Composition of native Cu, Cu isotope and mineral analysis from different samples of ODP and DSDP

Ocean drilling has revealed that, although a minor mineral phase, native Cu ubiquitously occurs in the oceanic crust. Cu isotope systematics for native Cu from a set of occurrences from volcanic basement and sediment cover of the oceanic crust drilled at several sites in the Pacific, Atlantic and Indian oceans constrains the sources of Cu and processes that produced Cu**0. We propose that both hydrothermally-released Cu and seawater were the sources of Cu at these sites. Phase stability diagrams suggest that Cu**0 precipitation is favored only under strictly anoxic, but not sulfidic conditions at circum-neutral pH even at low temperature. In the basaltic basement, dissolution of primary igneous and potentially hydrothermal Cu-sulfides leads to Cu**0 precipitation along veins. The restricted Cu-isotope variations (delta 65Cu = 0.02-0.19 per mil) similar to host volcanic rocks suggest that Cu**0 precipitation occurred under conditions where Cu+-species were dominant, precluding Cu redox fractionation. In contrast, the Cu-isotope variations observed in the Cu**0 from sedimentary layers yield larger Cu-isotope fractionation (delta 65Cu = 0.41-0.95 per mil) suggesting that Cu**0 precipitation involved redox processes during the diagenesis, with potentially seawater as the primary Cu source. We interpret that native Cu precipitation in the basaltic basement is a result of low temperature (20°-65 °C) hydrothermal processes under anoxic, but not H2S-rich conditions. Consistent with positive delta 65Cu signatures, the sediment cover receives major Cu contribution from hydrogenous (i.e., seawater) sources, although hydrothermal contribution from plume fallout cannot be entirely discarded. In this case, disseminated hydrogenous and/or hydrothermal Cu might be diagenetically remobilized and reprecipitated as Cu**0 in reducing microenvironment.

Contents and isotopic speciation of sedimentary carbon and nitrogen in sediment core MD01-2404, the Okinawa Trough

Total organic carbon to total nitrogen ratio (C/N) and their isotopic composition (d13CTOC vs. d15NTN) are oft-applied proxies to discern terrigenous from marine sourced organics and to unravel the ancient environmental information. In high depositional Asian marginal seas, matrixes, including N-bearing minerals, dilution leads to illusive and even contradictive interpretations. We use KOH-KOBr to separate operationally defined total organic matter into oxidizable (labile) and residual fractions for content and isotope measurements. In a sediment core in the Okinawa Trough, significant amounts of carbon and nitrogen existed in the residual phase, in which the C/N ratio was ~9 resembling most documented sedimentary bulk C/N ratios in the China marginal seas. Such similarity creates a pseudo-C/N interrupting the application of bulk C/N. The residual carbon, though composition unknown, it displayed a d13C range (-22.7 to -18.9 per mil, mean -20.7 per mil) similar to black carbon (-24.0 to -22.8 per mil) in East China Sea surface sediments. After removing residual fraction, we found the temporal pattern of d13CLOC in labile fraction (LOC) was more variable but broadly agreed with the atmospheric pCO2-induced changes in marine endmember d13C. Thus, we suggested adding pCO2-induced endmember modulation into two-endmember mixing model for paleo-environment reconstruction. Meanwhile, the residual nitrogen revealed an intimate association with illite content suggesting its terrestrial origin. Additionally, d15N in residual fraction likely carried the climate imprint from land. Further studies are required to explore the controlling factors for carbon and nitrogen isotopic speciation and to retrieve the information locked in the residual fraction.

