Dans cette étude, nous cherchons à dresser le bilan de l’altération à l’échelle de l’île de Mayotte (en surface et en souterrain), à contraindre l’impact des facteurs de contrôle dominant l’altération, puis à caractériser les processus impliqués dans les fractionnements des isotopes du silicium à l’échelle du profil d’altération.Deux campagnes d’échantillonnage incluant des eaux de rivières et des eaux souterraines ont été réalisées en saison humide et sèche, complétées par le prélèvement mensuel de 5 rivières. La prise en compte des crues (3 % de l’année) dans le calcul des taux d’altération moyens annuels en rivière a entraîné une augmentation de ≈32 % du bilan annuel. Le taux d’altération chimique global de l’île de Mayotte s’élève à 94 t/km²/an (81 t/km²/an en surface & 131 t/km²/an en souterrain). Nos résultats mettent en avant le rôle prépondérant des écoulements souterrains dans le transport de matériel dissous directement à l’océan. La contribution du domaine souterrain au bilan de l’altération diminue avec l’âge des formations, soulignant l’implication de l’âge des roches du bassin versant comme paramètre clé dans le contrôle des taux d’altération.Les isotopes du Si ont été analysés sur des roches totales le long de profils d’altération associés à différentes conditions d'altération du régolite : météorique (basse température) ou hydrothermale (haute température). À l’échelle du profil, les deux types de régimes ont montré un appauvrissement en 30Si en fonction du degré d’altération. À l’échelle du minéral, le fractionnement des isotopes du Si s’est révélé plus négatif pendant la précipitation de kaolinite secondaire à haute température qu’à basse température. / In this study, we seek to establish the weathering budget at the scale of the island of Mayotte (rivers and groundwater), to constrain the impact of dominant control factors to the weathering both locally and at a global scale, and then to characterize the processes involved in the fractionation of silicon isotopes across the weathering profile.Two field campaigns, in order to sample river water and groundwater, were carried out during wet and dry season, supplemented by the monthly monitoring of 5 rivers. By taking account of river floods (3% of the year) in the calculation of average annual weathering rates in the river has increased the annual weathering budget by ≈32%. The overall rate of Mayotte Island chemical weathering is 94 t/km²/yr (81 t/km²/yr from surface & 131 t/km²/yr from underground). Our results highlight the important role of groundwater flow to the dissolved material export directly to the ocean. The contribution of groundwater to the weathering budget decreases with the age of the geological formations, highlighting the involvement of the age of the rocks of the watershed as a key parameter in the weathering rates control.Si isotopes were analyzed for whole rock along two weathering profiles associated with different alteration conditions of the regolith: meteoric (low temperature) or hydrothermal (high temperature). At the weathering profile scale, the two types of alteration regimes showed 30Si depletion as a function of the degree of weathering. At the mineral scale, Si isotope fractionation was more negative during the secondary kaolinite precipitation at high temperatures than at low temperatures.

Mit dem Grundwasserwiederanstieg in Braunkohleabraumkippen werden die aus der Pyritverwitterung resultierenden Stoffausträge an Sulfat-, Eisen-, Schwermetall- und H+-Ionen gelöst. Im Rahmen dieser Dissertation wurde eine Methodik entwickelt, mit deren Hilfe Problembereiche ausgehalten und somit Maßnahmen im aktiven mitteldeutschen Tagebaubetrieb ergriffen werden können, um die zukünftige Beeinflussung der umgebenden Grund- und Oberflächenwasserkörper zu minimieren. An Vorfeldsedimenten konnten in Feld-eluaten, Stoßbeprobungen und Verwitterungsversuchen geochemische Eigenschaften ermittelt werden. In resultierenden Pufferungsversuchen aus karbonathaltigen Geschiebe-mergeln und Hauptaciditätsträgern konnte eine langfristige Minderung der Aciditätswirkung nachgewiesen werden und ein adaptierter Regelkippenaufbau mit laminaren, alterierenden Sichtaufbau begründet werden. In umliegenden Altkippengrundwässern sind Pufferung und Sulfatreduktion als Wiederfestlegungsprozesse der AMD-Problemstoffe belegt worden.:Versicherung 3 Zusammenfassung 8 1 Aktualität und Bedeutung der gesteuerten Abraumverkippung 