Stable oxygen isotope ratios in zircons from oceanic crust

Lower ocean crust is primarily gabbroic, although 1-2% felsic igneous rocks that are referred to collectively as plagiogranites occur locally. Recent experimental evidence suggests that plagiogranite magmas can form by hydrous partial melting of gabbro triggered by seawater-derived fluids, and thus they may indicate early, high-temperature hydrothermal fluid circulation. To explore seawater-rock interaction prior to and during the genesis of plagiogranite and other late-stage magmas, oxygen-isotope ratios preserved in igneous zircon have been measured by ion microprobe. A total of 197 zircons from 43 plagiogranite, evolved gabbro, and hydrothermally altered fault rock samples have been analyzed. Samples originate primarily from drill core acquired during Ocean Drilling Program and Integrated Ocean Drilling Program operations near the Mid-Atlantic and Southwest Indian Ridges. With the exception of rare, distinctively luminescent rims, all zircons from ocean crust record remarkably uniform d18O with an average value of 5.2 ± 0.5 per mil (2SD). The average d18O(Zrc) would be in magmatic equilibrium with unaltered MORB [d18O(WR) ~5.6-5.7 per mil], and is consistent with the previously determined value for equilibrium with the mantle. The narrow range of measured d18O values is predicted for zircon crystallization from variable parent melt compositions and temperatures in a closed system, and provides no indication of any interactions between altered rocks or seawater and the evolved parent melts. If plagiogranite forms by hydrous partial melting, the uniform mantle-like d18O(Zrc) requires melting and zircon crystallization prior to significant amounts of water-rock interactions that alter the protolith d18O. Zircons from ocean crust have been proposed as a tectonic analog for >3.9 Ga detrital zircons from the earliest (Hadean) Earth by multiple workers. However, zircons from ocean crust are readily distinguished geochemically from zircons formed in continental crustal environments. Many of the >3.9 Ga zircons have mildly elevated d18O (6.0-7.5 per mil), but such values have not been identified in any zircons from the large sample suite examined here. The difference in d18O, in combination with newly acquired lithium concentrations and published trace element data, clearly shows that the >3.9 Ga detrital zircons did not originate by processes analogous to those in modern mid-ocean ridge settings.

Stable oxygen isotope. Mg/Ca and Temperature record of Caribbean and Pacific sediments

The final phase of the closure of the Panamanian Gateway and the intensification of Northern Hemisphere Glaciation (NHG) both occurred during the Late Pliocene. Glacial-interglacial (G-IG) variations in sea level might, therefore, have had a significant impact on the remaining connections between the East Pacific and the Caribbean. Here, we present combined foraminiferal Mg/Ca and d18O measurements from Ocean Drilling Program (ODP) Site 1241 from the East Pacific and ODP Site 999 from the Caribbean. The studied time interval covers the first three major G-IG Marine Isotope Stages (MIS 95-100, ~2.5 Ma) after the intensification of NHG. Analyses were performed on the planktonic foraminifera Neogloboquadrina dutertrei and Globigerinoides sacculifer, representing water mass properties in the thermocline and the mixed-layer, respectively. Changes in sea water temperature, relative salinity, and water column stratification strongly suggest that the Panamanian Gateway temporarily closed during glacial MIS 98 and 100, as a result of changes in ice volume equivalent to a drop in sea level of 60-90 m. Reconstructed sea surface temperatures (SST) from G. sacculifer show a glacial decrease of 2.5°C at Site 1241, but increases of up to 3°C at Site 999 during glacial MIS 98 and 100 suggesting that the Panamanian Gateway closed during these glacial periods. The Mg/Ca-temperatures of N. dutertrei remain relatively stable in the East Pacific, but do show a 3°C warming in the Caribbean at the onset of these glacial periods suggesting that the closing of the gateway also changed the water column stratification. We infer that the glacial closure of the gateway allowed the Western Atlantic Warm Pool to extend into the southern Caribbean, increasing SST (G. sacculifer) and deepening the thermocline (N. dutertrei). Additionally, ice volume appears to have become large enough during MIS 100 to survive the relatively short lasting interglacial MIS 99 so that the gateway remained closed. Towards the end of MIS 98, during MIS 97 and into MIS 96 temperatures on both sides are mostly similar suggesting water masses exchanged again. Additionally, Caribbean variations in SST and d18Owater follow a precession-like cyclicity rather than the obliquity-controlled variations characteristic of the East-Pacific and many other tropical areas, suggesting that regional atmospheric processes related to the trade winds and the Intertropical Convergence Zone (ITCZ) had a dominant impact in the Caribbean.

