L'atmosphère terrestre a subi, au cours de son histoire précoce, de très violents changements dans sa composition chimique. L'émergence des premiers êtres vivants photosynthétique a provoqué la mise en place et la modification des grands cycles biogéochimiques. L'usage des isotopes comme traceurs des processus physico-chimiques actifs pendant ces périodes s'est développé depuis les années 80. L'observation de compositions isotopiques anormales dans certaines molécules atmosphériques (ozone notamment), similaires à celles observées dans les météorites par Clayton (1973), pose question. De nombreuses hypothèses ont été proposées pour expliquer ce phénomène "anormal". L'objectif principal de cette thèse de doctorat est de développer, par l'expérimentation, l'étude d'un certain nombre de réactions en phase plasma du point de vue isotopique. Seront particulièrement étudiées des réactions appelées réactions à trois corps de formation de l'ozone, où la formation d'un complexe intermédiaire excité entre en jeu dans les mécanismes de génération de ces fractionnements isotopiques anormaux. / The Earth's atmosphere has undergone, during its early history, very violent changes in its chemical composition. The emergence of the first photosynthetic living beings has led to the establishment and modification of major biogeochemical cycles. The use of isotopes as tracers of active physico-chemical processes during these periods has been developed since the 1980s. The observation of abnormal isotopic compositions in certain atmospheric molecules (ozone in particular), similar to those observed in meteorites by Clayton (1973), raises questions. Many hypotheses have been proposed to explain this "abnormal" phenomenon. The main objective of this doctoral work is to develop, through experimentation, the study of plasma reactions from an isotopic point of view. In particular, ozone formation third-body reactions, where the formation of an excited intermediate complex is involved in the mechanisms of generating these abnormal isotopic fractionations, will be studied.

Growth rates, δ18O and δ13C of five stalagmites from the west coasts of North and South Islands, New Zealand, provide records of millennial-scale climate variability over the last ~75 kyr. Thirty-five uranium-series ages were used to provide the chronology. δ18O of stalagmite calcite was influenced by changes in moisture source region, temperature and both δ18O and δ13C primarily display a negative relationship with rainfall. To assist interpretation of climatic signals δ18O profiles were adjusted for the ice-volume effect. Changes in these proxies reflect changes in the strength of the circumpolar westerly circulation and the frequency of southwesterly flow across New Zealand. MIS 4 was a period of wet and cool climate lasting from 67.7 to 61.3 kyr B.P., expressed in the stalagmites by an interval of strongly negative isotope ratios and increased growth rate. This contrasts with less negative δ18O and δ13C, and slow growth, interpreted as dry and cold climate, during much of MIS 2. This difference between MIS 2 and MIS 4 provides an explanation for why glacial moraines in the Southern Alps of MIS 4 age lie beyond those deposited during the last glacial maximum (MIS 2). Heinrich events, with the exception of H0 (the Younger Dryas), are interpreted from high-resolution South Island stalagmite HW05-3, from Hollywood Cave, West Coast, as times of wetter and cooler climate. Minima in δ18O and δ13C (wet periods) occurred at 67.7-61.0, 56-55, 50.5-47.5, 40-39, 30.5-29, 25.5-24.3 and 16.1-15. kyr B.P. matching Heinrich events H6-H1 (including H5a) respectively. This demonstrates a robust teleconnection between events in the North Atlantic and New Zealand climate. Minima in δ18O also occurred at similar times in less well-dated North Island stalagmite RK05-3 from Ruakuri Cave, Waitomo. Speleothems from low-latitudes have revealed that Heinrich events forced southerly displacement of the Intertropical Convergence Zone. This caused steepening of the temperature gradient across mid-southern latitudes, increased westerly circulation and resulted in wet conditions on the west coast of both islands. Immediately following H1 in the HW05-3 stable isotope profiles is another excursion to more negative isotopic values, suggesting wet and cold climate, lasting from 14.6 to 13.0 kyr B.P. Such a climate on the West Coast at this time has been previously suggested from glacier advance (e.g. Waiho Loop moraine) and decreased abundance of tall trees on the landscape. This event occurred too early to be a response to H0, but is synchronous with a return to cool climate in Antarctica. Thus West Coast climate appears to have been sensitive to changes in Antarctica as well as the North Atlantic. Isotopic minima (wet and cool climate) in South Island stalagmite GT05-5, which formed during the Holocene, first occurred 4.6 kyr B.P. This began a series of four oscillations in isotope ratios, the last terminating when the stalagmite was collected (2006). Onset of these oscillations is associated with initiation of ice advance in the Southern Alps, and beginning of the Neoglacial. The last oscillation displays enriched isotope ratios lasting from 1.2 to 0.8 kyr B.P. succeeded by depleted ratios lasting until 0.15 kyr B.P., mirroring the Medieval Climate Optimum and Little Ice Age, respectively, of European palaeoclimate records.

