La lithosphère continentale est physiquement et chimiquement segmentée. La cartographie des isotopes radiogéniques de roches plutoniques acides, représentatives de la croûte continentale, et de laves basiques, représentatives du manteau, possède des similarités avec la cartographie sismique de la lithosphère sous-jacente. Ces similitudes permettent d'interpréter les observations sismiques en étudiant leurs caractéristiques chimiques et leur âge. Les isotopes du plomb permettent de dater et d'identifier l'empilement de segments crustaux qui forment la croûte. L'écart des âges modèles du plomb avec d'autres systèmes identifie le recyclage crustal et le réchauffement de la croûte au dessus de la température du système plomb-plomb. Le système plomb-plomb donne également accès au sous-étudié rapport Th/U qui contraint la profondeur de la source des roches continentales. Certains échantillons de l'ouest U.S.A. proviennent de la croute inférieure, et se sont formés par l'extension crustale ou par un flux de matériel au sein de la croûte. Les isotopes du néodyme et de l'hafnium marquent la fusion du manteau lithosphérique enrichis sous le Colorado Plateau, une région où est observée le détachement du manteau lithosphérique sub-continental. Ce manteau fond par décompression adiabatique, par extension localisée ou remontée asthénosphérique engendrée par la convection locale. Au final, l'association des systèmes isotopiques du plomb, du néodyme, et de l'hafnium avec la sismologie est une approche puissante pour étudier la formation et la déformation de la lithosphère continentale.

Numerous glacial advances over the past 2 million years have covered the entire Canadian and Fennoscandian Shield outcrop. During glacial advance and retreat, permafrost is expected to form in front of the glacier. The question of how permafrost and freezing impact the formation and evolution of brines in natural systems may be vital to understanding the chemistry of groundwater in crystalline rocks. Investigations of groundwater conditions beneath thick permafrost can provide valuable information that can be applied to assessing safety of deep, underground nuclear waste repositories and understanding analogues to potential life-bearing zones on Mars. However, very little scientific investigation of cryogenic processes and hydrogeology deep within crystalline systems has been published. The purpose of this research is to evaluate the impacts of thick permafrost (>300m) formation on groundwater chemical and flow system evolution in the crystalline rock environment over geologic timescales. A field investigation was conducted at the Lupin Mine in Nunavut, Canada, to characterize the physical and hydrogeochemical conditions within and beneath a thick permafrost layer. Taliks, or unfrozen channels within the permafrost, are found beneath large lakes in the field area, and provide potential hydraulic connections through the permafrost. Rock matrix waters are dilute and do not appear to affect groundwater salinity. Permafrost waters are Na-Cl and Na-Cl-SO4 type, and have been contaminated with chloride and nitrate by mining activities. Sulfide oxidation in the permafrost may be naturally occurring or is enhanced by mining activities. Basal permafrost waters (550 to 570 mbgs) are variably affected by mining. The less contaminated basal waters have medium sulfate concentrations and are Ca-Na dominated. This is similar to deeper, uncontaminated subpermafrost waters, which are Ca-Na-Cl or Na-Ca-Cl type with a wide range of salinities (2.6 to 40 g•L-1). The lower salinity subpermafrost waters are attributed to dissociation of methane hydrate and drawdown of dilute talik waters by the hydraulic gradient created by mine dewatering. This investigation was unable to determine the influence of talik waters to