilität der Quantität und δ2H-/δ18O-Isotopie von Niederschlagswässern 5.1 Zweck dieses Kapitels 5.2 Herkunft der analysierten Daten 5.3 Niederschlagsmengen und Schneehöhen (DAT1) 5.4 Verteilung der Isotopensignaturen (DAT2) 5.5 Dämpfung des Jahresganges / Berücksichtigung der Überdeckung 5.6 Bewertung / Zwischenfazit 6 Bewertung des Transportverhaltens und der Stabilität von Niederschlagswässern im porösen Medium 6.1 Zweck dieses Kapitels 6.2 Durchströmungsversuche mit künstlicher Isotopenmarkierung (LAB1) 6.3 Durchströmungsversuche mit natürlichen Niederschlagswässern (LAB2, LAB3) 6.4 Bedeutung des isotopischen Signal-Rausch-Verhältnisses (MOD1) 6.5 Batchversuche zur weiteren Stabilitätsbewertung (LAB4, LAB5) 6.6 Modellgestützte Analyse der beobachteten EC-Wert-Modifikation (MOD2) 6.7 Bewertung / Zwischenfazit 7 Bewertung des Transportverhaltens auf kleiner Feldskala 7.1 Zweck dieses Kapitels (inklusive Verfahrensauswahl) 7.2 Feldskala-Vorversuche mit Deuteriumoxid-Markierung (FELD1, FELD2) 7.3 Realisierung eines Feldskala-Versuchs mit Schneeschmelzwasser (FELD3) 7.4 Modellgestützte Abschätzung von Wassermengen (MOD3) 7.5 Bewertung / Zwischenfazit 8 Verhalten der δ2H-, δ18O- und EC-Signalkomponenten in komplexen Systemen 8.1 Zweck dieses Kapitels 8.2 Dynamische Mischungsberechnung im 3-Komponenten-System (LAB6) 8.3 Thermisch-bedingte Veränderungen der Transportbedingungen (LAB7) 8.4 Bewertung / Zwischenfazit 9 Abschließende Bewertung und Ausblick 9.1 Zusammenfassung der Erkenntnisse aus den Untersuchungen 9.2 Schlussfolgerungen für den aktiven Einsatz von Niederschlagswässern als Tracer 9.3 Ausblick / Empfehlungen für die künftige Forschung Referenzliste / Literaturverzeichnis Anhang A / Fachartikel Hydrogeology Journal : Binder et al. (2019a) - Hauptmanuskript Hydrogeology Journal : Binder et al. (2019a) - Ergänzungsmaterialien Journal of Hydrology : Binder et al. (2019b) - Hauptmanuskript Journal of Hydrology : Binder et al. (2019b) - Ergänzungsmaterialien Water Resources Research : Binder et al. (in Revision) - Hauptmanuskript Water Resources Research : Binder et al. (in Revision) - Ergänzungsmaterialien Anhang B / Sonstige Ergänzungen Erläuterung der Kernthesen sowie der ergänzenden Thesen Peer-Review-Veröffentlichungen als Co-Autor mit Nennung in dieser Arbeit Zu Kapitel 2 – Theorie Zu Kapitel 5 – Datenrecherche Zu Kapitel 6 – Laborskala-Untersuchungen Zu Kapitel 7 – Feldskala-Untersuchungen Zu Kapitel 8 – Verhalten in komplexen Systemen / The exploration and characterization of subsurface catchments is one of the central tasks in hydrogeology. Here, exploiting detected fluctuations in the chemical-physical properties of the groundwater is a cornerstone of numerous studies. These variations are triggered, among others, by precipitation waters flowing into the groundwater systems. This can happen either due to the natural infiltration process or as a result of technical applications (e.g., as part of artificial groundwater recharge). Being the end product of the natural meteorologically induced distillation process, typical precipitation waters differ from natural groundwater and surface waters in terms of their mineral content (salinity) and their isotopic signatures. Therefore, most monitoring and exploration concepts, which exploit such differences, employ a combination of several analytical methods, such as the identification of the isotopic fingerprint by stable isotope analysis and salinity determination by, e.g., conductometry or ion analysis. However, precipitation waters, groundwaters as well as the porous medium itself are materials of natural origin and, therefore, are physicochemically rather complex system components. Hence, an unmodified and perfectly conservative migration behaviour is not to be expected; it is equally unlikely that the analytical detection procedure always runs smoothly. In this context, this doctoral dissertation gives a critical assessment on the influence of analytical uncertainties and signal modifications on the overall quality of the water tracing. For this purpose, precipitation