A foraminiferal d18O record of sediment core GT90-3 covering the last 2,200 years

For many years the Torino Cosmogeophysics group has been studying sediment cores drilled from the Gallipoli Terrace in the Gulf of Taranto (Ionian Sea) and deposited in the last millennia. The gravity core GT90-3, in which the 18O series was measured, was drilled from the Gallipoli Terrace in the Gulf of Taranto (Ionian Sea) at 39°45'53''N, 17°53'33''E. It was extracted at a depth of 178 m and its length is 3.57 m. Thanks to its geographical location, the Gallipoli Terrace is a favourable site for climatic studies based on marine sediments, because of its closeness to the volcanically active Campanian area, a region that is unique in the world for its detailed historical documentation of volcanic eruptions. Tephra layers corresponding to historical eruptions were identified along the cores, thus allowing for accurate dating and determination of the sedimentation rate. The measurements performed in different cores from the same area showed that the sedimentation rate is uniform across the whole Gallipoli Terrace. We measured the oxygen isotope composition d18O of planktonic foraminifera. These measurements provided a high-resolution 2,200-year-long record. We sampled the core using a spacing of 2.5 mm corresponding to 3.87 years. Each sample of sediment (5 g) was soaked in 5% calgon solution overnight, then treated in 10% H2O2 to remove any residual organic material. Subsequently it was washed with a distilled-water jet through a sieve with a 150 µm mesh. The fraction > 150 µm was kept and oven-dried at 5°C. The planktonic foraminifera Globigerinoides ruber were picked out of the samples under a microscope. For each sample, 20-30 specimens were selected from the fraction comprised between 150 µm and 300 µm. The use of a relatively large number of specimens for each sample reduces the isotopic variability of individual organisms, giving a more representative d18O value. The stable isotope measurements were performed using a VG-PRISM mass spectrometer fitted with an automated ISO-CARB preparation device. Analytical precision based on internal standards was better than 0.1 per mil. Calibration of the mass spectrometer to VPDB scale was done using NBS19 and NBS18 carbonate standards. The strategic location of the drilling area makes this record a unique tool for climate and oceanographic studies of the Central Mediterranean.

(Table T2) Stable carbon and oxygen isotopes of DSDP Leg 30, Leg 33, ODP Leg 130 and Leg 192 sites, Ontong Java Plateau

Stable isotopic analyses of bulk carbonates recovered from Ontong Java Plateau during Ocean Drilling Program (ODP) Leg 192 (Holes 1183A and 1186A) show an ~0.5 per mil increase in d18O values from the upper Campanian/lower Maastrichtian to the upper Maastrichtian. This shift is consistent with widespread evidence for cooling at this time. Similar shifts were found at other localities on Ontong Java Plateau (Deep Sea Drilling Project [DSDP] Sites 288 and 289 and ODP Site 807) and at DSDP Site 317 on Manihiki Plateau. These data extend evidence for Maastrichtian cooling into the southwestern tropical and subtropical Pacific. The record of apparent cooling survives despite a significant diagenetic overprint at all sites. Comparing average Maastrichtian d18O values among sites suggests that diagenesis caused d18O to first be shifted toward higher values and then back toward lower values as burial depth increased. Carbon isotopes at the six sites show no apparent primary shifts, but at four sites, the Cretaceous/Tertiary boundary interval coincides with a negative excursion attributed to alteration of sediments near the boundary.

Sulfur-isotope analyses of gypsium samples from the Southeast Greenland margin, southern Alaska and Gulf of Alaska (Table 1)

Gypsum grains were identified in Miocene-Pleistocene sediment cores from two deep-water ODP sites, Site 918 off the SE Greenland margin and Site 887 in the Gulf of Alaska, and in Holocene sediment cores from shallow-water localities in Disenchantment Bay and Muir Inlet in southern Alaska. Although initial morphologic and textural observations suggested a complex system in which the gypsum may have had more than one origin, quantitative sulfur isotope analyses of the gypsum provide evidence of its detrital nature. d34S values in gypsum from southern Alaska range between +0.0 and +7.1 per mil. Gypsum has d34S values between -27.1 and -27.5 per mil in the Gulf of Alaska and values between -28.5 and +0.2 per mil off the SE Greenland margin. All of these isotopic signatures are too highly depleted in d34S to have precipitated from seawater, present or past. In addition there is no significant change in d34S values for gypsum crystals with differing physical characteristics (abraded vs. unabraded) from the same stratigraphic horizon, suggesting all the gypsum is detrital regardless of the degree of abrasion. The isotopic and physical evidence, in combination with the onshore geology the environmental setting, and site characteristics of the gypsum-bearing marine localities, lead us to propose that the ultimate source of the gypsum is precipitation from freeze-induced terrestrial sediment or soil brines. Furthermore the combined evidence suggests that the subsequent occurrence of gypsum in glacimarine sediments results from ice-rafting (by icebergs or sea ice) of the frozen regolith and/or, in the proximal glacimarine setting of southern Alaska, very rapid burial via turbidity currents.