the subpermafrost zone in undisturbed conditions. Pressures are also highly variable, and do not correlate with salinity. Fracture infillings are scarce and calcite δ18O and δ13C values have a large range. Microthermometry indicates a large range in salinities and homogenization temperatures as well, indicative of a boiling system. In situ freezing of fluids and methane hydrate formation may have concentrated the remaining fluids. Field activities at the Lupin mine also provided an opportunity to study the nature of gases within crystalline rocks in a permafrost environment. Gases were generally methane-dominated (64 to 87), with methane δ13C and δ2H values varying between -56 and -42‰ VPDB and -349 to -181 ‰ VSMOW, respectively. The gases sampled within the Lupin mine have unique ranges of chemical and isotopic compositions compared with other Canadian and Fennoscandian Shield gases. The gases may be of thermogenic origin, mixed with some bacteriogenic gas. The generally low δ2H-CH4 ratios are somewhat problematic to this interpretation, but the geologic history of the site, a metaturbidite sequence, supports a thermogenic gas origin. The presence of gas hydrate in the rock surrounding Lupin was inferred, based on temperature measurements and hydrostatic pressures. Evidence also suggests fractures near the mine have been depressurized, likely due to mine de-watering, resulting in dissipation of methane hydrate near the mine. Modeling results indicate methane hydrates were stable throughout the Quaternary glacial-interglacial cycles, potentially limiting subglacial recharge. The effects of deep permafrost formation and dissipation during the Pleistocene glacial/interglacial cycle to deep groundwaters in the Canadian Shield were also investigated by compiling data from thirty-nine sites at twenty-four locations across the Canadian Shield. Impacts due to glacial meltwater recharge and surficial cryogenic concentration of fluids, which had been previously considered by others, and in situ freeze-out effects due to ice and/or methane hydrate formation were considered. At some Canadian Shield sites, there are indications that fresh, brackish, and saline groundwaters have been affected by one of these processes, but the data were not sufficient to differentiate between mixed, intruded glacial meltwaters, or residual waters resulting from either permafrost or methane hydrate formation. Physical and geochemical data do not support the cryogenic formation of Canadian Shield brines from seawater in glacial marginal troughs. The origin and evolution of Canadian and Fennoscandian Shield brines was explored with a survey of chlorine and bromine stable isotope ratios. The δ37Cl and δ81Br isotopic ratios varied between -0.78 ‰ and 1.52 ‰ (SMOC) and 0.01 ‰ and 1.52 ‰ (SMOB), respectively. Variability of chlorine and bromine isotope ratios decreases with increasing depth. Fennoscandian Shield groundwaters tend to be more enriched than Canadian Shield groundwaters for both 37Cl and 81Br. Other sources and processes which may affect δ37Cl and δ81Br composition are also explored. Primary processes such as magmatic and/or hydrothermal activity are thought to be responsible for the isotopic composition of the most concentrated fluids at each site. Positive correlations between δ81Br, and δ37Cl with δ2H-CH4 and δ13C-CH4 were noted. At this time the cause of the relationship is unclear, and may be a result of changing redox, pH, temperature, and/or pressure conditions during hydrothermal, metamorphic, or volcanogenic processes. The data suggest solute sources and fluid evolution at individual sites would be better constrained utilizing a multi-tracer investigation of δ37Cl, δ81Br, and 87Sr/86Sr ratios comparing fluids, rocks, and fracture filling minerals (including fluid inclusions).