10 2 Theoretische Grundlagen, Ziele, Aufgaben und Technik 15 2.1 Das System Kippe mit Verwitterungsstufen und Stufen der Gegenmaßnahmen 16 2.1.1 Phasen der Tagebauentwicklung in Bezug auf die Sauerwasserbildung 16 2.1.2 Systematik der Gegenmaßnahmen 18 2.2 Pyritbildung, Verwitterung, Pufferung und Wiederfestlegung 22 2.2.1 Pyritbildung 22 2.2.2 Pyritverwitterung 22 2.2.3 Pufferreaktionen 24 2.2.4 Wiederfestlegung durch autochthone mikrobielle Sulfatreduktion 26 2.2.5 Wiederfestlegung durch technisch- biologisch forcierte Sulfatreduktion 28 2.3 Geochemische Verhältnisse der Kippen Zwenkau und Witznitz 30 2.4 Geräteeinsatz im Tagebau des Untersuchungsgebietes 33 3 Ableitung einer Untersuchungsmethodik 35 3.1 Bearbeitungsziel und Ableitung der notwendigen Methoden 35 3.1.1 Geologisches Modell 36 3.1.2 Geochemisches Modell 38 3.1.3 Gewinnungstechnologisches Modell 39 3.2 Vorfeldbohrungen, Korngrößenbestimmung, stoffliche Charakterisierung und RFA 41 3.2.1 Vorfeldbohrungen 41 3.2.2 Lagerung und Probenahme 42 3.2.3 Körnungsanalyse und Wassergehaltsbestimmung 43 3.2.4 Feststoffcharakterisierung Kohlenstoff / Schwefel mittels CS-Mat 44 3.2.5 Röntgenfluoreszenzanalytik 44 3.3 Feldeluate, HCl-Test und organoleptische Ansprache 46 3.3.1 Feldelution 46 3.3.2 Salzsäure-Test (HCl-Test) 47 3.3.3 Organoleptische Ansprache 47 3.3.4 Hydrolytische Acidität 48 3.4 Verwitterungsversuche 49 3.5 Stoßbeprobung 51 3.6 Pufferungsversuche 52 3.7 Kippengrundwassermonitoring 54 3.7.1 Grundwassermessstellen und Probenahmeequipment 54 3.7.2 Feldanalytik 55 3.7.3 Laboranalytik 56 3.7.4 Hydrogeochemische Modellierung 56 4 Grundlagen und geologische Beschreibung des Untersuchungsgebietes 58 4.1 Untersuchungsgebiet 58 4.2 Tertiäre Einheiten 59 4.3 Quartäre Einheiten 61 4.4 Abgrenzung und Festlegung der Auswerteeinheiten 61 4.5 Vorfeldbohrungen 62 5 Anwendung der Methodik für den Tagebau Vereinigtes Schleenhain 65 5.1 Baufeld Schleenhain 65 5.1.1 Vorfeldbohrungen und Feldeluate 65 5.1.2 Stoffliche C/S-Charakterisierung 69 5.1.3 Verwitterungsversuche 72 5.1.4 Stoßbeprobung 85 5.1.5 Pufferungsversuche 90 5.1.6 Körnungsanalyse und Verwitterungszugänglichkeit 99 5.2 Baufeld Peres 103 5.2.1 Feldeluate 103 5.2.2 Vorfeldbohrungen und stoffliche Charakterisierung 105 5.2.3 Verwitterungsversuche 107 5.2.4 Pufferungsversuche 113 5.3 Beschaffenheit der Kippengrundwässer 114 5.3.1 Grundlegende hydrogeochemische Charakterisierung 115 5.3.2 Verwitterungszonen 117 5.3.3 Spurenmetallgehalte 118 5.3.4 Wirksamkeit der geogenen Puffer 119 5.3.5 Kennzeichnung der Sulfatreduktion als natürlicher Rückhalteprozess 121 5.3.6 Hydrochemische Modellierung 124 5.4 Fehlerdiskussion 126 6 Übertragung der Ergebnisse, Bewertung und Schlussfolgerung 127 6.1 Geologisches Modell und technische Verschnittmöglichkeiten 127 6.1.1 Geologisch-genetische Charakteristik der Auswerteeinheiten 127 6.1.2 Verbreitung und Mächtigkeit wesentlicher Auswerteeinheiten im Tagebau „Vereinigtes Schleenhain“ 128 6.1.3 Tagebautechnologische Verschnittmöglichkeiten 130 6.2 Geochemische Möglichkeiten bei der Umstellung der Tagebautechnologie – Massenversatz und Mischung 132 6.2.1 Gewinnungsscheiben 132 6.2.2 Regelkippenaufbau 134 6.2.3 „Schnelle Fahrweise“ und (Zwischen-) Abdeckung 134 6.2.4 Einmischung der Sedimente 135 6.3 RFA-Analytik und Bewertung von Sedimenteigenschaften 137 7 Zusammenfassung und weiterer Handlungsbedarf 139 7.1 Zusammenfassung - Ergebnisse Vorfeldbohrungen 139 7.2 Zusammenfassung – Verwitterungsversuche Labor und Feld 139 7.3 Zusammenfassung – Pufferungsversuche Schleenhain und Peres 141 7.4 Zusammenfassung – Gütemonitoring Kippengrundwässer 141 7.5 Zusammenfassung – Geologisches Modell/ Verschnitt/Technologie 142 7.6 Nachweis der Anwendbarkeit der Methode 144 7.7 Ausblick und weiterer Handlungsbedarf 145 Literatur und Quellen 146 Tabellenverzeichnis 151 Abbildungsverzeichnis 151 Abkürzungsverzeichnis 157 Anlagen 159 / For lignite mining extensive overburden masses have to be moved. Due to the ventilation of the overburden by atmospheric oxygen, there is a weathering of mostly tertiary sulfides. The rebound of groundwater in future tippings dissolves sulfate, iron, heavy metal and H+ ions, resulting from the pyrite weathering. The partial mobilization of overburden sulfides are opposed to hydrogeochemical buffer reactions e.g. the buffering by carbonates as the first step of buffering. Therefore, there are the questions to the mining operators