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Th. univ.--Rennes 1, 1996. / Bibliogr. p. 239-248. Résumé.

Arsenic contamination of circum-Himalayan groundwater is leading to one of the greatest humanitarian disasters of modern times, poisoning at least 70 million people who are mostly poor and rural. The groundwater is hosted in Holocene aquifers consisting of Himalayan sediments deposited by the great Asian rivers in deltaic environments. Arsenic is released when organic material (OM) reacts with the iron-oxide minerals co-deposited in the sediments onto which arsenic is adsorbed. The source of OM is one of the most important questions facing researchers and policy makers. There are generally accepted to be three potential sources of OM: 1) sedimentary bound OM (SOM) co-deposited with sediments; 2) thermally mature petroleum upwelled from reservoirs below the aquifers; 3) dissolved organic carbon (DOC) some of which might be drawn in to the aquifer through modern pumping and irrigation. In this thesis the nature of organic material in the aquifer is researched and the processes and timescales which lead to arsenic release are studied. Here evidence for a new conceptual model of arsenic release is presented. Isotopic tracing combined with a new geochemical model and organic geochemical techniques, shows that OM driving arsenic release pre-dates agriculture in the region and was from natural grasslands in the early Holocene. The geochemical model utilises strontium isotopes to correct the radiocarbon age of dissolved inorganic carbon (DIC) to find only the age and isotopic signature of DIC from oxidation of organic material. This shows that DIC from oxidation of OM was from the early Holocene and had an isotopic signature consistent with the early Holocene SOM in this region. A study of the sediments in the region built upon a geomorphological history shows that the most oxidised SOM is from early Holocene sediments. Thus both techniques separately indicate that pre-agricultural organic material drove arsenic release. This conceptual model however reveals the "arsenic sand paradox", because whilst release is from early Holocene clays, today highest concentrations of arsenic are in younger sands. Explaining this paradox is the most important next step leading on from this research.

This thesis investigates the potential of the bivalve Arctica islandica (Linnaeus, 1767) from fjordic sites in NW Scotland for reconstructing past marine environmental /climatic variability. Using dendrochronological and sclerochronological techniques, six master chronologies were created which when compared show little common variability between the sites, indicating no common response to regional scale forcing. The chronologies were compared to local and regional scale SST and land based datasets, with no significant, time stable responses to climate found. It is clear the growth/climate response of A. islandica from these sites is complex, potentially due to the shallow nature of the sample sites, direct local drivers such as food availability and, potentially, anthropogenic activity in the region. Geochemical analyses of the shell material were undertaken to examine the timing and magnitude of the radiocarbon bomb-peak and the stable carbon isotope signature of the oceanic Suess Effect. The timing of the radiocarbon bomb-peak in Loch Etive does not appear to match previously published results from other marine locations and are a potentially serious challenge to the assumption that A. islandica GI are always annual features. Results comparing δ¹³C values and the age of the specimen when these values are incorporated into the shell material strongly indicate an ontogenetic control over δ¹³C, meaning the Suess Effect could not be effectively investigated. To take these ontogenetic influences into account it is suggested that any data from the juvenile period of shell life is not used. Analysis of shell biometrics and morphology indicate significant relationships between shell age and height and age and weight, however the errors for these are large (±78 years and ±80 years respectively). These results indicate that despite large errors shell height, as a predictor of age, has the potential to be used for in situ population studies.