Iron is the most important metal for modern industry and Sweden is the number one iron producer in Europe. The main sources for iron ore in Sweden are the apatite-iron oxide deposits of the "Kiruna-type", named after the iconic Kiruna ore deposit in Northern Sweden. The genesis of this ore type is, however, not fully understood and various schools of thought exist, being broadly divided into "ortho-magmatic" versus the "hydrothermal replacement" approaches. This study focuses on the origin of apatite-iron oxide ore of the Grängesberg Mining District (GMD) in Central Sweden, one of the largest iron reserves in Sweden, employing oxygen and iron isotope analyses on massive, vein and disseminated GMD magnetite, quartz and meta-volcanic host rocks. As a reference, oxygen and iron isotopes of magnetites from other Swedish and international iron ores as well as from various international volcanic materials were also analysed. These additional samples included both "ortho-magmatic" and "hydrothermal" magnetites and thus represent a basis for a comparative analysis with the GMD ore. The combined data and the derived temperatures support a scenario that is consistent with the GMD apatite-iron oxides having originated dominantly (ca. 87 %) through ortho-magmatic processes with magnetite crystallisation from oxide-rich intermediate magmas and magmatic fluids at temperatures of 600 °C to 900 °C. A minor portion of the GMD magnetites (ca. 13 %), exclusively made up of vein and disseminated ore types, is in equilibrium with a high-δ18O and low-δ56Fe hydrothermal fluid at temperatures below 400 °C, indicating the existence of a hydrothermal system associated with the GMD volcano.

Middle Ordovician carbonates in the Lake Simcoe area, south-central Ontario were examined to determine if: (1) The δ18O values of early-stage calcite cement in hardgrounds are useful proxies for Ordovician seawater δ18O values; (2) a regional hydrothermal event affected middle Ordovician strata in the Lake Simcoe area. Whole rock samples of middle Ordovician hardgrounds and immediately overlying limestones containing early calcite cement have δ13C values ranging from -1.7 to +2.9‰ (PDB) and δ18O values ranging from -6.9 to -2.9‰ (PDB). Hardground δ18O values and the similarity of the isotopic composition between the hardgrounds and overlying limestones are consistent with diagenetic alteration during shallow burial, which indicates the hardgrounds are not useful proxies. Late-stage calcite cements have δ13C values from -8.4 to +2.9‰ (PDB) and δ18O values from -11.4 to -6.0‰ (PDB). Late-stage microcrystalline dolomites have δ13C values from -3.9 to +0.4‰ and δ18O values from -10.7 to -7.6‰. Late-stage saddle dolomites have δ13C values from -1.7 to 1.9‰ and δ18O values from -13.8 to -8.5‰. The late-stage carbonate δ18O values are more negative than the early-stage carbonate δ18O values and are interpreted to reflect progressively deeper burial diagenesis. Four types of fluid inclusions were identified in late-stage calcite, saddle dolomite, barite, and quartz. Type 1 inclusions are aqueous liquid-rich with very consistent low to very low vapour-liquid ratios and are of primary, secondary pseudosecondary and indeterminate origins. Type 2 inclusions are aqueous liquid-only and are of primary and secondary origins. Type 3 inclusions are oil-bearing, liquid-rich with low to medium vapor-liquid ratios and are of secondary origin. Type 4 inclusions are vapour-only and are of indeterminate origin. The type 4 inclusions analyzed did not yield any microthermometric data suggesting they are empty cavities that have lost all their fluid. Fluid inclusions of primary, secondary and pseudosecondary origins in calcite, dolomite and quartz have overlapping homogenization temperatures ranging from 43 to 188°C. Fluid inclusions of indeterminate origin in calcite and barite have homogenization temperatures from 80 to greater than 200°C. Petrographic and microthermometric evidence indicates that fluid inclusion homogenization temperatures greater than 150°C most likely are caused by stretching or leaking; therefore, are discounted. Fluid inclusion types 1 and 2 represent two fluid inclusion assemblages (FIA) based on final ice melting temperatures. The high salinity (10 to 30 wt%CaCl2) inclusions in FIA 1 are of primary, secondary, pseudosecondary and indeterminate origin in calcite, dolomite, barite and quartz. Fluid inclusions in FIA 1 are interpreted as reflecting saline basin brines from which the host minerals precipitated during burial diagenesis. The low salinity (0 to 2.7 wt%CaCl2) inclusions in FIA 2 are of secondary and indeterminate origin in calcite. Fluid inclusions in FIA 2 may reflect a meteoric origin such as in a vadose or phreatic environment based on inclusions containing different phases and variable vapor-liquid ratios. Alternatively the low salinity inclusions may reflect alteration from an influx of meteoric fluids that migrated through basement faults and fractures during periods of uplift and erosion. Early and late-stage carbonates from this study precipitated from 18O-depleted pore fluids and/or at progressively higher temperatures accompanying deeper burial. The FIA 1 homogenization temperatures support burial diagenesis at 66 to 80°C if it is assumed the rocks were buried 2 km, the surface temperature was 20°C and the geothermal gradient was between 23 to 30°C/km. An alternative interpretation is mineral precipitation during a regional hydrothermal event. Burial diagenesis does not explain the fluid inclusion homogenization temperatures of 90°C and greater unless geothermal gradients are higher than 35°C/km or burial depth is increased to 3 km or more. However, thermal maturity of organic matter in the Michigan Basin suggests Ordovician strata were never buried more than 2 km. Four models for regional hydrothermal fluid migration are: (1) gravity-driven flow; (2) ‘squeegee-type’ fluid flow; (3) convection cell fluid flow; and (4) structurally-controlled fluid flow. The gravity-driven model relies on continental heat flow and an influx of meteoric water from basin catchment areas. For the ‘squeegee, convection cell and structurally controlled models, hot fluids could have entered the region from several conduits concurrently during episodic reactivation of basement faults and fracture systems in response to intracratonic stresses created by the continuous interaction of tectonic plates. Determining which of the models best explains regional hydrothermal fluid flow in the Michigan Basin is difficult for several reasons; (1) surface temperatures and maximum burial temperatures at the time of mineral precipitation in the Michigan Basin during the Ordovician are unknown; (2) the timing of mineral precipitation in relation to tectonic pulses is undetermined; (3) there is as yet no known deep-seated heat sources in the Michigan Basin for convection to occur; and (4) it is unknown whether advection is a major process in the Michigan Basin. A collaborative multi-disciplinary research project covering geology, geophysics and hydrogeology would provide much more integrated data than is currently available from stable isotopes, fluid inclusions and organic matter.