of the measures that can be taken to minimize the geochemical influence of the surrounding ground and surface water bodies. Object of this PhD-thesis is to lead a methodology that helps to characterize the future tilting substrates to find technological and strategic measures for minimizing the acid water formation in the active open pit operation. In Field eluates and weathering tests in the laboratory and in the field, sediments from dry drill holes in the forefront of open pits “Schleenhain” and “Peres” it could be shown that the geological facies formation of sediments has a decisive influence on geochemical characteristics. As the main acidifying sediment the tertiary aquifer number 2 (lying part) and number 3 can be identified with their high sulfur contents. With increasing time of oxygen exposure sulfate, iron, heavy metal and H + ions released massively. Furthermore, it appears that carbonate buffer essentially are available as glacial till only in cohesive Quaternary. With the resulting buffering experiments from glacial till and the most acidic aquifer sediments a long-term retention of iron, heavy metal and H + - ion and a reduction of sulfate release can be shown, if there is a share of at least 40% glacial till to the lying aquifer number 2 sediments or 20% glacial till to the aquifer number 3. The groundwater quality monitoring of unstructured resaturated old dumps near to the active open pits is comparable to a field test. In addition to weathering zones with high levels of pollutants in the presence of carbonates, buffering processes and sulfate reduction with precipitation of problematic substances in secondary mineral phases can be detected. Blending the research results of geological and geochemical data, an important, in principle selectively recoverable, buffer potential already exists. The determined mixing ratio from 80-60 mass-% acidic sediments to 20-40 mass-% buffering sediment from the buffering experiments can be realized in tilting. In the open pit “Schleenhain” the missing buffering material can be compensated by mass offset from the open pit “Peres”. With the use of the already existing equipment, it is possible to establish a laminar, alternately tipping body with good geochemical and geotechnical conditions.:Versicherung 3 Zusammenfassung 8 1 Aktualität und Bedeutung der gesteuerten Abraumverkippung 10 2 Theoretische Grundlagen, Ziele, Aufgaben und Technik 15 2.1 Das System Kippe mit Verwitterungsstufen und Stufen der Gegenmaßnahmen 16 2.1.1 Phasen der Tagebauentwicklung in Bezug auf die Sauerwasserbildung 16 2.1.2 Systematik der Gegenmaßnahmen 18 2.2 Pyritbildung, Verwitterung, Pufferung und Wiederfestlegung 22 2.2.1 Pyritbildung 22 2.2.2 Pyritverwitterung 22 2.2.3 Pufferreaktionen 24 2.2.4 Wiederfestlegung durch autochthone mikrobielle Sulfatreduktion 26 2.2.5 Wiederfestlegung durch technisch- biologisch forcierte Sulfatreduktion 28 2.3 Geochemische Verhältnisse der Kippen Zwenkau und Witznitz 30 2.4 Geräteeinsatz im Tagebau des Untersuchungsgebietes 33 3 Ableitung einer Untersuchungsmethodik 35 3.1 Bearbeitungsziel und Ableitung der notwendigen Methoden 35 3.1.1 Geologisches Modell 36 3.1.2 Geochemisches Modell 38 3.1.3 Gewinnungstechnologisches Modell 39 3.2 Vorfeldbohrungen, Korngrößenbestimmung, stoffliche Charakterisierung und RFA 41 3.2.1 Vorfeldbohrungen 41 3.2.2 Lagerung und Probenahme 42 3.2.3 Körnungsanalyse und Wassergehaltsbestimmung 43 3.2.4 Feststoffcharakterisierung Kohlenstoff / Schwefel mittels CS-Mat 44 3.2.5 Röntgenfluoreszenzanalytik 44 3.3 Feldeluate, HCl-Test und organoleptische Ansprache 46 3.3.1 Feldelution 46 3.3.2 Salzsäure-Test (HCl-Test) 47 3.3.3 Organoleptische Ansprache 47 3.3.4 Hydrolytische Acidität 48 3.4 Verwitterungsversuche 49 3.5 Stoßbeprobung 51 3.6 Pufferungsversuche 52 3.7 Kippengrundwassermonitoring 54 3.7.1 Grundwassermessstellen und Probenahmeequipment 54 3.7.2 Feldanalytik 55 3.7.3 Laboranalytik 56 3.7.4 Hydrogeochemische Modellierung 56 4 Grundlagen und geologische Beschreibung des Untersuchungsgebietes 58 4.1 Untersuchungsgebiet 58 4.2 Tertiäre Einheiten 59 4.3 Quartäre Einheiten 61 4.4 Abgrenzung und Festlegung der Auswerteeinheiten 61 4.5 Vorfeldbohrungen 62 5 Anwendung der Methodik für den Tagebau Vereinigtes Schleenhain 65 5.1 Baufeld Schleenhain 65 5.1.1 Vorfeldbohrungen und Feldeluate 65 5.1.2 Stoffliche C/S-Charakterisierung 69 5.1.3 Verwitterungsversuche 72 5.1.4 Stoßbeprobung 85 5.1.5 