In-situ Iron isotope measurements and mineral compositions from ODP Hole 206-1256D and IODP Hole 335-U1256D

In-situ Fe isotope measurements have been carried out to estimate the impact of the hydrothermal metamorphic overprint on the Fe isotopic composition of Fe-Ti-oxides and Fe-sulfides of the different lithologies of the drilled rocks from IODP Hole 1256D (eastern equatorial Pacific; 15 Ma crust formed at the East Pacific Rise). Most igneous rocks normally have a very restricted range in their 56Fe/54Fe ratio. In contrast, Fe isotope compositions of hot fluids (> 300 °C) from mid-ocean-ridge spreading centers define a narrow range that is shifted to lower delta 56Fe values by 0.2 per mil - 0.5 per mil as compared to igneous rocks. Therefore, it is expected that mineral phases that contain large amounts of Fe are especially affected by the interaction with a fluid that fractionates Fe isotopes during exsolution/precipitation of those minerals. We have used a femtosecond UV-Laser ablation system to determine mineral 56Fe/54Fe ratios of selected samples with a precision of < 0.1 per mil (2 sigma level) at micrometer-scale. We have found significant variations of the delta 56Fe (IRMM-014) values in the minerals between different samples as well as within samples and mineral grains. The overall observed scale of delta 56Fe (magnetite) in 1256D rocks ranges from - 0.12 to + 0.64 per mil, and of delta 56Fe (ilmenite) from - 0.77 to + 0.01 per mil. Pyrite in the lowermost sheeted dike section is clearly distinguishable from the other investigated lithological units, having positive delta 56Fe values between + 0.29 and + 0.56 per mil, whereas pyrite in the other samples has generally negative delta 56Fe values from - 1.10 to - 0.59 permil. One key observation is that the temperature dependent inter-mineral fractionations of Fe isotopes between magnetite and ilmenite are systematically shifted towards higher values when compared to theoretically expected values, while synthesized, well equilibrated magnetite-ilmenite pairs are compatible with the theoretical predictions. Theoretical considerations including beta-factors of different aqueous Fe-chlorides and Rayleigh-type fractionations in the presence of a hydrous, chlorine-bearing fluid can explain this observation. The disagreement between observed and theoretical equilibrium fractionation, the fact that magnetite, in contrast to ilmenite shows a slight downhole trend in the delta 56Fe values, and the observation of small scale heterogeneities within single mineral grains imply that a general re-equilibration of the magnetite-ilmenite pairs is overprinted by kinetic fractionation effects, caused by the interaction of magnetite/ilmenite with hydrothermal fluids penetrating the upper oceanic crust during cooling, or incomplete re-equilibration at low temperatures. Furthermore, the observation of significant small-scale variations in the 56Fe/54Fe ratios of single minerals in this study highlights the importance of high spatial-resolution-analyses of stable isotope ratios for further investigations.

Studies of the microbial diversity on analyzed samples from from Peru Margin, Equatorial Pacific, Hydrate Ridge, and Juan de Fuca Ridge

Marine sediments harbor an enormous quantity of microorganisms, including a multitude of novel species. The habitable zone of the marine sediment column begins at the sediment-water interface and probably extends to depths of several thousands of meters. Studies of the microbial diversity in this ecosystem have mostly relied on molecular biological techniques. We used a complementary method - analysis of intact polar membrane lipids - to characterize the in-situ microbial community in sediments covering a wide range of environmental conditions from Peru Margin, Equatorial Pacific, Hydrate Ridge, and Juan de Fuca Ridge. Bacterial and eukaryotic phospholipids were only detected in surface sediments from the Peru Margin. In contrast, deeply buried sediments, independent of their geographic location, were dominated by archaeal diether and tetraether lipids with various polar head groups and core lipids. We compared ring distributions of archaeal tetraether lipids derived from polar glycosidic precursors with those that are present as core lipids. The distributions of these related compound pools were distinct, suggestive of different archaeal sources, i.e., the polar compounds derive from sedimentary communities and the core lipids are fossil remnants from planktonic communities with possible admixtures of decayed sedimentary archaea. This in-situ production of distinct archaeal lipid populations potentially affects applications of the TEX86 paleotemperature proxy as demonstrated by offsets in reconstructed temperatures between both pools. We evaluated how varying cell and lipid stabilities will influence the sedimentary pool by using a box-model. The results are consistent with (i) a requirement of continuous inputs of freshly synthesized lipids in subsurface sediments for explaining the observed distribution of intact polar lipids, and (ii) decreasing lipid inputs with increasing burial depth.