Stable carbon and oxygen isotope record of live benthic foraminifera from Swedish fjords

In a previous 16-month seasonal study on living (stained) benthic foraminifera from two fjords on the Swedish west coast, it was reported that foraminifera proliferated in response to phytodetritus input; the strongest response came from the opportunistic species Stainforthia fusiformis. In this study, our objective was to find out if that phytodetritus input resulted in a change in the carbon isotopic composition of the foraminiferal tests. We also wanted to examine if variations in salinity and temperature (due to seasonality or deep-water exchanges) were reflected in the delta18O values. From S. fusiformis that were obtained from the Havstens Fjord (20 m) and the Gullmar Fjord (119 m) during the 16-month study, we developed a time series of delta18O and delta13C. After the spring blooms in the Havstens and the Gullmar Fjord, decreases of about 0.2 per mil to 0.3 per mil in the foraminiferal delta13C values were noted; in the Gullmar Fjord after the autumn blooms, decreases of the same order were also noted. Comparing the Havstens and the Gullmar Fjord, we found a 1 per mil difference in both delta13C and delta18O; we attribute this to hydrographic differences between the two fjords. Using calculated values of delta18O, together with the measured ones, we noticed that S. fusiformis in the Gullmar Fjord seems to calcify close to equilibrium with respect to the oxygen isotopes. During autumn, water temperatures were relatively high in the Havstens Fjord, and foraminiferal abundance in the fjord was also high after a phytodetritus input; but, the measured delta18O values do not reflect these higher temperatures. This apparently contradictory combination of results might be explained by a varying delta18O composition of the water during the year, which counterbalances the temperature effect.

Sulfur isotope rations in oceanic basement samples

Low temperature alteration of oceanic basement rocks is characterized by net gain of sulfur, which commonly yields low d34S values, suggesting involvement of microbial sulfate reduction. In order to test whether secondary sulfide minerals are consistent with a biogenic source, we apply high precision multiple sulfur isotope analysis to bulk rock sulfide and pyrite isolates from two contrasting types of altered oceanic basement rocks, namely serpentinized peridotites and altered basalts. Samples from two peridotite sites (Iberian Margin and Hess Deep) and from a basalt site on the eastern flank of the Juan de Fuca Ridge yield overlapping d34S values ranging from 0 per mil to -44 per mil. In contrast, sulfides in the basalt site are characterized by relatively low D33S values ranging from -0.06 per mil to 0.04 per mil, compared to those from peridotite sites (0.00 per mil to 0.16 per mil). The observed D33S signal is significant considering the analytical precision of 0.014 per mil (2 sigma). We present a batch reaction model that uses observed d34S and D33S relationships to quantify the effect of closed system processes and constrain the isotope enrichment factor intrinsic to sulfate reduction. The estimated enrichment factors as large as 61 per mil and 53 per mil, for peridotite and basalt sites respectively, suggest the involvement of microbial sulfate reduction. The relatively high D33S values in the peridotite sites are due to sulfate reduction in a closed system environment, whereas negative D33S values in the basalt site reflect open system sulfate reduction. A larger extent of sulfate reduction during alteration of peridotite to serpentinite is consistent with its higher H2 production capacity compared to basalt alteration, and further supports in-situ microbial sulfate reduction coupled with H2 production during serpentinization reactions.