Pufferungsversuche 90 5.1.6 Körnungsanalyse und Verwitterungszugänglichkeit 99 5.2 Baufeld Peres 103 5.2.1 Feldeluate 103 5.2.2 Vorfeldbohrungen und stoffliche Charakterisierung 105 5.2.3 Verwitterungsversuche 107 5.2.4 Pufferungsversuche 113 5.3 Beschaffenheit der Kippengrundwässer 114 5.3.1 Grundlegende hydrogeochemische Charakterisierung 115 5.3.2 Verwitterungszonen 117 5.3.3 Spurenmetallgehalte 118 5.3.4 Wirksamkeit der geogenen Puffer 119 5.3.5 Kennzeichnung der Sulfatreduktion als natürlicher Rückhalteprozess 121 5.3.6 Hydrochemische Modellierung 124 5.4 Fehlerdiskussion 126 6 Übertragung der Ergebnisse, Bewertung und Schlussfolgerung 127 6.1 Geologisches Modell und technische Verschnittmöglichkeiten 127 6.1.1 Geologisch-genetische Charakteristik der Auswerteeinheiten 127 6.1.2 Verbreitung und Mächtigkeit wesentlicher Auswerteeinheiten im Tagebau „Vereinigtes Schleenhain“ 128 6.1.3 Tagebautechnologische Verschnittmöglichkeiten 130 6.2 Geochemische Möglichkeiten bei der Umstellung der Tagebautechnologie – Massenversatz und Mischung 132 6.2.1 Gewinnungsscheiben 132 6.2.2 Regelkippenaufbau 134 6.2.3 „Schnelle Fahrweise“ und (Zwischen-) Abdeckung 134 6.2.4 Einmischung der Sedimente 135 6.3 RFA-Analytik und Bewertung von Sedimenteigenschaften 137 7 Zusammenfassung und weiterer Handlungsbedarf 139 7.1 Zusammenfassung - Ergebnisse Vorfeldbohrungen 139 7.2 Zusammenfassung – Verwitterungsversuche Labor und Feld 139 7.3 Zusammenfassung – Pufferungsversuche Schleenhain und Peres 141 7.4 Zusammenfassung – Gütemonitoring Kippengrundwässer 141 7.5 Zusammenfassung – Geologisches Modell/ Verschnitt/Technologie 142 7.6 Nachweis der Anwendbarkeit der Methode 144 7.7 Ausblick und weiterer Handlungsbedarf 145 Literatur und Quellen 146 Tabellenverzeichnis 151 Abbildungsverzeichnis 151 Abkürzungsverzeichnis 157 Anlagen 159

Cette étude traite du vieillissement des ouvrages en pierres calcaires en interaction avec leur environnement, en se basant à la fois sur la caractérisation des matériaux et des conditions climatiques locales. L’objectif de cette thèse est d’étudier le rôle des conditions climatiques sur la dégradation des pierres par une estimation quantitative du poids des différents processus physiques de dégradation : gel-dégel, condensation and dilatations hygro-thermiques empêchées. Deux sites majeurs ont été sélectionnés : le Château de Chambord en France et le site d’Al-Namrud en Irak, qui est une ancienne capitale assyrienne datant de 1280 BC. Les matériaux français étudiés sont le tuffeau et la pierre de Richemont, qui a été abondamment utilisée comme pierre de substitution durant les restaurations du 20ème siècle. Les matériaux irakiens utilisés sont issus de prélèvements sur des pierres d’origines altérées, des pierres d’origine saines, ainsi que la pierre candidate pour la restauration du site. L’approche choisie pour l’estimation du risque d’endommagement commence par la réalisation d’une campagne expérimentale de caractérisation multi-physiques et multi-échelles des pierres calcaires utilisées à Chambord, ajouté à la collecte des données météorologiques à Chambord grâce à une station et des mesures dans la pierre. L’estimation du risque d’endommagement est obtenue en combinant l’utilisation des données climatiques et de la caractérisation des matériaux, grâce au calcul de l’impact des différents processus physiques de dégradation, qui a nécessité plusieurs développements méthodologiques. La méthodologie proposée pour l’estimation du risque d’endommagement est ensuite appliquée au site d’Al-Namrud. Finalement, un carnet de santé numérique préliminaire du plus édifiant monument d’Al-Namrud – la Ziggurat – est réalisé pour son diagnostic de durabilité. / This study deals with the ageing of limestone structures as a result of the interaction with their environment. It is based on the characterization of both the material and the local climatic conditions. The objective of this thesis is to study the role of climatic conditions in the degradation of stone by quantitative estimation of the weight of the different physical weathering processes: freezing-thawing, condensation and restrained hygro-thermal dilations. Two major historic sites were selected: the Château of Chambord in France and the site of Al-Nimrud City in Iraq, an ancient Assyrian capital, built in 1280 BCE. The French materials studied are tuffeau and Richemont stone, extensively used as a substitute for tuffeau restoration