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My study was designed to identify the relationships between climate variables, such as precipitation and temperature, and δ 18 O values of tree ring &alpha-cellulose extracted from exactly dated tree rings of Pterocarpus angolensis growing in the arid to semiarid Mzola region of western Zimbabwe. This species is known to be sensitive to seasonal variation in rainfall. In this region, the wet season occurs during the austral summer from mid November to early April followed by a dry winter season from around June through October. Overall, the total annual rainfall exhibits a high degree of spatial and temporal variation with a mean of less than 600 mm per year. I applied the Modified Brendel technique to isolate &alpha-cellulose from raw wood samples extracted from two P. angolensis trees and measured the α-cellulose δ 18 O values using continuous flow isotope ratio mass spectrometry. I developed a 30-year (1955-1984) &alpha-cellulose δ 18 O chronology and correlated it with tree-ring width, meteoric water δ 18 O values, monthly and seasonal precipitation totals, and mean seasonal temperature. The δ 18 O values of meteoric water for this region were obtained from the Global Network of Isotopes in Precipitation (GNIP) and correlated with the δ 18 O values of tree ring &alpha-cellulose. The strongest correlations were observed between &alpha-cellulose δ 18 O values and February total precipitation (r = -0.49, p = 0.006) and to a lesser degree total wet season (NDJFMA) precipitation, In particular, unusually rainy wet seasons were significantly correlated (r = -0.79, P = 0.007) with &alpha-cellulose δ 18 O. This relationship is consistent with 18 O-depleted values measured in summer precipitation during periods of high rainfall, which is most likely the result of the isotopic amount effect reported in tropical regions. I also identified a positive correlation (r = 0.49, p = 0.03) between &alpha-cellulose δ 18 O and the δ 18 O values of meteoric water, and investigated the possibility of an isotopic temperature effect for δ 18 O in meteoric water, which also may be reflected in the δ 18 O values in tree ring &alpha-cellulose. The strongest correlation with mean temperature was observed during the wet summer season (r = 0.56, p = 0.01). My results suggest that the δ 18 O values of P. angolensis tree rings can be used as natural indicators of paleoclimate in southern Africa.

The Summitville high-sulfidation gold deposit is hosted by a volcanic dome consisting of the South Mountain Quartz Latite that was erupted 23 Ma ago during formation of the Platoro Caldera complex in the San Juan volcanic field of south central Colorado. Alteration and mineralization developed during or shortly after dome emplacement as a result of metal-rich magmatic fluids and vapor emanating from a crystallizing intrusion at depth. Copper, arsenic, silver and gold are enriched in the deposit with two of the last paragenetic stages, the barite-base metal sulfide and goethite stages, containing the highest gold grades. Barite contains magmatic sulfur with a range of δ34S values (19.3 – 31.8 ‰) that reflects SO42– – H2S isotopic equilibration over a temperature range of 115 to 180 °C, which is consistent a calculated temperature of 147 °C based on the sulfur isotopic fractionation between intergrown barite and galena. Barite δ18O values (19.3 – 31.8 ‰) indicate the barite fluids contained a minor component of meteoric water. Barite growth zones with acicular crystals (wires) of emplectite (CuBiS2), a mineral not previously reported from Summitville, contained primary fluid inclusions that yielded a wide range of vapor to liquid homogenization temperatures as a result of stretching but consistent freezing point depressions that infer an average salinity of 5.1 wt. % NaCl equivalent. These data indicate that the barite fluids were modestly enriched in magmatic sulfur and metals (Cu, As, Bi, Pb, Zn, Au, Ag) and that barite precipitation was likely triggered by cooling during mixing with meteoric waters. The goethite stage developed during weathering of the deposit that likely occurred during uplift and exposure around 9 to 7.7 Ma ago based on 40Ar/39Ar dates on jarosite. The assemblage goethite + hematite ± jarosite ± scorodite ± gold filled open spaces and coated barite of the barite-base metal sulfide stage. Inclusions of barite and bladed alunite in the iron oxide/hydroxide (FeOx) matrix have the texture, composition and isotopic values of their earlier formed counterparts in the deposit and therefore represent residual material that survived the weathering event. Three 40Ar/39Ar dates on the bladed alunite ranged from 23.15 to 22.88 Ma, confirming their origin as magmatic hydrothermal alteration alunite. Layers of compositionally zoned, small rhombohedral crystals of alunite were also discovered in the FeOx matrix. Although these could not be successfully dated, they had a distinct texture, chemistry and isotopic composition (δ34S = 0.8 ‰ δ18O = 4.7 ‰) that indicated they formed during the weathering event. The acidic, oxidizing supergene fluids remobilized and broadly enriched the top of the deposit in Cu and Ag and locally in native gold (5 wt. % Ag).