Biogeochemical processes in anoxic sediment from Lake Plußsee, Germany

In anoxic environments, volatile methylated sulfides like methanethiol (MT) and dimethyl sulfide (DMS) link the pools of inorganic and organic carbon with the sulfur cycle. However, direct formation of methylated sulfides from reduction of dissolved inorganic carbon has previously not been demonstrated. When studying the effect of temperature on hydrogenotrophic microbial activity, we observed formation of DMS in anoxic sediment of Lake Plußsee at 55 °C. Subsequent experiments strongly suggested that the formation of DMS involves fixation of bicarbonate via a reductive pathway in analogy to methanogenesis and engages methylation of MT. DMS formation was enhanced by addition of bicarbonate and further increased when both bicarbonate and H2 were supplemented. Inhibition of DMS formation by 2-bromoethanesulfonate points to the involvement of methanogens. Compared to the accumulation of DMS, MT showed the opposite trend but there was no apparent 1:1 stoichiometric ratio between both compounds. Both DMS and MT had negative d13C values of -62 per mil and -55 per mil, respectively. Labeling with NaH**13CO3 showed more rapid incorporation of bicarbonate into DMS than into MT. The stable carbon isotopic evidence implies that bicarbonate was fixed via a reductive pathway of methanogenesis, and the generated methyl coenzyme M became the methyl donor for MT methylation. Neither DMS nor MT accumulation were stimulated by addition of the methyl-group donors methanol and syringic acid or by the methyl-group acceptor hydrogen sulphide. The source of MT was further investigated in a H2**35S labeling experiment, which demonstrated a microbially-mediated process of hydrogen sulfide methylation to MT that accounted for only <10% of the accumulation rates of DMS. Therefore, the major source of the 13C-depleted MT was neither bicarbonate nor methoxylated aromatic compounds. Other possibilities for isotopically depleted MT, such as other organic precursors like methionine, are discussed. This DMS-forming pathway may be relevant for anoxic environments such as hydrothermally influenced sediments and fluids and sulfate-methane transition zones in marine sediments.

Molar gas ratios and stable oxygen and nitrogen isotopes of air entrapped in ice, North America

The molar ratios of atmospheric gases change during dissolution in water due to differences in their relative solubilities. We exploited this characteristic to develop a tool to clarify the origin of ice formations in permafrost regions. Extracted from ice, molar gas ratios can distinguish buried glacier ice from intrasedimental ground ice formed by freezing groundwaters. An extraction line was built to isolate gases from ice by melting and trapping with liquid He, followed by analysis of N2, O2, Ar, 18O-O2 and 15N-N2, by continuous flow mass spectrometry. The method was tested using glacier ice, aufeis ice (river icing) and intrasedimental ground ice from sites in the Canadian Arctic. O2/Ar and N2/Ar ratios clearly distinguish between atmospheric gas in glacial ice and gases from intrasedimental ground ice, which are exsolved from freezing water. 615NN2 and 618OO2 in glacier ice, aufeis ice and intrasedimental ground ice do not show clear distinguishing trends as they are affected by various physical processes during formation such as gravitational settling, excess air addition, mixing with snow pack, and respiration.