during part of the 20th century. The Iraqi materials studied are samples cored in situ in original weathered stones, original healthy stones, and the stone that could be used as a substitute for restoration. The approach chosen for damage risk assessment starts by the realization of a multiphysics and multiscale experimental characterization campaign of the limestone used at Chambord, added to the collection of meteorological data at Chambord thanks to a weather station supplemented by situ stone measurements. The damage risk assessment is obtained by the combined use of climate data and material characterization, through the calculation of the impact of thedifferent physical weathering processes, which required some methodological developments. The proposed damage risk assessment methodology is then applied to Al-Nimrud site. Finally, a preliminary digital health record of the most prominent monument of Al-Nimrud - the Al-Ziggurat - is carried out to diagnose its durability.

La Zone Critique de la Terre désigne la fine pellicule recouvrant sa surface, à l’interface du cycle de l’eau, de lithosphère et de la biosphère. Cette couche est produite à sa base par altération chimique et détruite à son sommet par érosion mécanique. Parce que le lithium et ses isotopes ont la particularité de se partager entre la phase dissoute et la phase solide au cours des réactions d’interactions eaux-roches, nous explorons, dans cette thèse, le potentiel des isotopes du lithium dissous dans les rivières comme traceurs des processus d’altération chimique des continents. Nous nous sommes focalisés, dans un premier temps, sur le Bassin Congolais. Cette étude met en évidence le caractère équivoque de la réponse de la composition isotopique du Li (δ7Li) dissous des rivières aux topographies plates (et aux intensités d’altération élevées). Deux valeurs extrêmes de δ7Li dissous sont, en effet, produites dans le bassin du Congo, qui tracent deux styles d’altération continentale distincts, dans lesquels les processus d’altération chimique sont différents. D’autre part, nous proposons une nouvelle estimation du flux moyen de Li et de sa composition isotopique moyenne exportés à l’océan par les rivières aujourd’hui (5,5×1010 g.an−1 et 19±2‰, respectivement). Nous montrons que le δ7Li dissous dans les grands fleuves est contrôlé, au premier ordre, par la réincorporation du Li dans les minéraux secondaires (dans les sols et les plaines d’inondation) et, d’une manière équivoque, de l’intensité d’altération. En outre, l’étude des δ7Li dissous dans les rivières drainant les îles volcaniques (Islande, Java, Martinique, Sao Miguel et Réunion) montre que l’hydrothermalisme continental, générant des eaux très concentrées en Li avec une valeur basse de δ7Li (car très peu fractionnée par rapport à la roche mère basaltique), influence le δ7Li dissous des rivières des îles volcaniques et peut avoir un impact significatif sur le flux de Li (et son δ7Li) transféré(s) à l’océan à l’échelle globale. Enfin, nous proposons une interprétation de l’augmentation de l’ordre de 9‰ qu’a connue la signature isotopique du Li de l’eau de mer au cours du Cénozoïque à l’aide d’un modèle de boîtes simple de l’océan et au regard de nos résultats. Il émane de ce travail de thèse que les isotopes du Li dissous dans les rivières prouvent là encore leur capacité à être de bons traceurs des régimes d’altération des roches silicatées continentales (et ce, même en contexte anthropisé, comme le montre notre étude du bassin de l’Orgeval, en Seine-et-Marne). Le Li et ses isotopes constituent donc des traceurs prometteurs de la Zone Critique de la Terre et des paléo-processus d’altération chimique ainsi que de l’évolution géodynamique des continents voire des grands mouvements verticaux affectant la lithosphère continentale / The Critical Zone of the Earth is the layer covering its surface, at the interface between the water cycle, the lithosphere and the biosphere. This layer is produced at its base by chemical weathering and destroyed at its top by mechanical erosion. We explore the potential of lithium isotopes dissolved in rivers as tracers of continental chemical weathering processes as lithium and its isotopes are highly fractionated between the dissolved and solid phases during water-rock interaction processes. First, we are focused on the Congo Bassin. This study demonstrates the equivocal response of the isotopic composition of the