Calcareous nannofossils in sediments of the Japan Sea

Preliminary results of the biostratigraphic analysis of calcareous nannofossils recovered from Ocean Drilling Program Leg 128, Sites 798 and 799, provide clues to the Quaternary oceanography of the Japan Sea. The distribution of calcareous nannofossils from the Quaternary sediments at Site 798 (903 m water depth) may record the position of an Oceanographic frontal boundary between warm water derived from a branch of the Kuroshio Current as it entered the Japan Sea through the Tsushima Straits to the south, and colder water introduced into the western portion of the Japan Sea derived from the winter chilling of northern Japan Sea surface waters. This Oceanographic front probably oscillated north-south over Site 798 in response to glacial/interglacial cycles, or perhaps to some other climatic event or combination of events unique to the Japan Sea. During the last 1.5 m.y., six major intervals are recognized when the Oceanographic front may have been north of Site 798 separated by five major intervals when the frontal boundary may have been south of the site. These migrations were centered around approximately 0.125, 0.29, 0.56, 0.62, 0.85, 0.91, 0.98, 1.0, 1.11, and 1.5 Ma, which correspond to the boundaries separating nannofossil-rich sediments from barren or nearly barren, low-carbonate intervals. Nannofossil-rich intervals may represent times when the frontal boundary was north of Site 798, and the site was above the CCD. Barren or nearly barren intervals represent times when the frontal boundary may have been south of Site 798 and the CCD was probably higher. The distribution of calcareous nannofossils at Site 799 (2073 m water depth) appears to be controlled more by the depth of the CCD than by any climatic effects. The FOD (first occurrence datum) of Emiliania huxleyi, the LOD (last occurrence datum) of Psuedoemiliania lacunosa, Helicosphaera sellii, Calcidiscus macintyrei (10 ?m), and the FOD and LOD of Reticulofenestra asanoi are recognized from Site 798 cores. The LOD of P. lacunosa is observed in sediments from Site 799. Only in the sediments younger than 1.5 Ma are the nannofossils from Sites 798 and 799 preserved well enough and sufficiently numerous for age dating and paleoceanographic conjecture. In-situ dissolution in older sediments at both sites precludes any dating or paleoenvironmental interpretations.

Plio-Pleistocene Mg/Ca and TEX86 sea surface temperature records of ODP Sites 184-1143 and 165-999,

The western warm pools of the Atlantic and Pacific oceans are a critical source of heat and moisture for the tropical climate system. Over the past five million years, global mean temperatures have cooled by 3-4 °C. Yet, current reconstructions of sea surface temperatures indicate that temperature in the warm pools has remained stable during this time. This stability has been used to suggest that tropical sea-surface temperatures are controlled by some sort of thermostat-like regulation. Here we reconstruct sea surface temperatures in the South China Sea, Caribbean Sea and western equatorial Pacific Ocean for the past five million years, using a combination of the Mg/Ca, TEXH86-and Uk'37 surface temperature proxies. Our data indicate that during the period of Pliocene warmth from about 5 to 2.6 million years ago, the western Pacific and western Atlantic warm pools were about 2 °C warmer than today. We suggest that the apparent lack of warming seen in the previous reconstructions was an artefact of low seawater Mg/Ca ratios in the Pliocene oceans. Taking this bias into account, our data indicate that tropical sea surface temperatures did change in conjunction with global mean temperatures. We therefore conclude that the temperature of the warm pools of the equatorial oceans during the Pliocene was not limited by a thermostat-like mechanism.

Organic geochemistry of ODP Sites 128-798 and 128-799

Miocene to Quaternary sediments from the Oki Ridge (Site 798) and the Kita-Yamato Trough (Site 799) in the Japan Sea contain organic carbon ranging from about 0.6% in light-colored layers to almost 6% in dark layers. The organic matter consists of a variable mixture of marine and terrigenous contributions, the ratio of which is not correlated to the total organic carbon content. Marine organic particles clearly dominate in the deeper section of Hole 799B. The extractable bitumen is strongly dominated by long-chain alkenones from microalgae in the shallower sediments, whereas bishomohopanoic acid (C32) of eubacterial origin is the single most abundant compound in deeper samples. Normal alkanes and straight-chain carboxylic acids, both of which show a bimodal distribution with odd and even carbon-number predominance, respectively, are two other groups of compounds which are important constituents of the extracts. The deepest samples at Site 799 contain a considerable amount of short-chain components, which probably migrated upward from thermally more altered deeper sediments.