Ostracods were obtained from two cores in the southern North Sea area: the Sand Hole and Swarte Bank Formations of Tappin (1991) in BGS borehole 81/52A, cored from the Inner Silver Pit, southern North Sea, and a core from Shoeburyness in Essex, borehole S 1. The faunal assemblages in 131-181/52A were dominated by Sarsicytheridea punctillata, Elo/sonella concinna and Acanthocvthereis clunelmnensis. The assemblages recovered reflect a transition from glacio-marine conditions in the Swarte Bank Formation up into a cold-temperate marine environment in the Sand Hole Formation with deteriorating temperatures indicated at the top of the interval studied. In BHSI a freshwater to brackish transition occurred in the core, the freshwater section being dominated by Darwinula slevensoni and llyocypris spp., and the brackish section by Cyprideis torosa and C ytheromor pha fiiscata. The palaeoecology of the ostracod assemblages recovered is compared to other palaeoecological data from the same sections in each core and to ostracod data from other Hoxnian/l lolsteinian sites in north western Europe. These data are also discussed in the light of evidence indicating that there was a barrier across the southern North Sea when the sediments examined were deposited. Sarsicytheridea spp. and (yprideis terosa were used for trace element (Mg: Ca, Sr: Ca) and stable isotope (cS'"O, ö'3C) analyses. A calibration equation for the calculation of temperature from Mg: Ca ratio was successfully established from analysis of modern Sarsicytheridea. Modern Sr: Ca data could not be used to establish a calibration for salinity since there was too much scatter in the data. (' prideis torosa has been used for trace element and stable isotope work by other authors who have published relationships between ('yprideis and the water chemistry. Ostracods were also analysed down core to examine the changing ratios of Mg and Sr as a proxy for temperature and salinity changes in the I-loxnian of the southern North Sea. In BH81/52A, Mg: Ca data indicated a deterioration in temperature from 36.20 m to the top of the section studied of 9°C. Oxygen stable isotopic analyses from the same species, measured through the same core intervals, did not exhibit a trend, but their values were indicative of normal marine salinities. Carbon stable isotope analyses, performed at the same time as the oxygen analyses, indicate that there may have been high productivity in the region of deposition of the Sand Hole Formation, implying deposition in a region of freshwater influence. However, C/N analyses indicated that the sediments in the Inner Silver Pit were deposited under fully marine conditions. In III ISI, both the Mg: Ca and Sr: Ca data suggested that salinity had increased upcore. Ilowever, there was a lot of scatter in the data, indicating that the estuarine environment, under which the palaeoecology suggests the sediments were deposited, was a highly fluctuating one. These data compare favourably with previously published records. Published partition coefficients were used to compare the trace element data obtained to mean river and seawater values.

Over the course of my PhD, I developed the analytical capability to measure calcium isotopes at the University of Cambridge and analyzed calcium isotopes in a range of fluids and minerals in modern and past environments. After discussing my methodological development, I report my work in the glacial precursor to the Dead Sea. Here, the calcium isotope composition of aragonite varies synchronously with lake level fluctuations over the last 70,000 years. My numerically reconstructed lake calcium budget led me to conclude that 20,000 years ago, the Dead Sea was wetter than modern conditions, rather than colder and drier, as had previously been proposed. The primary focus of my PhD research was understanding the sedimentary sink for carbon. The formation of authigenic carbonate in marine sediments is caused by the microbial degradation of organic matter. I used pore fluid measurements and a numerical model to identify zones of authigenic carbonate precipitation. This knowledge was then combined with an understanding of the microbial processes that occur beneath the seafloor to determine the link between microbial activity and authigenic carbonate formation. Two processes, sulfate reduction and the anaerobic oxidation of methane were determined to be the main drivers of authigenic carbonate precipitation. In order to assess the importance of the carbon isotope signal imparted by each of the two identified processes, I created Artificial Neural Networks to predict the areal extent of authigenic carbonate precipitation and the dominant microbial process driving the precipitation. My ANNs identified that 37% of the modern seafloor is precipitating authigenic carbonate, which leads to a flux of 1.2*10^12 moles of carbon per year, of which 88% is due to the anaerobic oxidation of methane, and 12% is due to sulfate reduction. This represents 2-3% of the modern global carbon deposition, however I was able to show that this would be significantly higher in the geological past when ocean conditions were vastly different to how they are today. Finally, I conclude by proposing that some variations in the global carbon cycle in the past can be explored by linking marine calcium concentrations to authigenic carbonate formation and the flux of alkalinity from the seafloor.

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