No description available.

The shape of the thermocline and the depth of the lysoline in the western tropical Pacific are both influenced by the overlying atmosphere, and both the shape of thermocline and the depth of the lysocline can be reconstructed from foraminifera-based paleo-proxies. Paleoclimate proxy evidence suggests a southward shift of the Intertropical Convergence Zone (ITCZ) during times of Northern Hemisphere cooling, including the Last Glacial Maximum (LGM), 19-23 ka before present. However, evidence for movement over the Pacific has mainly been limited to precipitation reconstructions near the continents, and the position of the Pacific marine ITCZ is less well constrained. In this study, I address this problem by taking advantage of the fact that the upper ocean density structure reflects the overlying wind field. I reconstruct changes in the upper ocean density structure during the LGM using oxygen isotope measurements on the planktonic foraminifera G. ruber and G. tumida in a transect of sediment cores from the Western Tropical Pacific. The data suggest a ridge in the thermocline just north of the present-day ITCZ persists for at least part of the LGM, and a structure in the Southern Hemisphere that differs from today. The reconstructed structure is consistent with that produced in a General Circulation Model with both a Northern and Southern Hemisphere ITCZ. I also attempt to reconstruct the upper ocean density structure for Marine Isotope Stages 5e and 6, the interglacial and glacial periods, respectively, previous to the LGM. The data show a Northern Hemisphere thermocline ridge for both of these periods. There is insufficient data to draw any conclusions about the Southern Hemisphere thermocline. Using the same set of sediment cores, I also attempt to reconstruct lysocline depth over the last 23,000 years using benthic foraminiferal carbon isotope ratios, planktonic foraminiferal masses, and sediment coarse fraction percentage. Paleoclimate proxy evidence and modeling studies suggest that the deglaciation following the LGM is associated with a deepening of the lysocline and an increase in sedimentary calcite preservation. Although my data lack the resolution to constrain the depth of the lysocline, they do show an increase in calcite preservation during the last deglaciation, consistent with lysocline deepening as carbon moves from the deep ocean to the atmosphere.