Benthic and planktonic foraminifera in the Japan Sea

Biostratigraphy and paleoenvironmental history of deep and surficial waters of the Japan Sea are addressed using sequences recovered from the floor of the backarc basin. The study is divided into two parts: (1) foraminifer biostratigraphy and paleoenvironmental assessment of sedimentary sequences recovered from above igneous basement at the four sites and (2) detailed planktonic foraminifer paleoenvironmental analysis of Quaternary and Pliocene sequences from Sites 794 and 797 in the Yamato Basin. A total of 253 samples were examined for the foraminifer biostratigraphy and 325 samples for the detailed paleoenvironmental study of Quaternary and Pliocene sequences. Low abundance and sporadic occurrence of foraminifers limited interpretation of results. Foraminifer-bearing intervals were correlated where possible to diatom and calcareous nannofossil zonations, and the sequences were successfully assigned to the foraminifer zonation of Matsunaga. Unfortunately, extensive barren intervals and sporadic occurrences of planktonic foraminifers prevented zonation of Quaternary and Pliocene intervals, although some interesting conclusions about paleoenvironment were possible and are listed below. A sequence of Neogene (sensu lato) paleoenvironmental events were identified: (1) deepening of the Yamato basins to middle bathyal depths by the early to middle Miocene, an event contemporaneous with the age of some deep basins known from uplifted sections adjacent to the Japan Basin; (2) cooling of the Japan Sea in the early middle Miocene; (3) oxygenation of deep waters in the late Miocene; (4) further cooling of surficial water masses between the Olduvai Subchron and the Brunhes/Matuyama Boundary; and (5) extermination of lower middle bathyal faunas and replacement by upper middle bathyal faunas near the base of the Quaternary.

Pliocene and Pleistocene abundance of siliceous microfossil assemblages in ODP Leg 127 sites

A close examination of the siliceous microfossil assemblages from the sediments of ODP Leg 127, Japan Sea Sites 794, 795, and 797, reveals that upper Pliocene and Pleistocene assemblages have been subjected to more dissolution than have lower Pliocene assemblages. This conclusion is based on semiquantitative observations of samples processed for diatoms and radiolarians. Although preservation of opaline microfossils in some upper Pliocene and Pleistocene samples is better than others, in general, the poorly preserved state of these assemblages supports the notion that opal dissolution, in response to lowered productivity, is responsible for the paucity of siliceous microfossils in upper Pliocene and Pleistocene sediments. The lithological transition from diatomaceous oozes to silts and clays corresponds to a change between dominantly well preserved to more poorly preserved siliceous assemblages, and is termed the late Pliocene Japan Sea opal dissolution transition zone (ODTZ). The base of the ODTZ is defined as the uppermost occurrence of high abundances of moderately to well preserved valves of the diatom Coscinodiscus marginatus. The dissolution transition zone is characterized by partially dissolved refractory assemblages of radiolarians, the presence of C. marginatus girdles, C. marginatus fragments, siliceous sponge spicules, and a general decrease in weakly silicified, less solution resistant diatoms upward in the section. The top of the dissolution transition zone marks the level where whole C. marginatus valves and C. marginatus fragments are no longer present in significant numbers. Dissolution of the late Pliocene and Pleistocene opaline assemblages is attributed mainly to changes in paleoceanographic circulation patterns and decreased nutrient (dissolved silicon) contents of the water column, and possibly dissolution at the sediment/water interface, rather than to post-depositional dissolution or diagenesis. We suggest that the transition from silica-rich to silica-poor conditions in the Japan Sea was due to fluctuations of deep-water exchange with the Pacific through the Tsugaru Strait between 2.9 and 2.3 Ma.

EPICA Dome C Ice Core 800KYr deuterium data and temperature estimates

A high-resolution deuterium profile is now available along the entire European Project for Ice Coring in Antarctica Dome C ice core, extending this climate record back to marine isotope stage 20.2, ~800,000 years ago. Experiments performed with an atmospheric general circulation model including water isotopes support its temperature interpretation. We assessed the general correspondence between Dansgaard-Oeschger events and their smoothed Antarctic counterparts for this Dome C record, which reveals the presence of such features with similar amplitudes during previous glacial periods. We suggest that the interplay between obliquity and precession accounts for the variable intensity of interglacial periods in ice core records. Temperature was estimated after correction for sea-water isotopic composition (Bintanja et al, 2005) and for ice sheet elevation (Parrenin et al, 2007) on EDC3 age scale (Parrenin et al, 2007).