water is treated as de-facto artificial groundwater tracer and evaluated according to the requirements defined for this tracer group. Furthermore, experiments and model simulations were carried out on the laboratory and on the field scale to assess which special requirements must be complied when rain waters or snowmelt waters are used as tracers. The investigations show on the one hand, that technical limitations of stable isotope analysis must be considered in the evaluation of tests with natural precipitation waters, as the limited isotopic differences typically differ only a fewfold from the background noise of the measurement device. This has a significant impact on the quality of the inversely determined parameters. Furthermore, it is highlighted that the stable isotopes, although showing an almost inert migration behaviour, are still subject to physically induced transfer processes. These transfer processes, in turn, depend on various experimental conditions such as temperature. Finally, it was found that the migration of the low mineralized waters in the po-rous medium is accompanied by a suite of chemical reactions (e.g. mineral reactions, ion exchange), which in turn lead to a modification of the proxy parameter 'electrical conductivity'.:Erklärung (mit Auflistung der Veröffentlichungen) Kurzzusammenfassung / Abstract (English) Thesen der Dissertation Danksagung und Förderinformationen Inhaltsverzeichnis Abbildungsverzeichnis Tabellenverzeichnis Abkürzungs- und Symbolverzeichnis 1 Einleitung / Hintergrund 1.1 Motivation dieser Arbeit 1.2 Forschungsfragen im Kontext des Projektes „Regen als Grundwassertracer“ 1.3 Struktur dieser Arbeit 1.4 Hinweis zum kumulativen Charakter dieser Arbeit 2 Theorie I - Markierungsversuche und Parameterermittlung im wassergesättigten, porösen Medium 2.1 Beschreibung von Lockersedimenten als poröse Medien 2.2 Hydrogeologische Markierungsversuche 2.3 Parameterermittlung anhand von Observationsdaten aus Markierungsversuchen 3 Theorie II - Die stabilen Isotope des Wassermoleküls und ihre Nutzung 3.1 Definitionen, Konventionen und Unsicherheiten 3.2 Wassermoleküle in der Hydrosphäre 3.3 Anwendungen in der Hydrogeologie 4 Methodik 4.1 Vorwort zur Methodik / Übersicht zu den Untersuchunge 4.2 Bestimmung der Stabilisotopensignaturen mittels IRMS 4.3 Konduktometrie zur Bestimmung des EC-Wertes 4.4 Verfahren zur Bestimmung weiterer Messgrößen und Parameter 4.5 Versuchsaufbauten auf Laborskala 4.6 Feldstandorte 4.7 Modellsysteme / Modellcodes 4.8 Weitere Hinweise zu den Untersuchunge 5 Variabilität der Quantität und δ2H-/δ18O-Isotopie von Niederschlagswässern 5.1 Zweck dieses Kapitels 5.2 Herkunft der analysierten Daten 5.3 Niederschlagsmengen und Schneehöhen (DAT1) 5.4 Verteilung der Isotopensignaturen (DAT2) 5.5 Dämpfung des Jahresganges / Berücksichtigung der Überdeckung 5.6 Bewertung / Zwischenfazit 6 Bewertung des Transportverhaltens und der Stabilität von Niederschlagswässern im porösen Medium 6.1 Zweck dieses Kapitels 6.2 Durchströmungsversuche mit künstlicher Isotopenmarkierung (LAB1) 6.3 Durchströmungsversuche mit natürlichen Niederschlagswässern (LAB2, LAB3) 6.4 Bedeutung des isotopischen Signal-Rausch-Verhältnisses (MOD1) 6.5 Batchversuche zur weiteren Stabilitätsbewertung (LAB4, LAB5) 6.6 Modellgestützte Analyse der beobachteten EC-Wert-Modifikation (MOD2) 6.7 Bewertung / Zwischenfazit 7 Bewertung des Transportverhaltens auf kleiner Feldskala 7.1 Zweck dieses Kapitels (inklusive Verfahrensauswahl) 7.2 Feldskala-Vorversuche mit Deuteriumoxid-Markierung (FELD1, FELD2) 7.3 Realisierung eines Feldskala-Versuchs mit Schneeschmelzwasser (FELD3) 7.4 Modellgestützte Abschätzung von Wassermengen (MOD3) 7.5 Bewertung / Zwischenfazit 8 Verhalten der δ2H-, δ18O- und EC-Signalkomponenten in komplexen Systemen 8.1 Zweck dieses Kapitels 8.2 Dynamische Mischungsberechnung im 3-Komponenten-System (LAB6) 8.3 Thermisch-bedingte Veränderungen der Transportbedingungen (LAB7) 8.4 Bewertung / Zwischenfazit 9 Abschließende Bewertung und Ausblick 9.1 Zusammenfassung der Erkenntnisse aus den Untersuchungen 