Helium and oxygen isotope ratios of ODP Sites 193-1188 and 193-1189

Fluid mixing processes and thermal regimes within the Snowcap and Roman Ruins vent sites of the PACMANUS hydrothermal system, Papua New Guinea, were investigated using 3He/4He ratios from fluid inclusions within pyrite and anhydrite and the d18O signature of anhydrite. Depressed 3He/4He ratios of 0.2-6.91RA appear to be caused by significant atmospheric diffusive exchange, whilst He-Ne diffusive fractionation precludes correction using 20Ne. 40Ar/36Ar ratios of 295-310 are elevated above seawater, indicating the majority of argon is seawater derived but with a magmatic component. d18O anhydrite ratios are 6.5 per mil to 11 per mil for Snowcap and 6.4 per mil to 11.9 per mil for Roman Ruins. Using oxygen isotope fractionation factors for the anhydrite-water system, the temperatures calculated assuming isotopic equilibrium at depth are up to 100 °C cooler than fluid inclusion trapping temperatures. It is likely that anhydrite is precipitated rapidly, preventing d18O equilibration. By comparing new d18O values for anhydrite with corresponding published 87Sr/86Sr ratios, seawater is inferred to penetrate deep into the Snowcap system with little conductive heating. A simple fluid mixing model has been constructed whereby the differing venting styles can be explained by a plumbing system at depth which favors delivery of end-member hydrothermal fluid to the high temperature sites.

Sedimentology, age models and stable isotope ratios of sediment cores from the equatorial Pacific

Based on detailed reconstructions of global distribution patterns, both paleoproductivity and the benthic d13C record of CO2, which is dissolved in the deep ocean, strongly differed between the Last Glacial Maximum and the Holocene. With the onset of Termination I about 15,000 years ago, the new (export) production of low- and mid-latitude upwelling cells started to decline by more than 2-4 Gt carbon/year. This reduction is regarded as a main factor leading to both the simultaneous rise in atmospheric CO2 as recorded in ice cores and, with a slight delay of more than 1000 years, to a large-scale gradual CO2 depletion of the deep ocean by about 650 Gt C. This estimate is based on an average increase in benthic d13C by 0.4-0.5 per mil. The decrease in new production also matches a clear 13C depletion of organic matter, possibly recording an end of extreme nutrient utilization in upwelling cells. As shown by Sarnthein et al., [1987], the productivity reversal appears to be triggered by a rapid reduction in the strength of meridional trades, which in turn was linked via a shrinking extent of sea ice to a massive increase in high-latitude insolation, i.e., to orbital forcing as primary cause.

Stable carbon and oxygen isotope ratios of benthic foraminifera from the East Atlantic Ocean

The glacial to interglacial delta13C records of the benthic foraminifera Cibicidoides wuellerstorfi and the Uvigerina peregrina group from deep-sea cores cannot be adjusted by a generally valid constant. The delta13C values of the U. peregrina group largely correlate with the accumulation rates of organic carbon, suggesting a local "habitat effect"; those of C. wuellerstorfi vary independently with respect to the carbon flux and record fluctuations in the delta13C of the ambient bottom water isotopic composition.

Stable carbon and oxygen isotope ratios of calcareous dinoflagellate cysts and planktic foraminifera from the Campanian/Maastrichtian section of ODP Hole 113-690C in the Weddell Sea (Table 1)

Delta18O and delta13C values for the calcareous dinoflagellate species Orthopithonella? globosa (Fütterer 1984) Lentin and Williams 1985 and Pirumella krasheninnikovii (Bolli 1974) Lentin and Williams 1993 from lates Campanian and earliest Maastrichtian of ODP Hole 690C (Weddell Sea, Antarctic Ocean) have been studied in order to evaluate the species' depth habitat in the water column and their applicability in paleoceanographic studies. The calcareous dinoflagellates show isotopic values comparable to probably shallow-dwelling planktic foraminifera from the same sample in delta18O, but have an offset of about -5 ? to -7? in delta13C. This suggests that calcareous dinoflagellate oxygen isotopes may provide information for paleoceanographic reconstructions of sea-surface water temperatures, whereas their extremely light carbon isotope values are probably due to photosynthetic processes.