Geochemistry of ODP Sites 128-798 and 128-799 sediments

Nineteen trace elements, including seven rare earth elements (REE's), and 10 major and minor elements in 76 sediment samples from Sites 798 (Oki Ridge) and 799 (Yamato Trough) were determined by means of instrumental neutron activation analysis and X-ray fluorescence spectrometry. Most REE patterns (chondrite-normalized) of the sediments from both sites were nearly identical to the patterns of terrigenous materials. The cerium anomaly (slightly positive) frequently appeared in REE patterns of the sediments (200-750 mbsf) from Site 799. Cerium may be selectively incorporated into the sediments with hydrogenous manganese precipitation. However, the degree of the anomaly was not well correlated with manganese content, suggesting that cerium may behave as a trivalent REE (like the other REE's) during diagenesis while manganese is transported in the sediment column accompanied by reduction to a lower oxidation state. The Th/Sc ratio of the sediments from Sites 798 and 799 tended to decrease with penetration depth. Such a depth profile may indicate a decrease in basic volcanism activities from the Pliocene (Site 798) and Miocene (Site 799). The La/Yb ratio and degree of europium anomaly also varied with depth, which may imply that two or more components with different REE patterns were supplied throughout sedimentation at sites in the Japan Sea.

Temperature proxies of sediment cores from the Sea of Marmara

Reconstructing ocean temperature values is a major target in paleoceanography and climate research. However, most temperature proxies are organism-based and thus suffer from an "ecological bias". Multiproxy approaches can potentially overcome this bias but typically require more investment in time and resources, while being susceptible to errors induced by sample preparation steps necessary before analysis. Three lipid-based temperature proxies are widely used: UK'37 (based on long chain alkenones from phytoplanktonic haptophytes), TEX86 [based on glycerol dialkyl glycerol tetraethers (GDGTs) from pelagic archaea] and LDI (based on long chain diols from phytoplanktonic eustigmatophytes). So far, separate analytical methods, including gas chromatography (GC) and liquid chromatography (LC), have been used to determine these proxies. Here we present a sensitive method for determining all three in a single normal phase high performance LC-atmospheric pressure chemical ionization mass spectrometry (NP-HPLC-APCI-MS) analysis. Each of the long chain alkenones and long chain diols was separated and unambiguously identified from the accurate masses and characteristic fragmentation during multiple stage MS analysis (MS2). Comparison of conventional GC and HPLC-MS methods showed similar results for UK'37 and LDI, respectively, using diverse environmental samples and an Emiliania huxleyi culture. Including the three sea surface temperature (SST) proxies; the NP-HPLC-APCI-MS method in fact allows simultaneous determination of nine paleoenvironmental proxies. The extent to which the ecology of the source organisms (ecological bias) influences lipid composition and thereby the reconstructed temperature values was demonstrated by applying the new method to a sediment core from the Sea of Marmara, covering the last 21 kyr BP. Reconstructed SST values differed considerably between the proxies for the Last Glacial Maximum (LGM) and the period of Sapropel S1 formation at ca. 10 kyr BP, whereas the trends during the late Holocene were similar. Changes in the composition of alkenone-producing species at the transition from the LGM to the Bølling/Allerød (B/A) were inferred from unreasonably high UK'37-derived SST values (ca. 20 °C) during the LGM. We ascribe discrepancies between the reconstructed temperature records during S1 deposition to habitat change, e.g. a different depth due to changes in nutrient availability.

Calcareous nannofossil biostratigraphy of ODP Leg 127 sites

Calcareous nannofossils were studied by light microscopy in Neogene sedimentary rocks recovered at four sites of the Ocean Drilling Program Leg 127 in the Japan Sea. Nannofossils occur sporadically at all sites, and allow recognition of seven zones and two subzones; four zones in the Holocene to the uppermost Pliocene, and three zones and two subzones in the middle to lower Miocene. Forty-eight nannofossil species are recognized in 95 of the 808 irregularly-spaced samples taken from all the sites. The nannofossil assemblages in the Miocene are more diverse than those in the Holocene to Pliocene sedimentary interval. The greater diversity and the presence of warm-water taxa, such as Sphenolithus and discoasters in the upper lower Miocene to lower middle Miocene, suggest a relatively warm and stable surface-water condition, attributed to an increased supply of warm water from the subtropical western Pacific Ocean. Site 797 in the southern part of the Yamato Basin contains the most complete and the oldest nannofossil record so far reported from the Japan Sea. The lowermost nannofossil zone at this site, the Helicosphaera ampliaperta Zone (15.7-18.4 Ma) gives a minimum age for the Yamato Basin. This age range predates rotation of southwest Japan, an event previously believed to be caused by the opening of the Japan Sea.