Variability in the tropical ocean-atmospheric system causes global scale climate anomalies, most evident in the El Niño-Southern Oscillation’s coupled climate feedbacks. Despite being an area of high interest, many questions still remain regarding the west Pacific warm pool’s response to external forcing, particularly its response to increases in anthropogenic greenhouse gases. Paleoclimate reconstructions coupled with model simulations provide insight into the tropical Pacific’s role in past climate variability necessary to the development of robust climate projections. Most paleoclimate records, however, still lack the resolution, length, and chronological control to resolve rapid variability against a background of orbital-scale variations. Here we present stalagmite oxygen isotope (δ18O) reconstructions from Gunung Mulu National Park (4oN, 115oE ), in northern Borneo, that provide reproducible centennial-scale records of western Pacific hydrologic variability that are precisely U/Th-dated and continuous throughout most of the late Pleistocene (0-160 thousand years ago, kybp). The record comprises an entire glacial-interglacial cycle, which allows us to investigate orbital-scale climate forcings and compare two well-dated glacial terminations in the western tropical Pacific. The ice- volume-corrected δ18O records suggest that glacial boundary condtions, which include significantly lower atmospheric carbon dioxide levels, did not drive significant changes in Mulu rainfall δ18O. Similarly, Borneo stalagmite δ18O is poorly correlated to either global sea level shifts or Sunda Shelf areal exposure is not evident. The Borneo record does vary in phase with local mid-fall equatorial insolation, suggesting that precessional forcing may impart a strong influence on hydroclimate variability in the warm pool. This is best illustrated across Glacial Termination II, when the oscillation of equatorial fall insolation is large and out of phase with ice sheet decay. We also use a subset of well-dated, high-resolution stalagmite δ18O records from Mulu to investigate millennial-scale climate variability during Marine Isotope Stages 3-5 (30-100kybp). We find that regional convection likely decreased during the six massive iceberg discharges defined in the North Atlantic sediment records (“Heinrich events”). The inferred drying (increased stalagmite δ18O) during Heinrich events is consistent with a southward shift of the Intertropical Convergence Zone – the dominant paradigm to explain global climate anomalies originating in the north Atlantic (ref). However, any hydrologic variability related to Dansgaad-Oeschgar (D/O) events, millennial-scale sawtooth temperature anomalies of the last glacial period first evident in the Greenland ice records, is notably absent in the stalagmite records. . The Mulu stalagmite record’s absence of D/O signal, however, is in marked contrast to the regional west Pacific marine records and suggests D/O events and Heinrich events may be characterized by fundamentally different climate mechanisms and feedbacks.