9.2 Schlussfolgerungen für den aktiven Einsatz von Niederschlagswässern als Tracer 9.3 Ausblick / Empfehlungen für die künftige Forschung Referenzliste / Literaturverzeichnis Anhang A / Fachartikel Hydrogeology Journal : Binder et al. (2019a) - Hauptmanuskript Hydrogeology Journal : Binder et al. (2019a) - Ergänzungsmaterialien Journal of Hydrology : Binder et al. (2019b) - Hauptmanuskript Journal of Hydrology : Binder et al. (2019b) - Ergänzungsmaterialien Water Resources Research : Binder et al. (in Revision) - Hauptmanuskript Water Resources Research : Binder et al. (in Revision) - Ergänzungsmaterialien Anhang B / Sonstige Ergänzungen Erläuterung der Kernthesen sowie der ergänzenden Thesen Peer-Review-Veröffentlichungen als Co-Autor mit Nennung in dieser Arbeit Zu Kapitel 2 – Theorie Zu Kapitel 5 – Datenrecherche Zu Kapitel 6 – Laborskala-Untersuchungen Zu Kapitel 7 – Feldskala-Untersuchungen Zu Kapitel 8 – Verhalten in komplexen Systemen

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MENVSC / Department of Mining and Environmental Gelogy / In the present study, the physico-chemical, applications, mineralogy, geochemistry and stable isotope of Lwamondo and Zebediela kaolin is documented, in order to understand the genesis, paleoenvironmental conditions and possible utilization. Mineral identification studies were conducted using X-ray diffractometer (XRD), Fourier transform infrared spectrophotometer (FTIR) and scanning electron microscope with energy dispersive X-ray micro analysis (SEM-EDX). Major oxides were identified by X-ray Florescence (XRF) whereas trace elements were identified by Laser Ablation Inductively Coupled Plasma-Mass Spectrometer (ICP-MS). Hydrogen and oxygen isotopic composition were determined by δ18O and δD isotopic measurements. Kaolinite was dominant mineral in all the kaolin samples whereas muscovite, quartz, goethite, hematite, smectite, anatase occurred in minor to trace quantities. The chemical data show that the kaolins are composed mainly of SiO2 and Al2O3 due to the presence of quartz and kaolinite, with minor to trace amounts of other elements such as Ca, Na, Cr, K, Fe, Mn, Mg, P and Ti which affected the kaolin application negatively. Lower concentration of Ca, Na, K, Fe, Mn, Mg, and Ti show the extent of the kaolinitisation. The samples were enriched in Ni and depleted in some other trace elements. The chondrite-normalised rare earth elements patterns show enrichmnent in Heavy Rare Earth Elements (HREE) than Light Rare Earth Elements (LREE) with slight positive Eu anomaly. The Rare Earth Elements (REE) pattern and the content of other trace elements show evidence of weathering processes related to kaolinitisatioon. Kaolin genesis is explained using kaolin mineralogy, particle morphology, structural order (functional group), major and trace elements geochemical data. The data suggest that kaolin is derived from the intensive chemical weathering of intermediate to mafic rocks deposited in non-marine environment. The stable isotopes were used to determine the paleoenvironmental conditions which influenced kaolinitisation of Lwamondo and Zebediela kaolins. Stable isotopes mean values for kaolinite from both Lwamondo and Zebediela were as follows: δ18O for Lwamondo= +18.57‰ and for Zebediela = +16.67 ‰ vii and δD for Lwamondo = -65‰ and for Zebediela = -64‰. The calculated mean temperatures were 26.94 ⁰C for Lwamondo kaolin and 36 ⁰C for Zebediela kaolin. Low temperatures were inferred from stable isotope values to have been involved in the kaolinitisation wherein hydrothermal processes were eliminated. The data suggests that kaolin was formed in a weathering environment. The kaolin is found to be suitable for brick making and based on the physico-chemical, mineralogical and chemical data it was suggested that the kaolin could also be used in producing low temperature ceramics, refractory materials, pottery and stoneware