Benthic and planktic foraminiferal stable isotope record and coccolith abundance spanning the last 500,000 years of ODP Hole 121-758C

The Indian Summer Monsoon (ISM) is an inter-hemispheric and highly variable ocean-atmosphere-land interaction that directly affects the densely populated Indian subcontinent. Here, we present new records of palaeoceanographic variability that span the last 500,000 years from the eastern equatorial Indian Ocean, a relatively under-sampled area of ISM influence. We have generated carbon and oxygen stable isotope records from three foraminiferal species from Ocean Drilling Program Site 758 (5°N, 90°E) to investigate the oceanographic history of this region. We interpret our resultant Dd18O (surface-thermocline) record of upper water-column stratification in the context of past ISM variability, and compare orbital phase relationships in our Site 758 data to other climate and monsoon proxies in the region. Results suggest that upper water-column stratification at Site 758, which is dominated by variance at precession and half-precession frequencies (23, 19 and 11 ka), is forced by both local (5°N) insolation and ISM winds. In the precession (23 ka) band, stratification minima at Site 758 lag northern hemisphere summer insolation maxima (precession minima) by 9 ka, which is consistent with Arabian Sea ISM phase estimates and suggests a common wind forcing in both regions. This phase implicates a strong sensitivity to both ice volume and southern hemisphere insolation forcing via latent heat export from the southern subtropical Indian Ocean. Additionally, we find evidence of possible overprinting of millennial-scale events during glacial terminations in our stratification record, which suggests an influence of remote abrupt climate events on ISM dynamics.

(Table 1) Stable carbon isotope record and calculated recycled DIC for sediment core ANDRA_HTM102

The prominent negative stable carbon isotope excursion in both carbonate and organic carbon recorded in organic-rich sediments deposited during the Toarcian oceanic anoxic event (OAE) has commonly been explained by recycling of 13C-depleted CO2 (the so-called Küspert model). More recently, the massive release of 13C-depleted methane or other forms of 13C-depleted carbon was also proposed to account for the observed negative d13C excursions in organic carbon of terrigenous as well as of marine origin. The occurrence of diagenetic products of the carotenoid isorenieratene (isorenieratane and other aryl isoprenoids) in Toarcian black shales has been regarded as supporting evidence for the Küspert hypothesis as they point to strong stratification of the epicontinental seas. A section of a drill core straddling the Toarcian of the Paris Basin (Cirfontaine-en-Ornois) contained intact isorenieratane, providing evidence that photosynthetic green sulphur bacteria were present at the time of deposition, even prior to the OAE. However, the isorenieratane abundances are very low in the section where the negative d13C excursion in organic carbon and phytane, a chemical fossil derived from chlorophyll, occurs. The abundance of the isorenieratene derivatives increases, once the d13C records have shifted to more positive values. The d13C of isorenieratane (generally circa -13.1 ± 0.5 per mil) indicates that the respired CO2 contribution at the chemocline was low and is thus not likely to be the main cause of the prominent up to 7per mil negative d13C shift recorded in Toarcian organic carbon records.

(Table 2) Stable isotopes in foraminifers at DSDP Leg 78

Analyses of stable isotopes of monospecific planktonic foraminifers (G. quadrilobatus group) and monogeneric benthic foraminifers (Cibicidoides spp.) from late Neogene Atlantic Site 502 and Pacific Site 503 were conducted in order to determine the paleoceanographic changes resulting from the late Neogene uplift of the Panama Isthmus and from climatic cooling. In general, results at each site are similar to those from previous studies for the late Miocene and late Pliocene time interval, documenting the late Miocene (6 Ma) shift in carbon isotopes and the inferred growth of permanent Northern Hemisphere continental ice sheets beginning about 3.2 Ma. Comparison of Atlantic-Pacific planktonic-benthic isotope data for four stratigraphic intervals (~6-8, ~5-6, ~3-5, and ~2-3 Ma) suggests that increasing isolation of Atlantic and Pacific low-latitude waters may be related to the emergence of the Panama Isthmus. The contrast between Atlantic and Pacific benthic foraminiferal d13C increased in two steps from 0.60 per mil to 1 per mil (the modern contrast) at about 6 Ma and 3 Ma. The first increase (0.15 per mil) may represent the end of previously limited deep-water communication between the Atlantic and Pacific at the present location of Panama. The second increase (0.25 per mil) may be due to increased production of North Atlantic Deep Water. This probably reflects the development of modern deep-sea circulation. The d18O of planktonic foraminifers begins to increase in Atlantic Site 502 at 4.2 Ma and may reflect the increasing salinity of the North Atlantic Ocean arising from diminishing surface-water exchange across Panama. This increase is clearly shown by contrasting the d18O of Atlantic and Pacific planktonic foraminifers, as well as the d18O of planktonic and benthic foraminifers at Site 502. This inferred increase in surface-water salinity begins at the time of increasing provinciality of Atlantic and Pacific planktonic foraminifers.