Hydrogeological investigations in the upper Ouémé catchment in Benin, West Africa

The scope of this PhD thesis was the hydrogeological conceptualisation of the Upper Ouémé river catchment in Benin. The study area exceeds 14,500 km**2 and is underlain by a crystalline basement. At this setting the typical sequence of aquifers - a regolith aquifer at the top and a fractured bedrock aquifer at the bottom - is encountered, which is found in basement areas all over Africa and elsewhere in the world. The chosen regional approach revealed important information about the hydrochemistry and hydrogeology of this catchment. Based on the regional conceptual model a numerical groundwater flow model was designed. The numerical model was used to estimate the impact of climate change on the regional groundwater resources. This study was realised within the framework of the German interdisciplinary research project IMPETUS (English translation: "Integrated approach to the efficient management of scarce water resources in West Africa"), which is jointly managed by the German universities of Bonn and Cologne. Since the year 2000 the Upper Ouémé catchment was the principal target for investigations into the relevant processes of the regional water cycle. A first study from 2000 to 2003 (Fass, 2004, http://nbn-resolving.de/urn:nbn:de:hbz:5n-03849) focused on the hydrogeology of a small local catchment (~30 km**2). In the course of this thesis five field campaigns were underdone from the year 2004 to 2006. In the beginning of 2004 a groundwater monitoring net was installed based on 12 automatic data loggers. Manual piezometric measurements and the sampling of groundwater and surface water were realised for each campaign throughout the whole study area. Water samples were analysed for major ions, for a choice of heavy metals and for their composition by deuterium, oxygen-18 and tritium. The numerical model was performed with FEFLOW. The hydraulic and hydrochemical characteristics were described for the regolith aquifer and the bedrock aquifer. The regolith aquifer plays the role of the groundwater stock with low conductivity while the fractures of the bedrock may conduct water relatively fast towards extraction points. Flow in fractures of the bedrock depends on the connectivity of the fracture network which might be of local to subregional importance. Stable isotopes in combination with hydrochemistry proved that recharge occurs on catchment scale and exclusively by precipitation. Influx of groundwater from distant areas along dominant structures like the Kandi fault or from the Atacora mountain chain is excluded. The analysis of tritium in groundwater from different depths revealed the interesting fact of the strongly rising groundwater ages. Bedrock groundwater may possibly be much older than 50 years. Equilibrium phases of the silicate weathering products kaolinite and montmorillonite showed that the deeper part of the regolith aquifer and the bedrock aquifer feature either stagnant or less mobile groundwater while the shallow aquifer level is influenced by seasonal groundwater table fluctuations. The hydrochemical data characterised this zone by the progressive change of the hydrochemical facies of recently infiltrated rainwater on its flow path into deeper parts of the aquifers. Surprisingly it was found out that seasonal influences on groundwater hydrochemistry are minor, mainly because they affect only the groundwater levels close to the surface. The transfer of the hydrogeological features of the Upper Ouémé catchment into a regional numerical model demanded a strong simplification. Groundwater tables are a reprint of the general surface morphology. Pumping or other types of groundwater extraction would have only very local impact on the available groundwater resources. It was possible to integrate IMPETUS scenario data into the groundwater model. As a result it was shown that the impact of climate change on the groundwater resources until the year 2025 under the given conditions will be negligible due to the little share of precipitation needed for recharge and the low water needs for domestic use. Reason for concern is the groundwater quality on water points in the vicinity of settlements because of contamination by human activities as shown for the village of Dogué. Nitrate concentrations achieved in many places already alerting levels. Health risks from fluoride or heavy metals were excluded for the Upper Ouémé area.