Numerous glacial advances over the past 2 million years have covered the entire Canadian and Fennoscandian Shield outcrop. During glacial advance and retreat, permafrost is expected to form in front of the glacier. The question of how permafrost and freezing impact the formation and evolution of brines in natural systems may be vital to understanding the chemistry of groundwater in crystalline rocks. Investigations of groundwater conditions beneath thick permafrost can provide valuable information that can be applied to assessing safety of deep, underground nuclear waste repositories and understanding analogues to potential life-bearing zones on Mars. However, very little scientific investigation of cryogenic processes and hydrogeology deep within crystalline systems has been published. The purpose of this research is to evaluate the impacts of thick permafrost (>300m) formation on groundwater chemical and flow system evolution in the crystalline rock environment over geologic timescales. A field investigation was conducted at the Lupin Mine in Nunavut, Canada, to characterize the physical and hydrogeochemical conditions within and beneath a thick permafrost layer. Taliks, or unfrozen channels within the permafrost, are found beneath large lakes in the field area, and provide potential hydraulic connections through the permafrost. Rock matrix waters are dilute and do not appear to affect groundwater salinity. Permafrost waters are Na-Cl and Na-Cl-SO4 type, and have been contaminated with chloride and nitrate by mining activities. Sulfide oxidation in the permafrost may be naturally occurring or is enhanced by mining activities. Basal permafrost waters (550 to 570 mbgs) are variably affected by mining. The less contaminated basal waters have medium sulfate concentrations and are Ca-Na dominated. This is similar to deeper, uncontaminated subpermafrost waters, which are Ca-Na-Cl or Na-Ca-Cl type with a wide range of salinities (2.6 to 40 g•L-1). The lower salinity subpermafrost waters are attributed to dissociation of methane hydrate and drawdown of dilute talik waters by the hydraulic gradient created by mine dewatering. This investigation was unable to determine the influence of talik waters to the subpermafrost zone in undisturbed conditions. Pressures are also highly variable, and do not correlate with salinity. Fracture infillings are scarce and calcite δ18O and δ13C values have a large range. Microthermometry indicates a large range in salinities and homogenization temperatures as well, indicative of a boiling system. In situ freezing of fluids and methane hydrate formation may have concentrated the remaining fluids. Field activities at the Lupin mine also provided an opportunity to study the nature of gases within crystalline rocks in a permafrost environment. Gases were generally methane-dominated (64 to 87), with methane δ13C and δ2H values varying between -56 and -42‰ VPDB and -349 to -181 ‰ VSMOW, respectively. The gases sampled within the Lupin mine have unique ranges of chemical and isotopic compositions compared with other Canadian and Fennoscandian Shield gases. The gases may be of thermogenic origin, mixed with some bacteriogenic gas. The generally low δ2H-CH4 ratios are somewhat problematic to this interpretation, but the geologic history of the site, a metaturbidite sequence, supports a thermogenic gas origin. The presence of gas hydrate in the rock surrounding Lupin was inferred, based on temperature measurements and hydrostatic pressures. Evidence also suggests fractures near the mine have been depressurized, likely due to mine de-watering, resulting in dissipation of methane hydrate near the mine. Modeling results indicate methane hydrates were stable throughout the Quaternary glacial-interglacial cycles, potentially limiting subglacial recharge. The effects of deep permafrost formation and dissipation during the Pleistocene glacial/interglacial cycle to deep groundwaters in the Canadian Shield were also investigated by compiling data from thirty-nine sites at twenty-four locations across the Canadian Shield. Impacts due to glacial meltwater recharge and surficial cryogenic concentration of fluids, which had been previously considered by others, and in situ freeze-out effects due to ice and/or methane hydrate formation were considered. At some Canadian Shield sites, there are indications that fresh, brackish, and saline groundwaters have been affected by one of these processes, but the data were not sufficient to differentiate between mixed, intruded glacial meltwaters, or residual waters resulting from either permafrost or methane hydrate formation. Physical and geochemical data do not support the cryogenic formation of Canadian Shield brines from seawater in glacial marginal troughs. The origin and evolution of Canadian and Fennoscandian Shield brines was explored with a survey of chlorine and bromine stable isotope ratios. The δ37Cl and δ81Br isotopic ratios varied between -0.78 ‰ and 1.52 ‰ (SMOC) and 0.01 ‰ and 1.52 ‰ (SMOB), respectively. Variability of chlorine and bromine isotope ratios decreases with increasing depth. Fennoscandian Shield groundwaters tend to be more enriched than Canadian Shield groundwaters for both 37Cl and 81Br. Other sources and processes which may affect δ37Cl and δ81Br composition are also explored. Primary processes such as magmatic and/or hydrothermal activity are thought to be responsible for the isotopic composition of the most concentrated fluids at each site. Positive correlations between δ81Br, and δ37Cl with δ2H-CH4 and δ13C-CH4 were noted. At this time the cause of the relationship is unclear, and may be a result of changing redox, pH, temperature, and/or pressure conditions during hydrothermal, metamorphic, or volcanogenic processes. The data suggest solute sources and fluid evolution at individual sites would be better constrained utilizing a multi-tracer investigation of δ37Cl, δ81Br, and 87Sr/86Sr ratios comparing fluids, rocks, and fracture filling minerals (including fluid inclusions).