Stable oxygen and carbon isotope ratios of the planktonic foraminifera Pulleniatina obliquiloculata and the benthic foraminifera Uvigerina excellens of ODP Site 117-723 in the Arabian Sea (Table 1)

Site 723 is located in a water depth of 808 m at the center of the oxygen minimum zone and the middle part of the main thermocline on the Oman Margin. Oxygen isotope curves of planktonic delta18OP and benthic delta18OB can be traced back continuously to Stage 23 with high resolution measurements. A tentative correlation to Stage 53 has been tried using oxygen isotope stratigraphy. The amplitudes of the fluctuations of the benthic delta18OB curve are small, compared with the planktonic delta18OP curve. The delays of benthic oxygen isotopes delta18OB related to the planktonic delta18OP appear in the transgressive stages. Carbon isotopes of benthic delta13CB and planktonic delta13CP generally show an inverse correlation with oxygen isotope values delta18OB and delta18OB and delta18OP, however, the changes of delta13C are more gradual than those of delta18O during transgressive stages in spite of the synchronized changes of delta13C with those of delta18O during regressive stages. The difference of oxygen isotope between benthic and planktonic foraminifers represents the degree of pushing up the thermocline by upwelling, and the difference of carbon isotope represents the relative amount of upwelling Sigma[CO2] to the biological uptake in the surface water. These isotopic differences can be used as indicators of upwelling and show strong upwelling in the interglacial and weak upwelling in the glacial stages. The organic carbon content is correlated with the isotopic upwelling indicators, and higher content is correlated with the isotopic upwelling indicators and higher content appears in the interglacial stages. The calculated rate of sedimentation based on oxygen isotope stratigraphy in glacial stages is significantly high, two to four times that of interglacial stages, and the absolute flux of fluvial sediments with variability of lithofacies increased in the glacial stage. The present glacial-interglacial cycle with the fluctuation of upwelling relating to the southwest monsoon can be traced back to Stage 8, 250 ka. From Stage 8 to 12, 250-450 ka, the upwelling indicator of oxygen isotope difference did not show such distinct cyclicity. For Stages 12-15, 450-600 ka, the upwelling can be estimated as strong as in interglacial stage of the present cycles, with slightly weak upwelling in the glacial stage. This upwelling and climate can be traced back to the late Pliocene. The strongest upwelling can be estimated in the Pliocene-Pleistocene time by the isotopic indicators and the high organic carbon content.

Carbon and oxygen isotope ratios of Selinde River, southeastern Siberian platform

Carbon isotopic data from the Selinde section in the southeastern part of the Siberian platform area are correlated with the reference isotopic profile from the Lower Cambrian stratotype sections of the Lena Aldan region, but also show additional d13C excursions unrecognized there. The chemostratigraphic correlation suggests that the geological and fossil record of the lower Pestrotsvet Formation in the Selinde section has a deeper history than the stratotype region. This conclusion is important for both constraining the age of the earliest Cambrian marine transgression on the Siberian platform and providing a clearer understanding of the pace and order of early Cambrian geochemical and biological events.

(Appendix) Carbon and nitrogen isotope ratios of ODP Site 160-964

Nitrogen isotopes of chlorins, degradation products of chlorophyll, reflect the isotopic composition of nutrient N utilized by marine phytoplankton communities. Here we show that in sediments of the eastern Mediterranean Pleistocene and Holocene, values of d15N for chlorins and total nitrogen vary in concert, with a consistent offset of ~5 per mil reflecting the fractionation imparted during chlorophyll biosynthesis. Samples from the Integrated Ocean Drilling Program Sites 964 and 969 were analyzed at a sampling resolution of ~4-10 cm, clustered around sapropel events 2, 3, 4 and 5 (~100-170 ka). In low organic content sediments, chlorin values of ~0 per mil coincident with total nitrogen values of ~+ 5 per mil indicate that the latter reflects the original biomass and is not a consequence of diagenetic isotope enrichment. In sapropel horizons, the chlorin and total nitrogen values are 5 per mil more negative (~-5 per mil and ~ 0 per mil, respectively), resembling previously-reported, modern-day water-column particulates (~0 per mil). We suggest that nutrient conditions in the Eastern Mediterranean correspond to three scenarios and that the similarity between sapropel and modern-day bulk d15N is coincidental. Organic-poor marl sediments formed under oligotrophic conditions where surface productivity resulted from upwelling of Atlantic-sourced nitrate. Sapropels were characterized by enhanced diazotrophy that was likely fueled by increased riverine P fluxes to surface waters. Present-day conditions are dominated by anthropogenic N sources. These scenarios agree with a model of sapropel formation in which stratification caused by increased fresh-water inputs led to N fixation due to P:N nutrient imbalance. Enhanced production combined with stratification promoted and maintained anoxic deep waters, consequently increasing organic matter preservation. Such a model may be relevant to interpreting other episodes of intense organic matter deposition in past oceans.