Chlorine stable isotopic composition of basement fluids from ODP Leg 168 sites

This paper presents chlorine stable isotope compositions (delta37Cl) of sediment pore waters collected by squeezing sediment cores from the sediment-basement interface along an East-West transect through the eastern flank of the Juan de Fuca Ridge (ODP Leg 168). These "near basement fluids" (NBF) are generally thought to be representative of low-temperature fluids circulating in the off-axis basaltic crust. The delta37Cl value of the fluid directly sampled from a flow at the base of Site 1026 (WSTP1026) is also reported. NBF display delta37Cl values between -2.09? and -0.12? relative to the Standard Mean Ocean Chloride (SMOC defined as 0?) and small variations in chlorinity (~4%). These data contrast with the homogeneity of delta37Cl values associated with highly variable chlorinities observed in high-temperature on-axis fluids [Bonifacie et al., 2005, doi:10.1016/j.chemgeo.2005.06.008]. The NBF delta37Cl values show a general decreasing trend with distance from the ridge-axis except for two fluids. When plotted against delta18O values, the delta37Cl of the NBF show two different trends. This paper discusses the possible contributions on NBF delta37Cl values of fluid-mixing, water-rock interactions and transport processes (diffusion, ion membrane filtration) that can occur in the igneous basement. However, as none of these processes can fully explain the observed delta37Cl variations, the potential effect of the sediment cover is also investigated. At site 1026, the interstitial pore fluid displays a delta37Cl signature significantly lower than that of the fluid discharge sample (-1.90? and -0.28?, respectively). This difference, demonstrated here cannot be an artifact of the sampling method, rather indicates the influence of the sediment cover on NBF delta37Cl values. The potential contributions of physical processes associated with transport/compaction (e.g., diffusion, ion membrane filtration, adsorption, ion exchange) on NBF delta37Cl values are qualitatively discussed here but require additional studies for further insights. However, this study indicates that "near basement fluids" (NBF) are not, at least for Cl isotopic compositions, necessarily as representative of fluids circulating in the basaltic crust as initially thought. These results add new constraints on Cl geodynamics and show that Cl-isotopes fractionate during low-temperature circulation of fluids in off-axis and off-margin flow contexts, but not to the extent observed for active margins. Fluids circulating at low-temperature in the magmatic and/or the sedimentary part of the oceanic crust might have played a major role on the delta37Cl evolution of seawater over geologic time.

Sedimentology and stable oxygen isotope ratios of foraminifera from cores of the Porcupine Seabight, Northeast Atlantic

Large carbonate mound structures have been discovered in the northern Porcupine Seabight (Northeast Atlantic) at depths between 600 and 1000 m. These mounds are associated with the growth of deep-sea corals Lophelia pertusa and Madrepra oculata. In this study, three sediment cores have been analysed. They are from locations close to Propeller Mound, a 150 m high ridge-like feature covered with a cold-water coral ecosystem at its upper flanks. The investigations are concentrated on grain-size analyses, carbon measurements and on the visual description of the cores and computer tomographic images, to evaluate sediment content and structure. The cores portray the depositional history of the past ~31 kyr BP, mainly controlled by sea-level fluctuations and the climate regime with the advance and retreat of the Irish Ice Sheet onto the Irish Mainland Shelf. A first advance of glaciers is indicated by a turbiditic release slightly older than 31 kyr BP, coherent with Heinrich event 3 deposition. During Late Marine Isotope Stage 3 (MIS 3) and MIS 2 shelf erosion prevailed with abundant gravity flows and turbidity currents. A change from glaciomarine to hemipelagic contourite sedimentation during the onset of the Holocene indicates the establishment of the strong, present-day hydrodynamic regime at intermediate depths. The general decrease in accumulation of sediments with decreasing distance towards Propeller Mound suggests that currents (turbidity currents, gravity flows, bottom currents) had a generally stronger impact on the sediment accumulation at the mound base for the past ~31 kyr BP, respectively.

Stable oxygen isotope ratios and grain size analyses of sediment cores from the Propeller Mound, Northeast Atlantic

The first detailed stratigraphic record from a deep-water carbonate mound in the Northeast Atlantic based on absolute datings (U/Th and AMS 14C) and stable oxygen isotope records reveals that its top sediment sequences are condensed by numerous hiatuses. According to stable isotope data, mainly sediments with an intermediate signal are preserved on the mound, while almost all fully glacial and interglacial sediments have either not been deposited or have been eroded later. The resulting hiatuses reduce the Late Pleistocene sediment accumulation at Propeller Mound to amounts smaller than the background sedimentation. The hiatuses most likely result due to the sweeping of the mound in turn with the re-establishment of vigour interglacial circulation patterns after sluggish current regimes during glacials. Thus, within the discussion if internal, fluid-driven or external environmentally driven processes control the evolution of such carbonate mounds, our findings for Propeller Mound clearly point to environmental forcing as the dominant mechanism shaping deep-water carbonate mounds in the NE Atlantic during the Late Pleistocene and Holocene.