Stable isotope composition of Neogene planktonic foraminifera from ODP Leg 130 sites

We produced a preliminary record for shallow-dwelling planktonic foraminifer d18O at Site 807 for the late Pleistocene, early Pliocene, and early Miocene. Site 807 d18O values between 4 and 5 Ma average 0.75 per mil more than Holocene values and show an average variation of 0.5 per mil. For the early Pliocene, peak maximum d18O at Site 807 attain values equivalent with the last glacial maximum whereas peak minimum d18O were never less than Holocene d18O. Shallow-dwelling planktonic d18O at Site 807 between 16 and 24 Ma average more than 1.0 per mil more positive than Holocene d18O and exhibit 0.5 per mil average amplitude. Assuming that the global ice budget for the early Pliocene and early Miocene was restricted to Antarctica, it is difficult to attribute the very positive Site 807 d18O for these intervals to ice on Antarctica. Site 807 d18O for these intervals more likely reflect sea-surface temperatures cooler than at present, sea-surface salinity greater than at present, increased dissolution, or some combination of these changes.

Late Paleocene to Eocene stable isotope record od ODP Site 143-865

An expanded and largely complete upper Paleocene to upper Eocene section was recovered from the pelagic cap overlying Allison Guyot, Mid-Pacific Mountains at Ocean Drilling Program (ODP) Site 865 (18°26'N, 179°33'W; paleodepth 1300-1500 m). Reconstructions show that the site was within a few degrees of the equator during the Paleogene. Because no other Paleogene sections have been recovered in the Pacific Ocean at such a low latitude, Site 865 provides a unique record of equatorial Pacific paleoceanography. Detailed stable isotopic investigations were conducted on three planktonic foraminiferal taxa (species of Acarinina, Morozovella, and Subbotina). We studied benthic foraminiferal isotopes at much lower resolution on species of Cibicidoides and Lenticulina, Nuttallides truempyi and Gavelinella beccariiformis, because of their exceptional rarity. The d18O and d13C stratigraphies from Site 865 are generally similar to those derived from other Paleocene and Eocene sections. The planktonic foraminiferal records at Site 865, however, include significantly less short-term, single-sample variability than those from higher-latitude sites, indicating that this tropical, oligotrophic location had a comparatively stable water column structure with a deep mixed layer and less seasonal variability. Low-amplitude (0.1-0.8 per mil) oscillations on timescales of 250,000 to 300,000 years correlate between the d13C records of all planktonic taxa and may represent fluctuations in the mixing intensity of surface waters. Peak sea surface temperatures of 24°-25°C occurred in the earliest Eocene, followed by a rapid cooling of 3-6°C in the late early Eocene. Temperatures remained cool and stable through the middle Eocene. In the late Eocene, surface water temperatures decreased further. Vertical temperature gradients decreased dramatically in the late Paleocene and were relatively constant through much of the Eocene but increased markedly in the late Eocene. Intermediate waters warmed through the late Paleocene, reaching a maximum temperature of 10°C in the early Eocene. Cooling in the middle and late Eocene paralleled that of surface waters, with latest Eocene temperatures below 5°C. Extinction patterns of benthic foraminifera in the latest Paleocene were similar to those observed at other Pacific sites and were coeval with a short-term, very rapid negative excursion in d13C values in planktonic and benthic taxa as at other sites. During this excursion, benthic foraminiferal d18O values decreased markedly, indicating warming of 4 to 6°C for tropical intermediate waters, while planktonic taxa show slight warming (1°C) followed by 2°C of cooling. Convergence of d18O values of planktonic and benthic foraminifera suggests that thermal gradients in the water column in this tropical location collapsed during the excursion. These data are consistent with the hypothesis that equatorial Pacific surface waters were a potential source of warm, higher salinity waters which filled portions of the deep ocean in the latest Paleocene. Oxygen isotopic data indicate that equator to high southern latitude sea surface thermal gradients decreased to as little as 4°C at the peak of the excursion, suggesting some fundamental change in global heat transport.