Pb and Ba concentrations and Pb isotope ratios in EPICA Dome C ice 2-217 ky BP

A record of Pb isotopic compositions and Pb and Ba concentrations are presented for the EPICA Dome C ice core covering the past 220 ky, indicating the characteristics of dust and volcanic Pb deposition in central East Antarctica. Lead isotopic compositions are also reported in a suite of soil and loess samples from the Southern Hemisphere (Australia, Southern Africa, Southern South America, New Zealand, Antarctica) in order to evaluate the provenance of dust present in Antarctic ice. Lead isotopic compositions in Dome C ice support the contention that Southern South America was an important source of dust in Antarctica during the last two glacial maxima, and furthermore suggest occasional dust contributions from local Antarctic sources. The isotopic signature of Pb in Antarctic ice is altered by the presence of volcanic Pb, inhibiting the evaluation of glacial-interglacial changes in dust sources and the evaluation of Australia as a source of dust to Antarctica. Consequently, an accurate evaluation of the predominant source(s) of Antarctic dust can only be obtained from glacial maxima, when dust-Pb concentrations were greatest. These data confirm that volcanic Pb is present throughout Antarctica and is emitted in a physical phase that is free from Ba, while dust Pb is transported within a matrix containing Ba and other crustal elements.

Planktic foraminiferal distribution and stable isotope ratios of sediment core MSM05/5_712-1 from the Arctic Ocean

The Arctic is responding more rapidly to global warming than most other areas on our planet. Northward flowing Atlantic Water is the major means of heat advection towards the Arctic and strongly affects the sea ice distribution. Records of its natural variability are critical for the understanding of feedback mechanisms and the future of the Arctic climate system, but continuous historical records reach back only ~150 years. Here, we present a multidecadal scale record of ocean temperature variations during the last 2000 years, derived from marine sediments off Western Svalbard (79°N). We find that early-21st-century temperatures of Atlantic Water entering the Arctic Ocean are unprecedented over the past 2000 years and are presumably linked to the Arctic Amplification of global warming.

Middle Miocene evolution and stable isotope ratios of Globorotalia (Fohsella) in the western equatorial Pacific

Evolution of the planktic foraminiferal lineage Globorotalia (Fohsella) occurred during the Miocene between 23.7 and 11.8 Ma and forms the basis for stratigraphic subdivision of the early middle Miocene (Zones N 10 through N 12). Important morphologic changes within the G. (Fohsella) lineage included a marked increase in test size, a transition from a rounded to an acute periphery, and the development of a keel in later forms. We found that the most rapid changes in morphology of G. (Fohsella) occurred between 13 and 12.7 Ma and coincided with an abrupt increase in the delta18O ratios of shell calcite. Comparison of isotopic results of G. (Fohsella) with other planktic foraminifers indicate that delta18O values of the lineage diverge from surface-dwelling species and approach deep-dwelling species after 13.0 Ma, indicating a change in depth habitat from the surface mixed layer to intermediate depth near the thermocline. Isotopic and faunal evidence suggests that this change in depth stratification was associated with an expansion of the thermocline in the western equatorial Pacific. After adapting to a deeper water habitat at 13.0 Ma, the G. (Fohsella) lineage became extinct abruptly at 11.8 Ma during a period when isotopic and faunal evidence suggest a shoaling of the thermocline. Following the extinction of G. (Fohsella), the ecologic niche of the lineage was filled by the Globorotalia (Menardella) group, which began as a deep-water form and later evolved to an intermediate-water habitat. We suggest that the evolution of G. (Fohsella) and G. (Menardella) were tightly linked to changes in the structure of the thermocline in the western equatorial Pacific.