Stable oxygen and carbon isotope ratios of Pliocene benthic foraminifera in the Atlantic Ocean

Large changes in benthic foraminiferal delta180 and delta13C occurred during the Pliocene (between 3.0 and 2.0 Ma) at Hole 665A. Oxygen isotopic compositions increased to maximum values at 2.4 Ma, correlating with an 18O enrichment observed at Hole 552A and other locations (Shackleton et al., 1984). As at Hole 606 (Keigwin, 1986), however, maximum delta180 values at 2.4 Ma were not as great as at Hole 552A, and enrichments in delta180 also occurred before 2.4 Ma. We believe that the section representing sediments from 2.5 to 2.7 or 2.8 Ma is missing at Hole 552A because of incomplete core recovery. Consequently, the older delta180 increases are not found at Hole 552A. Benthic foraminiferal delta13C values are much lower at Hole 665A than at Hole 552A, approaching the low values observed in the Pliocene Pacific Ocean. This geographic distribution of delta13C suggests that, like late Quaternary glaciations, the equatorial Atlantic Ocean was dominated during the Pliocene by deep water that originated in the Southern Ocean and had chemical characteristics very similar to the Pacific Ocean. Reduced O2 values were probably associated with low delta13C values and contributed to increased preservation of organic carbon during enriched 180 intervals of the Pliocene equatorial Atlantic.

Stable isotope analysis of benthic foraminifera and sedimentology on ODP Site 162-984

Sediments recovered at ODP Site 984 on the Reykjanes Ridge provided multicentennial-scale records (SST, planktic and benthic delta18O, IRD and magnetic susceptibility) of Late Pliocene climate change over the onset of Northern Hemisphere glaciation (NHG), 2.95-2.82 Ma. Short-term climate variations prior and after the onset of continent-wide glaciation were compared to test the hypothesis, whether Dansgaard-Oeschger (DO) cycles may have been triggered by continental ice breakouts. By means of spectral analyses for two selected interglacial stages prior to and after NHG (G15 and G1), we found that climate variability resembled that of the Holocene and the mid-Pliocene warm period. In contrast, DO-like periodicities near 1470, 2900, and 4400 yr indeed only occurred in glacial stages after the onset of NHG (G14, G6, and 104), but hardly in stage G20 prior to the onset. These results suggest a causal link between DO cycles and the Late Pliocene onset of major NHG and ice breakouts in the North Atlantic. This data set provides all primary data and spectral analysis related to this scientific work.

(Table 1) n-alkane distribution, and stable carbon and deuterium isotope ratios of DSDP Hole 10-94

Hydrology, source region, and timing of precipitation are important controls on the climate of the Great Plains of North America and the composition of terrestrial ecosystems. Moisture delivered to the Great Plains varies seasonally and predominately derives from the Gulf of Mexico/Atlantic Ocean with minor contributions from the Pacific Ocean and Arctic region. For this work, we evaluate long-term relationships for the past ~ 35 million years between North American hydrology, climate, and floral change, using isotopic records and average carbon chain lengths of higher plant n-alkanes from Gulf of Mexico sediments (DSDP Site 94). We find that carbon isotope values (d13C) of n-alkanes, corrected for variations in the d13C value of atmospheric CO2, provide minor evidence for contributions of C4 plants prior to the Middle Miocene. A sharp spike in C4 input is identified during the Middle Miocene Climatic Optimum, and the influence of C4 plants steadily increased during the Late Miocene into the Pleistocene - consistent with other North American records. Chain-length distributions of n-alkanes, indicative of the composition of higher plant communities, remained remarkably constant from 33 to 4 Ma. However, a trend toward longer chain lengths occurred during the past 4 million years, concurrent with an increase in d13C values, indicating increased C4 plant influence and potentially aridity. The hydrogen isotope values (dD) of n-alkanes are relatively invariant between 33 and 9 Ma, and then become substantially more negative (75 per mil) from 9 to 2 Ma. Changes in the plant community and temperature of precipitation can solely account for the observed variations in dD from 33 to 5 Ma, but cannot account for Plio-Pleistocene dD variations and imply substantial changes in the source region of precipitation and seasonality of moisture delivery. We posit that hydrological changes were linked to tectonic and oceanographic processes including the shoaling and closure of the Panamanian Seaway, amplification of North Atlantic Deep Water Production and an associated increase of meridional winds. The southerly movement of the Intertropical Convergence Zone near 4 Ma allowed for the development of a near-modern pressure/storm track system, driving increased aridity and changes in seasonality within the North American interior.