riverine dissolved Li isotope compositions (δ7Li) to flat topography (and high weathering intensities). Two extreme values of dissolved δ7Li are produced in the Congo Basin, which trace two distinct continental weathering styles in which chemical weathering processes are different. On the other hand, we refined the mean flux of Li and its average isotopic signature exported to the ocean by rivers today (5.5×1010 g. an-1 et 19±2‰, respectively). We show that dissolved δ7Li in large rivers is controlled, at first-order, by the re-incorporation of Li into secondary weathering minerals (in soils and floodplains) and in, an equivocal way, of the weathering intensity. Moreover, the study of dissolved δ7Li in rivers draining volcanic islands (Iceland, Java, Martinique, Sao Miguel and Reunion) shows that continental hydrothermal activity, producing waters with high Li concentration with low value of δ7Li (as low fractionated towards the basaltic bedrock), influences the dissolved δ7Li in rivers of volcanic islands and can have an impact on the Li flux (and its δ7Li) transferred to the ocean on a global scale. Finally, by using a simple box model of the ocean and our results, we suggest an interpretation of the 9‰ increase of seawater δ7Li during the Cenozoic. This thesis highlights that riverine dissolved Li isotopes confirm once again their capacity to be powerful tracers of the weathering regimes of continental silicate rocks (even in anthropized context, as showed by our study of the Orgeval catchment, in Seine-et-Marne). Li and its isotopes are thus promising tracers of the Critical Zone of the Earth and the chemical weathering paleo-processes as well as the long-term geodynamic evolution of the continents or even the large vertical movements affecting the continental lithosphere

[pt] Embora uma vasta área do Brasil esteja localizada em regiões que a formação de basalto se faz presente, são raros os estudos em perfis contendo solo e / ou rochas de caráter básico objetivando correlacionar características químicas e mineralógicas com características geotécnicas. A área do presente estudo localiza-se em um corte em solo na Ferrovia Norte-Sul, no Município de Arguianópolis-TO, em que durante sua execução ocorreram diversos escorregamentos. O maciço de solo do corte em questão é composto em sua maior parte por solos provenientes de alteração de basalto. O presente estudo foi realizado em duas etapas. A primeira refere-se à visita ao local do corte, onde foram realizadas coletas de amostras de solo de caráter indeformado e deformado, com as respectivas descrições morfológicas dos mesmos. A segunda refere-se aos trabalhos desenvolvidos nos laboratórios de Geotecnia e Meio Ambiente do DEC da PUC-Rio, EMBRAPA SOLOS e Departamento de Geologia do Instituto de Geociências da UFRJ, abrangendo ensaios de caracterização; ensaios mineralógicos; análises químicas; obtenção das curvas características solo-água; ensaios de erodibilidade; ensaios especiais para a determinação de parâmetros de resistência e de compressibilidade. A partir dos resultados obtidos, espera-se que os mesmos proporcionem uma contribuição para o melhor entendimento de perfis intempéricos em rochas de caráter básico. / [en] In spite of the fact that basalt formations are found in several regions in Brazil, it is difficult to find investigations on the subject relating chemical and mineralogical characteristics with geotechnical ones. The site of the present study comprises a soil slope on the North-South Railroad, at Arguianópolis, Tocantins State. Several landslides occurred during the construction of the railway. The soil mass is mostly composed by soils resulting from basalt alterations. The present study was developed in two stages. The first stage comprised a visit to the site, when a morphologic description of profiles was made and undisturbed and remoulded soil samples were extracted. The second stage refers to works developed at the Geotechnical and Environmental Laboratory of PUC-Rio, at EMBRAPA Soils and at the Geology Department of the Institute of Geosciences of the UFRJ. Such works comprised soil characterization tests; mineralogical tests; chemical analyses; definition of soil-moisture characteristic curves; erodobility tests and special tests to determine strength and compressibility parameters. The results obtained provide a contribution to a better understanding of weathering profiles in rocks of basic character.