La réduction des excursions glycémiques postprandiales a été proposée comme un moyen pour limiter le risque de développement du diabète de type 2. L’intérêt s’est donc porté sur les outils nutritionnels susceptibles de moduler la biodisponibilité des glucides et ainsi leur impact sur la glycémie postprandiale. Les travaux réalisés au cours de cette thèse avaient pour but d’étudier les effets de différents ingrédients modifiant la biodisponibilité du glucose, non seulement sur la glycémie postprandiale à court terme (2 heures) mais aussi sur les cinétiques du débit d’apparition et de disparition de glucose (total, exogène et endogène - isotopes stables) et les autres paramètres métaboliques de la phase postprandiale au cours de la journée. Dans la première étude (β-glucanes), nous avons montré que l’addition de fibres β-glucanes à un repas glucidique chez des sujets sains en surpoids ralentit l’absorption du glucose dans le plasma. Ceci a prolongé la réponse insulinique et par conséquent l’inhibition de la lipolyse et de la production endogène de glucose. Dans la deuxième étude (Eurostarch), nous avons montré que la diminution de la biodisponibilité du glucose au petit-déjeuner (amidon lentement digestible, index glycémique bas) diminue l’apparition du glucose exogène dans le plasma et pourrait avoir un effet second-repas chez des sujets sains en surpoids. Mais nous n’avons pas mis en évidence d’amélioration de ces effets métaboliques à plus long terme (5 semaines). Dans la troisième étude présentée (Nutriose), nous avons montré que l’addition de dextrine résistante NUTRIOSE®10 (fermentescible) au petit-déjeuner chez des sujets sains, diminue les réponses glycémiques, insuliniques postprandiales et le profil de ghréline au cours de la journée (en comparaison à une maltodextrine). En parallèle, la prolongation observée de la fermentation et l’oxydation du NUTRIOSE®10 pourraient fournir de l’énergie en phase postprandiale tardive. En conclusion, l’analyse des paramètres métaboliques au-delà de 2 heures après le repas, a permis de mettre en évidence les effets métaboliques à plus long terme de la modulation de l’apparition du glucose dans le plasma (ralentissement, prolongation, réduction) sur les cinétiques du glucose, la réponse insulinique, la lipolyse et l’oxydation des substrats / The reduction of the postprandial glycemic excursions has been proposed as to limit risk of type 2 diabetes. There has been growing interest in the development of dietary ingredients that could potentially modulate carbohydrates bioavailability and thus their impact on postprandial glycemia. The aim of this thesis was to investigate the effects of the the modulation of glucose bioavailability by different ingredients on 2-hour glycemic response but also on glucose kinetics (total, exogenous and endogenous – stable isotopes) and on other daylong metabolic parameters. In the first study (β-glucanes), we showed that the addition of β-glucan fiber to a carbohydrate meal in healthy overweight subjects reduced the appearance of glucose in plasma. As a consequence, insulin response was also prolonged and induced a prolonged inhibition on lipolysis and endogenous glucose production. In the second study (eurostarch), the reduction in glucose availability (slowly available glucose, low GI) at breakfast decreased plasma exogenous glucose appearance and tended to improve glucose control at the subsequent lunch. But we did not observe the improvement of such metabolic effects in the long-term (5 weeks). In the last study, we showed that the addition of a resistant dextrin, NUTRIOSE®10, decreased postprandial glycemic and insulinemic response as well as daylong satiety-related ghrelin profile, compared to maltodextrin. In parallel, the prolonged fermentation and oxidation pattern of NUTRIOSE®10 up to 10 hours after ingestion at breakfast could induced an extended energy release with NUTRIOSE®10 in the late postprandial phase. In conclusion, the follow-up of metabolic parameters beyond 2 hours after the meal have highlighted the longer-term metabolic effects of the modulation of glucose appearance in plasma (delay, extension, reduction) on glucose kinetics, insulin response, lipolysis and nutrients oxidation