Middle Ordovician carbonates in the Lake Simcoe area, south-central Ontario were examined to determine if: (1) The δ18O values of early-stage calcite cement in hardgrounds are useful proxies for Ordovician seawater δ18O values; (2) a regional hydrothermal event affected middle Ordovician strata in the Lake Simcoe area. Whole rock samples of middle Ordovician hardgrounds and immediately overlying limestones containing early calcite cement have δ13C values ranging from -1.7 to +2.9‰ (PDB) and δ18O values ranging from -6.9 to -2.9‰ (PDB). Hardground δ18O values and the similarity of the isotopic composition between the hardgrounds and overlying limestones are consistent with diagenetic alteration during shallow burial, which indicates the hardgrounds are not useful proxies. Late-stage calcite cements have δ13C values from -8.4 to +2.9‰ (PDB) and δ18O values from -11.4 to -6.0‰ (PDB). Late-stage microcrystalline dolomites have δ13C values from -3.9 to +0.4‰ and δ18O values from -10.7 to -7.6‰. Late-stage saddle dolomites have δ13C values from -1.7 to 1.9‰ and δ18O values from -13.8 to -8.5‰. The late-stage carbonate δ18O values are more negative than the early-stage carbonate δ18O values and are interpreted to reflect progressively deeper burial diagenesis. Four types of fluid inclusions were identified in late-stage calcite, saddle dolomite, barite, and quartz. Type 1 inclusions are aqueous liquid-rich with very consistent low to very low vapour-liquid ratios and are of primary, secondary pseudosecondary and indeterminate origins. Type 2 inclusions are aqueous liquid-only and are of primary and secondary origins. Type 3 inclusions are oil-bearing, liquid-rich with low to medium vapor-liquid ratios and are of secondary origin. Type 4 inclusions are vapour-only and are of indeterminate origin. The type 4 inclusions analyzed did not yield any microthermometric data suggesting they are empty cavities that have lost all their fluid. Fluid inclusions of primary, secondary and pseudosecondary origins in calcite, dolomite and quartz have overlapping homogenization temperatures ranging from 43 to 188°C. Fluid inclusions of indeterminate origin in calcite and barite have homogenization temperatures from 80 to greater than 200°C. Petrographic and microthermometric evidence indicates that fluid inclusion homogenization temperatures greater than 150°C most likely are caused by stretching or leaking; therefore, are discounted. Fluid inclusion types 1 and 2 represent two fluid inclusion assemblages (FIA) based on final ice melting temperatures. The high salinity (10 to 30 wt%CaCl2) inclusions in FIA 1 are of primary, secondary, pseudosecondary and indeterminate origin in calcite, dolomite, barite and quartz. Fluid inclusions in FIA 1 are interpreted as reflecting saline basin brines from which the host minerals precipitated during burial diagenesis. The low salinity (0 to 2.7 wt%CaCl2) inclusions in FIA 2 are of secondary and indeterminate origin in calcite. Fluid inclusions in FIA 2 may reflect a meteoric origin such as in a vadose or phreatic environment based on inclusions containing different phases and variable vapor-liquid ratios. Alternatively the low salinity inclusions may reflect alteration from an influx of meteoric fluids that migrated through basement faults and fractures during periods of uplift and erosion. Early and late-stage carbonates from this study precipitated from 18O-depleted pore fluids and/or at progressively higher temperatures accompanying deeper burial. The FIA 1 homogenization temperatures support burial diagenesis at 66 to 80°C if it is assumed the rocks were buried 2 km, the surface temperature was 20°C and the geothermal gradient was between 23 to 30°C/km. An alternative interpretation is mineral precipitation during a regional hydrothermal event. Burial diagenesis does not explain the fluid inclusion homogenization temperatures of 90°C and greater unless geothermal gradients are higher than 35°C/km or burial depth is increased to 3 km or more. However, thermal maturity of organic matter in the Michigan Basin suggests Ordovician strata were never buried more than 2 km. Four models for regional hydrothermal fluid migration are: (1) gravity-driven flow; (2) ‘squeegee-type’ fluid flow; (3) convection cell fluid flow; and (4) structurally-controlled fluid flow. The gravity-driven model relies on continental heat flow and an influx of meteoric water from basin catchment areas. For the ‘squeegee, convection cell and structurally controlled models, hot fluids could have entered the region from several conduits concurrently during episodic reactivation of basement faults and fracture systems in response to intracratonic stresses created by the continuous interaction of tectonic plates. Determining which of the models best explains regional hydrothermal fluid flow in the Michigan Basin is difficult for several reasons; (1) surface temperatures and maximum burial temperatures at the time of mineral precipitation in the Michigan Basin during the Ordovician are unknown; (2) the timing of mineral precipitation in relation to tectonic pulses is undetermined; (3) there is as yet no known deep-seated heat sources in the Michigan Basin for convection to occur; and (4) it is unknown whether advection is a major process in the Michigan Basin. A collaborative multi-disciplinary research project covering geology, geophysics and hydrogeology would provide much more integrated data than is currently available from stable isotopes, fluid inclusions and organic matter.

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.

The arid interior of South Africa lacks long, continuous and well-dated climate and environmental proxy records that can be compared with cultural sequences and with broader global climate records. This thesis develops the first substantial terrestrial environmental sequence for the interior of southern Africa at the site of Wonderwerk Cave, spanning two million years of prehistory. Changes in vegetation and humidity over time were investigated by means of carbon and oxygen stable isotope analysis on fossil herbivore enamel and ostrich eggshell, creating two independent proxy datasets. The Holocene record was used as a baseline for comparing the Pleistocene sequence, but required chronological tightening. Therefore, nine new radiocarbon dates were obtained, and calibrated and modelled with existing dates to provide a firmer chronology. The ostrich eggshell isotope record suggests arid but variable conditions, with distinct phases of increased humidity in the Early Pleistocene and mid-Holocene. Enamel stable isotope results show clear differences in local resource availability between the Early and Mid-Pleistocene, and then between the Pleistocene and Holocene, with an overall trend of increasing aridity. In particular, the onset of dietary specialisation in grazers at 0.8Ma is linked to expanding C4 grasslands. Aridity was not the driver behind the increase in C4 grasses, but changing pCO2 levels at the Mid Pleistocene transition were identified as a possible key factor. The presence of C3 and C4 grasses in the Early Pleistocene, when compared to the domination of C4 grasses today, was fostered by reduced rainfall seasonality. Regional independent developments have to be considered, as other regions in South and East Africa show C4 dominated diets in herbivores at earlier times than at Wonderwerk Cave. In the Holocene, higher temporal resolution indicates phases of environmental change coinciding with changes in the cultural record.