Le complexe granitique de Quérigut (Est de la zone axiale des Pyrénées) a été étudié par de nombreux auteurs, dont le premier et sans doute le plus illustre fut A. Lacroix. Son encaissant, varié, car formé de calcaires, de dolomies, de micaschistes, de gneiss, a été étudié de manière plus ponctuelle. Nous nous sommes intéressés à ce secteur car, contrairement à ce qui se passe autour d'autres granitoïdes pyrénéens comme Salau et Costabonne, on n'avait pas trouvé de skarns minéralisés en scheelite, alors que l'encaissant semblait a priori favorable (contacts granitoïdes intrusifs/calcaire). Les skarns existent néanmoins, sont même parfois minéralisés, mais leur ampleur est dans la plupart des cas très limitée, n'0ffrant aucun espoir d'exploitation fructueuse. Cette énigme a constitué le fil conducteur de notre travail. Mais ce travail a permis également de décrire et de comprendre de nouveaux skarns, les particularités des skarns stériles, la genèse des faciès "contaminés" des granitoïdes, et de progresser dans la connaissance de l'intéressant phénomène hydrothermal que constitue un skarn.

The work presented in this dissertation explores the nature of agro-pastoral strategies developed by Neolithic farmers as a way to understand how early food production was inter-twined with environmental and socio-economic opportunities and constraints. Towards this end, a multi-isotope approach is used to address questions of scale and intensity of crop cultivation and animal management at the archaeological sites of Kouphovouno, southern Greece, Makriyalos, northern Greece, and Çatalhöyük, south-central Turkey. Measurements of stable carbon, nitrogen, oxygen and strontium isotope values of carbonized plant remains, human and animal bone collagen and animal tooth enamel are used to examine the similarities and differences in the types of treatments that individual species of plants and animals received during the agricultural cycle at the distinct locations. The results show that farmers at the three sites developed variable methods for exploiting the arable and pastoral landscape and catering to their economic and culinary needs. The discussion considers the implications of these findings to our understanding of the complexity and adaptability of early farming systems.

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.

This research study investigated the level of bone collagen preservation of rat femora from Liang Bua cave on the island of Flores, Indonesia, as well as conducted carbon and nitrogen stable isotopic analyses on well preserved samples. Although Flores is located in a hot intermediate tropical zone and the burial environment of the bone samples within the cave is considered less than optimal for collagen preservation, significant preservation of the bone collagen was found. Collagen yields, C:N ratio and carbon and nitrogen concentrations were investigated. However, this research study argues that carbon and nitrogen concentrations are an appropriate means to determine preservation on its own. According to the carbon and nitrogen concentration data 32 samples were considered well preserved. Carbon and nitrogen stable isotopic analyses were conducted on the 32 preserved samples. According to the carbon data a significant shift in the δ13C values from a C3 signature to a C4 signature occurred prior to 2,750 years ago. This shift is indicative of the introduction of a non-endemic C4 plant, which is believed to be either foxtail millet or sugarcane. Since this shift occurs abruptly it indicates that the introduction of agriculture to Flores occurred at one time and has continued to present day

The Eurasian woodcock Scolopax rusticola (hereon woodcock) is a wader adapted to woodland and farmland habitats. It is an important quarry species, widely hunted across Europe, but owing to its cryptic plumage and elusive nature, there exists only poor information concerning its natural history. As such, the conservation status of the woodcock remains uncertain. One area that is particularly lacking is knowledge of its ecology outside the breeding season. Generally, avian ecological studies have focused on breeding season events due to the importance of reproductive success in determining fitness. However, it is now apparent that the non-breeding season represents an equally important period of the annual cycle. For example, recent studies have shown that declines in some migratory bird populations were due to events during the non-breeding season, either during migration, or on the wintering grounds. In Britain, the non-breeding woodcock population comprises both British breeding and non-British breeding birds, yet the origins and relative distribution of these sub-populations is not fully understood. Nor is it known whether ecological differences exist between them. This thesis addresses these two aspects of woodcock biology, using stable isotope and radio-tracking methods. The former was used to assign birds to their likely origins and determine population-specific distributions across Britain. The latter was used, in conjunction with the former, to determine whether ecological differences exist between locally-breeding and non-locally breeding birds residing in Hampshire in winter. A large degree of mixing between birds from different breeding populations was apparent for woodcock residing in Britain over winter. Russia and Fennoscandia comprised the most likely origins of migratory birds and regional differences in distributions were apparent. The highest proportions of birds from Russia were found in Norfolk and Wales, whilst the highest proportions of birds from Fennoscandia were found in Scotland. The presence of non-breeding residents in Cornwall and Ireland also provided strong evidence for the short-distance, south-westerly movements of resident birds, which probably originated from Scotland. Locally, the movements and behaviour of birds were found to vary with age (adult vs. juvenile) and/or predicted migratory status (resident vs. migrant), with adult residents potentially representing the dominant group. Differences in habitat use, commuting flights, home range size and activity patterns were all apparent. As such, these findings might have important consequences for the relative survival rates and breeding success of resident and migrant woodcock. This work has provided new insights into the non-breeding ecology of woodcock in Britain and contributes significantly to European efforts to better understand this bird species. Given the importance of seasonal interactions, an understanding of events throughout the annual cycle is necessary and this can only be achieved through concerted efforts. Indeed, an integrated approach is imperative to develop the conservation plans necessary to ensure the sustainability of the woodcock.