U, FE, AND LI ISOTOPE RATIOS IN THE MINERALIZED AND BARREN AREAS OF THE KOMBOLGIE BASIN

The Paleo- to Meso-Proterozoic Jabiluka unconformity related uranium mine is located within the Alligator River Uranium Field, found in the Northern Territories, Australia. The uranium ore is hosted in the late middle Paleoproterozoic Cahill Formation, which is unconformably overlain by a group of unmetamorphosed conglomerates known as the Kombolgie subgroup. The Kombolgie subgroup provided the source for oxidized basinal brines, carrying U as the mobile form U(VI), which interacted with reducing lithologies in the Cahill formation, thus reducing U(VI) to the solid U(IV), and leading to the precipitation of uraninite (UO2). In order to characterize fluid interaction with the ore body and compare that to areas without mineralization, several isotopic tracers were studied on a series of clay samples from drill core at Jabiluka as well as in barren areas throughout the ARUF. Among the potential tracers, three were selected: U (redox sensitive and recent fluid mobilization), Fe (redox sensitive), and Li (fractionated by hydrothermal fluids and adsorption reactions). δ238U values were found to be closely linked to the mineralogy, with samples with higher K/Al ratios (indicating high illite and low chlorite concentrations) having higher δ238U values. This demonstrates that 235U preferentially absorbs onto the surface of chlorite during hydrothermal circulation. In addition, δ234U values lie far from secular equilibrium (δ234U of 30‰), indicating there was addition or removal of 234U from the surface of the samples from recent (<2.5Ma) interactions of mobile fluids. δ57Fe values were found to be related to lithology and spatially to known uranium deposits. Decreasing δ57Fe values were found with increasing depth to the unconformity in a drill hole directly above the ore zone, but not in drill holes in the barren area. Similarly to δ238U, δ7Li is found to correlate with mineralogy, with higher δ7Li values associated with samples with more chlorite. In addition, higher δ7Li values are found at greater depth throughout the basin, indicating that the direction of the mineralizing fluid circulation was upwards from the Cahill formation to the Kombolgie subgroup.

Coupled Ge/Si and Ge isotope ratios as geochemical tracers of seafloor hydrothermal systems: Case studies at Loihi Seamount and East Pacific Rise 9°50’N

Germanium (Ge) and Silicon (Si) exhibit similar geochemical behaviour in marine environments but are variably enriched in seafloor hydrothermal fluids relative to seawater. In this study, Ge isotope and Ge/Si ratio systematics were investigated in low temperature hydrothermal vents from Loihi Seamount (Pacific Ocean, 18°54’N, 155°15’W) and results were compared to high-temperature vents from the East Pacific Rise (EPR) at 9°50’N. Loihi offers the opportunity to understand contrasting Ge and Si behaviour in low temperature seafloor hydrothermal systems characterized by abundant Fe oxyhydroxide deposition at the seafloor. The results show that both Ge/Si and δ74/70Ge in hydrothermal fluids are fractionated relative to the basaltic host rocks. The enrichment in Ge vs. Si relative to fresh basalts, together with Ge isotope fractionation (Δ74/70Ge fluid-basalt up to 1.15 ‰ at EPR 9°50’N and 1.64 ‰ at Loihi) are best explained by the precipitation of minerals (e.g. quartz and Fe-sulfides) during higher temperature seawater-rock reactions in the subsurface. The study of Fe-rich hydrothermal deposits at Loihi, largely composed of Fe-oxyhydroxides, shows that Ge isotopes are also fractionated upon mineral precipitation at the seafloor. We obtained an average Ge isotope fractionation factor between Fe-oxyhydroxide (ferrihydrite) and dissolved Ge in the fluid of -2.0 ± 0.6 ‰ (2sd), and a maximum value of -3.6 ± 0.6 ‰ (2sd), which is consistent with recent theoretical and experimental studies. The study of a hydrothermal chimney at Bio 9 vent at EPR 9°50’N also demonstrates that Ge isotopes are fractionated by approximately -5.6 ± 0.6 ‰ (2sd) during precipitation of metal sulfides under hydrothermal conditions. Using combined Ge/Si and estimated Ge isotope signatures of Ge sinks and sources in seawater, we propose a preliminary oceanic budget of Ge which reveals that an important sink, referred as the “missing Ge sink”, may correspond to Ge sequestration into authigenic Fe-oxyhydroxides in marine sediments. This study shows that combining Ge/Si and δ74/70Ge systematics provides a useful tool to trace hydrothermal Ge and Si sources in marine environments and to understand formation processes of seafloor hydrothermal deposits.