The solvent-induced swelling behaviour of Victorian brown coals was examined in detail to probe the bonding mechanisms in very low rank coals (in this case Victorian brown coal). Correlation of solvent properties with differences in observed swelling behaviour were interpreted in terms of the coal structure, and means of predicting the observed behaviour were considered. Modification of the coal structure via physical compression (briquetting), chemical digestion, thermal modification, and functional group alkylation was used to further elucidate those structural features which govern the swelling behaviour of Victorian brown coals. Briquette weathering (i.e. swelling and disintegration of briquettes when exposed to variations in humidity and temperature) was examined by making alterations to briquette feed material and observing the effects on swelling in water. The application of solubility parameter alone to prediction of coal swelling was rejected due to the many exceptions to any proposed trend. Brown coal swelling showed a minimum when the solvent electron-donor number (DN) minus its electron-acceptor number (AN) was closest to zero, i.e. when DN and AN were of similar magnitude. The degree of swelling increased either side of this point, as predicted by theory. In contrast to the solubility parameter approach (which suffers from the uncertainty caused by specific interaction between coal and solvent), the electron donor/acceptor approach is about specific interactions. It was concluded that a combination of total and three-dimensional solubility parameters and solvent electron donor/acceptor numbers may be used to predict solvent swelling of unextracted brown coals with some success. Solvent access to chemically densified coal was found to be insensitive to a reduction in pore volume, and chemical effects were dominant. Thermal modification of the digested coal resulted in reduced swelling for all solvents, indicating that the structure had adopted a minimum energy configuration due to decarboxylation and replacement of hydrogen bonds with additional covalent bonds. Swelling of oxygen-alkylated coals demonstrated that the more polar solvents are able to break relatively weak hydrogen bonded crosslinks. The large difference between the rate and extent of swelling in water (and hence weathering) of Yallourn and Morwell briquettes was shown to be almost entirely attributable to exchanged magnesium. Magnesium exchange significantly increases the rate and extent of swelling of Yallourn coal. It was also shown that the swelling of briquettes due to uptake of water by magnesium-exchanged coals is reduced significantly with controlled ageing of the briquettes. The solvent swelling behaviour of Victorian brown coals is consistent with the notion that coal is a both covalently and non-covalently crosslinked and entangled macromolecular network comprising extractable species, which are held within the network by a wide range of non-covalent, polar, electron donor/acceptor interactions. Solvents capable of significant extraction of whole brown coals are also capable of significant swelling, but not dissolution, of the macromolecular coal network, which supports the view that the network is comprised of both covalent and ionic bonding. Victorian brown coals have also been shown to exhibit polyelectrolytic behaviour due to a high concentration of ionisable surface functionalities.

Biomass energy is currently the largest renewable contributor to global energy supply and there is increasing demand for bioenergy feedstock. Consequently, the production of purpose-grown woody bioenergy crops, such as short rotation coppice (SRC) willow, is expected to proliferate. Although the economic and environmental benefits associated with SRC willow production are well documented, systematic assessments of nutrient cycling within these plantations are rare. The objective of this study was to examine biomass production and biogeochemical cycling of nitrogen (N), phosphorus (P), potassium (K), sulphur (S), calcium (Ca), and magnesium (Mg) during an initial four-year rotation of six willow varieties grown at four plantations along a 500 km north-south pedoclimatic gradient within Saskatchewan, Canada. Nutrient budgets were also calculated after quantifying various nutrient inputs (e.g., atmospheric deposition, soil mineral weathering, and organic matter mineralization), outputs (e.g., above- and below-ground biomass, leaching, and denitrification), and transfers (e.g., canopy exchange, leaf litter decomposition, and fine root turnover) affecting the plant available soil nutrient pool. Total stem, leaf litter, and below-ground (primarily fine roots) biomass production after four years averaged 19.0, 7.1, and 12.5 Mg ha-1, respectively, with corresponding soil nutrient budget deficits of 17, 39, 112, 271, and 74 kg ha-1 of N, P, K, Ca, and Mg, respectively, but a soil S surplus of 60 kg ha-1. Despite willow’s relatively low nutrient-demanding nature, negligible leaching and denitrification losses, and substantial nutrient cycling from leaf litter, the nutrient export in harvested biomass over multiple rotations will require soil nutrient amendments, particularly N and P, to maintain plantation productivity. Given the apparent eventual need for supplemental fertility to support adequate willow growth over the 22-yr plantation life span, the fate of broadcast 15N-labelled fertilizer was also examined. Though the willow accumulated less than ⅓ of the applied fertilizer N after one year, the majority of the residual fertilizer N (51%) remained available for willow uptake in subsequent years. Further research is needed to track the fate of applied fertilizers over multiple rotations to better understand fertilizer dynamics for optimizing SRC willow agronomy; thus helping to promote its viability as a biomass energy feedstock option.