The Pliocene world c.5.3 Ma to c.2.58 Ma exhibited a relatively stable climate with a warmer global mean surface temperature than present-day by ~2 °C to 3 °C, and palaeoclimate analysis from this interval is used to understand climate drivers in ‘warmer world’. Previous oxygen isotope thermometry investigations of Pliocene southern North Sea Basin (SNSB) Aequipecten opercularis from the Coralline Crag Formation in Suffolk, UK repeatedly reveal evidence of a cold-temperate climate regime. Contrastingly, other biological proxies record a warm-temperate/sub-tropical regime. This investigation concentrated on oxygen, carbon and microgrowth increment widths (MIWS) of fossil shell material from Pliocene SNSB spanning an interval of~4.4 Ma to ~2.5 Ma. The study sites included shallow marine Pliocene formations from the western and eastern SNSB, the Ramsholt Member of the Coralline Crag Formation, Suffolk UK, and the Luchtbal Sands and Oorderen Sands Members of the Lillo Formation, Belgium, and the Oosterhout Formation in the Netherlands. Oxygen isotopic palaeotemperature results showed cooler summer temperatures than presently in the SNSB, which were reflective of a cool-temperate regime. There was no evidence of warm-temperate or sub-tropical summer palaeotemperatures in the Pliocene SNSB as suggested by other planktonic proxies. This investigation discussed the possible causal factors for the cooler – than- expected winter and summer palaeotemperatures in the ‘warmer’ Pliocene world as recorded by this proxy. Discrepancies between the cool summer benthic palaeotemperatures from the bivalves and the warmer sub-tropical or warm-temperate summer palaeotemperature estimations from planktonic biological proxies was rectified by the application of a theoretical summer stratification factor (SSF). However, rectifying the discrepancies between cooler (cold-temperate) benthic winter palaeotemperatures and the warmer winter palaeotemperatures from other proxies was difficult because stratification does not occur during the winter. Dormancy behaviours in the warm- temperate –sub-tropical organisms was proposed as a suitable mechanism to allow their coexistence with the cool-tolerant bivalves, which were able to grow and feed underneath the thermocline during the summer months. Therefore, the investigation showed how the Pliocene SNSB exhibited a greater seasonality than occurs presently in the SNSB. The driver for the cooler winter temperatures in the Pliocene SNSB was not identified. Localised explanations including continental wind effects, interannual variations in MOC strength, and increased storm activity in the winter bringing cooler water into the SNSB were all suggested as potential drivers. Global features of climate including interglacial/glacial cycles and orbital forcing effects were factors also proposed for the overall mixed palaeotemperature signal in the Pliocene SNSB.

This project addressed if decaying macroalgae and leaf detritus play a major role in the detrital pool of a 7th-order karst riverine system. Decay rates, macroinvertebrates colonization patterns, and change in δ13C values of Cladophora, Platanus occidentalis, and a mix of Acer negundo and A. saccharinum were tracked during summer and autumn months for portions of multiple years. Packs of air-dried Cladophora, Acer, and P. occidentalis were placed in mesh bags and put in groups (n=4) in wire baskets. Seven baskets were submerged in riffle (0.5 m) and deeper run (2 m) habitats. Benthic organic matter was collected with each pack to see if there was a correlation with δ13C signatures of decaying macroproducers to help understand what is entering the detrital food web. Summer 2014 Cladophora and Acer were significantly faster to breakdown than Platanus in both habitats. In autumn‒spring 2014‒2015, Cladophora was significantly faster to breakdown than leaves. Isotopic values of Cladophora were not significantly different than leaves in summer 2014 but were significantly more δ13Cdepleted in the autumn‒spring 2014‒2015. There were no significant differences in macroinvertebrate abundance between the macroproducers for either season. Cladophora had significantly lower macroinvertebrate richness in both seasons, lower shredder abundance, but a significantly higher abundance of clingers. The mean δ13C values of benthic detritus were significantly different than all three macroproducers in the summer and significantly different than Cladophora in the run treatment for autumn‒spring. Seasonality had a strong influence on breakdown rates, leading to greater mass loss of all three species in the warm summer months compared to the cooler autumn‒spring months. The low macroinvertebrate richness and shredder abundance on the decaying macroalga suggests Cladophora may not be consumed by macroinvertebrates but used strictly as habitat. The implication of rapid Cladophora decay during warm seasons, plus few colonizing macroinvertebrate taxa, is that the decaying macroalgae may not pass through a decomposer food web before being remineralized as CO2.