Interstitial-water chemistry and stable isotope record of Prydz Bay sediments

Leg 119 of the Ocean Drilling Program (ODP) provided the first opportunity to study the interstitial-water chemistry of the eastern Antarctic continental margin. Five sites were cored in a northwest-southeast transect of Prydz Bay that extended from the top of the continental slope to within 30 km of the coastline. Geological studies of the cores reveal a continental margin that has evolved through terrestrial, glacial, and glacial-marine environments. Chemical and stable isotopic analyses of the interstitial-waters were performed to determine the types of depositional environments and the diagenetic and hydrologic processes that are operating in this unusual marine environment. Highly compacted glacial sediments provide an effective barrier to the vertical diffusion of interstitial-water solutes. Meteoric water from the Antarctic continent appears to be flowing into Prydz Bay sediments through the sequence of terrestrial sediments that lie underneath the glacial sediments. The large amounts of erosion associated with glacial advances appear to have had the effect of limiting the amount of marine organic matter that is incorporated into the sediments on the continental shelf. Although all of the sites cored in Prydz Bay exhibit depletions in dissolved sulfate with increasing depth, the greatest bacterial activity is associated with a thin layer of diatom ooze that coats the seafloor of the inner bay. Results of alkalinity modeling, thermodynamic calculations, and strontium analyses indicate that (1) ocean bottom waters seaward of Site 740 are undersaturated with respect to both calcite and aragonite, (2) interstitial waters at each site become saturated or supersaturated with respect to calcite and aragonite with increasing depth, (3) precipitation of calcium carbonate reduces the alkalinity of the pore waters with increasing depth, and (4) recrystallization of aragonite to calcite accounts for 24% of the pore-water strontium. Weathering of unstable terrestrial debris and cation exchange between clay minerals and pore fluids are the most probable chemical processes affecting interstitial water cation gradients.

Stable isotope record of DSDP Hole 81-552A in the northeastern Atlantic Ocean

Oxygen and carbon isotope ratios in benthic foraminifers have been determined at 10 cm intervals through the top 59 m of DSDP Hole 552A. This provides a glacial record of remarkable resolution for the late Pliocene and Pleistocene. The major glacial event which marked the onset of Pleistocene-like glacial-interglacial alternations was at about 2.4 m.y. ago. These very high-resolution data do not support the notion of significant Northern Hemisphere glaciation between 3.2 and 2.4 m.y. ago.

Sedimentology and stable isotope record of DSDP Hole 68-503B

Samples from the upper portion of a cyclic pelagic carbonate sediment sequence in Deep-Sea Drilling Project (DSDP) hole 503B (4.0°N, 95.6°W) are the first group to be analyzed for paleoceanographic and paleoclimatic proxy-indicators of ice volume, deep ocean and surface water circulation, and atmospheric circulation in order to resolve the complex origin of the cyclicity. Temporal resolution is taken from the delta18O time scale, most other parameters are calculated in terms of their mass flux to the seafloor. CaCO3 percent in the sediments fluctuates in the well-known Pacific pattern and is higher during glacial times. The fluxes of opal and organic carbon have patterns similar to each other and show a variability of a factor of 2.5 to 4. The longer organic carbon record shows flux maxima during both glacial and interglacial times. The accumulation patterns of both opal and organic carbon suggest that the variability in surface water productivity and/or seafloor preservation of those materials is not simply correlated to glacial or interglacial periods. Eolian dust fluxes are greater during interglacial periods by factors of 2 to 5, indicating that eolian source regions in central and northern South America were more arid during interglacial periods. The record of eolian grain size provides a semiquantitative estimation of the intensity of the transporting winds. The eolian data suggest more intense atmospheric circulation during interglacial periods, opposite to the anticipated results. We interpret this observation as recording the southerly shift of the intertropical convergence zone to the latitude of hole 503B during glaciations.