Mineralogy, geochemistry, isotopic ratios and foraminifer occurrence in ODP Hole 183-1139A

Mixed terrigenous-pelagic sediments from the Oligocene-lower Miocene interval of Hole 1139A accumulated on the flank of an eroded alkalic volcano, Skiff Bank. In this study, I explore relationships among sediment fluxes, especially of organic carbon and the clay mineral by-products of silicate weathering, and lithologic, tectonic, climatic, and biologic forcing factors. Benthic foraminifers indicate that Skiff Bank had subsided to lower bathyal depths (1000-2000 m) by the Oligocene. Two prominent maxima in noncarbonate concentration at 28 and 22 Ma correspond to peaks in the terrigenous flux; also, high noncarbonate concentrations are associated with larger grain sizes (silt) and higher opal concentrations. These and higher-frequency variations of noncarbonate concentration were probably controlled by glacioeustatic/climatic changes, with higher noncarbonate concentrations caused by increased erosion during glacial lowstands. Around 27 Ma, benthic foraminiferal d18O values decreased 0.7 per mil as the noncarbonate concentration decreased after the 28-Ma maximum. A paucity of clay-sized sediment and clay minerals suggests that physical erosion, by waves and/or ice, predominated under weathering-limited conditions. Low organic carbon concentrations (~0.13 wt%) also suggest a harsh environment and/or poor preservation in coarse (>2 µm) sediments that were extensively bioturbated below the oxygen minimum zone.

Stable oxygen, hydrogene and chlorine isotopes of mid-Atlantic abyssal peridotites

Serpentinized abyssal peridotites sampled by the Ocean Drilling Program Leg 209 along the mid-Atlantic Ridge near the 15°20'N Fracture Zone have been analyzed for oxygen, hydrogen, and chlorine isotope compositions in order to determine isotopic behavior under a wide range of serpentinization conditions and place constraints on fluid history. Oxygen and hydrogen thermometry suggests peak serpentinization temperatures of 300-500°C. Serpentine separates have low deltaD values possibly due to a magmatic fluid component or low-temperature exchange during seafloor weathering. Chlorine geochemistry focused on three holes: 1274A and 1272A (serpentinized peridotites) and 1268A (serpentinite locally altered to talc). Concentrations of both, water-soluble chloride (WSC) and structurally bound chloride (SBC) are significantly lower at Hole 1268A compared to Holes 1274A and 1272A. The delta37Cl values for WSC and SBC of serpentinites in Holes 1274A and 1272A are slightly positive (avg. WSC = 0.20 per mil, n = 22 and avg. SBC = 0.35 per mil, n = 22), representing typical seawater-hydration conditions commonly determined for abyssal peridotite. The SBC of serpentinites from Hole 1268A are also positive (avg. = 0.63 per mil); whereas, the SBC in talc-dominated samples is negative (avg. = -1.22 per mil). The WSC of both talc- and serpentine-dominated samples are also negative (avg. = -0.15 per mil). We interpret the chlorine isotope data to preserve a record of multiple fluid events. As seawater hydrated the peridotite, 37Cl was preferentially incorporated into the forming serpentine and water-soluble salts, yielding similar delta37Cl values on a regional scale as sampled by Holes 1268A, 1274A and 1272A. The resultant pore fluid was left depleted in 37Cl. Locally (Hole 1268A), this evolved fluid was remobilized possibly due to the initiation of hydrothermal circulation in response to emplacement of a mafic magma body. The low delta37Cl pore fluids attained elevated SiO2 and sulfur concentrations due to interaction with the gabbroic intrusion and, when ascending through the surrounding serpentinite, caused formation of isotopically negative talc. This secondary fluid also flushed the preserved serpentinite of its previously formed salts, resulting in negative delta37Cl WSC values. The delta37Cl SBC values of the serpentinite samples remained unmodified by reaction with the secondary fluid.