The Pilbara region of Western Australia hosts the Hamersley Province, an area of abundant iron ore resources located in the lower Hamersley Groups, Brockman and Marra Mamba Iron Formations. This study consists of a geotechnical and a geochemical and mineralogical investigation into the Banded Iron Formation (BIF) and shale deposits of the lower Hamersley Group that reside in the pit walls of RTIO mines in Western Australia. Areas throughout Tom Price, Paraburdoo, Marandoo and West Angelas iron ore mines are geotechnically investigated for rock mass conditions through the use of the Slope Mass Rating (SMR) classification system and through point load and slake durability testing. Selected samples from these areas were then geochemically and mineralogically tested by X-ray Fluorescence (XRF), X-ray Diffraction (XRD) and microscopic analysis, to determine the geochemical and mineralogical changes of BIF and shale as they alter and weather through hypogene and supergene alteration and Recent weathering. It was found that the most efficient method for determining the alteration and/or weathering of lower Hamersley Group BIF and shale deposits was by the use of a chemical alteration index, calculated from enriched and depleted major elements in the BIF and shale as they alter and weather. It has been suggested here that this Pilbara Iron alteration index can be calculated efficiently and effectively from geochemical testing in intervals down boreholes throughout future or developing open pit mines to assist in estimating slope stability conditions. It is also suggested that many boreholes should be analysed in section or in 3D space to create cross sections or block models showing the varying extent of alteration and weathering throughout the area being studied. From the geotechnical investigation, it was found that the weakest region, in terms of pit slope stability, were the highly and extremely altered and/or weathered regions with Pilbara Iron alteration indices of between 61 and 80, and 81 and 100, respectively. If these zones are identified, slope stability analysis can be focused on these geotechnically vulnerable areas. Slope stability analysis should be completed by using a suitable technique, such as by the use of SMR, which, along with other risk identification measures, will identify potentially unstable areas and suggest the required course of action. Further hazard and risk analysis should be undertaken in potentially unstable areas and remedial measures undertaken as appropriate. Thereby, the Pilbara Iron alteration index can be used in the Hamersley Province as a predictive tool for pit slope stability.

No description available.

L’analyse de sédiments totaux et de fractions granulométriques de la rivière Gandak (Himalaya) a montré que la variabilité des séries de l’uranium observée pour les sédiments himalayens est contrôlée par leur évolution minéralogique et granulométrique plutôt que par le mécanisme d’altération. Cette conclusion questionne les travaux antérieurs et souligne la nécessité d’étudier la mobilité des radionucléides à échelle minérale. A cette fin, une approche sur fractions minérales a mis en évidence des processus d’échange entre les minéraux, avec une mobilité significative de 230Th, fortement appauvri dans les zircons, et 226Ra, enrichis en particulier dans la fraction argileuse. Les déséquilibres observés semblent induits par un processus d’altération récent, de quelque ka.Ces résultats sont confirmés par l’analyse des déséquilibres 238U-234U-230Th dans des minéraux par SIMS, qui montre un enrichissement en 230Th à la surface des monazites et une perte de Th (232, 230) dans les zircons. / The analysis of total sediments and grain-size fractions from the Gandak river (Himalaya) showed that the Uranium series variability observed for the Himalayan sediments is controlled by their mineralogical and grain-size evolution, rather than by the weathering process.This conclusion called into question the transfer timescale in Himalayan plains estimated by previous works and highlighted the need to explore radionuclide mobility at the mineral scale. For this purpose, an approach on pure mineral fractions pointed out exchange processes between the mineral phases, with a significant mobility of 230Th, strongly depleted in zircon, and 226Ra, particularly enriched in the clay fraction. The observed disequilibria are attributed to a recent weathering process of a few ky. Those observations are confirmed by the SIMS analysis of 238U-234U-230Th disequilibria on mineral grains, which show a 230Th enrichment at the grain surface in monazites and a loss of Th, 230 and 232, in zircons.