Elemental contents, non-carbonate, fatty acids and alcohols analysis from different Holes of IODP Expedition 310

During IODP Expedition 310 (Tahiti Sea Level), drowned Pleistocene-Holocene barrier-reef terraces were drilled on the slope of the volcanic island. The deglacial reef succession typically consists of a coral framework encrusted by coralline algae and later by microbialites; the latter make up < 80% of the rock volume. Lipid biomarkers were analyzed in order to identify organisms involved in reef-microbialite formation at Tahiti, as the genesis of deglacial microbialites and the conditions favoring their formation are not fully understood. Sterols plus saturated and monounsaturated short-chain fatty acids predominantly derived from both marine primary producers (algae) and bacteria comprise 44 wt% of all lipids on average, whereas long-chain fatty acids and long-chain alcohols derived from higher land plants represent an average of only 24 wt%. Bacterially derived mono-O-alkyl glycerol ethers (MAGEs) and branched fatty acids (10-Me-C16:0; iso- and anteiso-C15:0 and -C17:0) are exceptionally abundant in the microbial carbonates (average, 19 wt%) and represent biomarkers of intermediate-to-high specificity for sulfate-reducing bacteria. Both are relatively enriched in 13C compared to eukaryotic lipids. No lipid biomarkers indicative of cyanobacteria were preserved in the microbialites. The abundances of Al, Si, Fe, Mn, Ba, pyroxene, plagioclase, and magnetite reflect strong terrigenous influx with Tahitian basalt as the major source. Chemical weathering of the basalt most likely elevated nutrient levels in the reefs and this fertilization led to an increase in primary production and organic matter formation, boosting heterotrophic sulfate reduction. Based on the observed biomarker patterns, sulfate-reducing bacteria were apparently involved in the formation of microbialites in the coral reefs off Tahiti during the last deglaciation.

Primary composition, alteration, and origin of Cretaceous volcaniclastic rocks at DSDP Site 89-585

An upper Aptian to middle Albian series of volcaniclastic rocks more than 300 m thick was drilled at Site 585 in the East Mariana Basin. On the basis of textural and compositional (bulk-rock chemistry, primary and secondary mineral phases) evidence, the volcaniclastic unit is subdivided into a lower (below 830 m sub-bottom) and an upper (about 670-760 m) sequence; the boundary in the interval between is uncertain owing to lack of samples. The rocks are dominantly former vitric basaltic tuffs and minor lapillistones with lesser amounts of crystals and basaltic lithic clasts. They are mixed with shallow-water carbonate debris (ooids, skeletal debris), and were transported by mass flows to their site of deposition. The lower sequence is mostly plagioclase- and olivine-phyric with lesser amounts of Ti-poor clinopyroxene. Mineralogical and bulk-rock chemical data indicate a tholeiitic composition slightly more enriched than N-MORB (normal mid-ocean ridge basalt). Transport was by debris flows from shallow-water sites, as indicated by admixed ooids. Volcanogenic particles are chiefly moderately vesicular to nonvesicular blocky shards (former sideromelane) and less angular tachylite with quench plagioclase and pyroxene, indicating generation of volcanic clasts predominantly by spalling and breakage of submarine pillow and/or sheet-flow lavas. The upper sequence is mainly clinopyroxene- and olivine-phyric with minor plagioclase. The more Ti-rich clinopyroxene and the bulk-rock analyses show that the moderately alkali basaltic composition throughout is more mafic than the basal tholeiitic sequence. Transport was by turbidity currents. Rounded epiclasts of crystalline basalts are more common than in the lower sequence, and, together with the occurrence of oxidized olivine pseudomorphs and vesicular tachylite, are taken as evidence of derivation from eroded subaerially exposed volcanics. Former sideromelane shards are more vesicular than in the lower sequence; vesicularity exceeds 60 vol.% in some clasts. The dominant clastic process is interpreted to be by shallow-water explosive eruptions. All rocks have undergone low-temperature alteration; the dominant secondary phases are "palagonite," chlorite/smectite mixed minerals, analcite, and chabazite. Smectite, chlorite, and natrolite occur in minor amounts. Phillipsite is recognized as an early alteration product, now replaced by other zeolites. During alteration, the rocks have lost up to 50% of their Ca, compared with a fresh shard and fresh glass inclusions in primary minerals, but have gained much less K, Rb, and Ba than expected, indicating rapid deposition prior to significant seafloor weathering.

Osmium isotope composition of ODP Hole 121-758A

This study presents osmium (Os) isotope and elemental data for cleaned planktic foraminifera, authigenic Fe-Mn oxyhydroxides and pelagic carbonate host sediments from ODP site 758 in the southernmost reaches of the Bay of Bengal. The Os in the bulk sediments appears to be dominantly hydrogeneous (sourced by carbonate and Fe-Mn oxyhydroxide), but variations in this particular core are controlled by the presence of volcanic ash. Fe-Mn oxyhydroxide leachates (of the bulk sediments) from Holocene samples also yield an Os isotope composition close to that of seawater, but the record diverges from that of foraminifera at a depth corresponding to the oxic/post-oxic boundary, suggesting diagenetic mobilization of Os at depths below this. Holocene planktic foraminifera, cleaned using oxidative-reductive techniques, also give Os isotope compositions indistinguishable from modern seawater, but the record obtained for the past 150 kyr shows strong covaraitions of 187Os/188Os with both the local and global oxygen isotope record, with less radiogenic Os isotope compositions during glacial intervals. These results indicate that foraminifera provide a robust record of seawater Os isotope compositions, and comparison of the data obtained here with records from the other major oceans demonstrate global changes in 187Os/188Os over this time interval, while the covariation with oxygen isotopes suggest a process controlling the Os isotope composition that is in phase with global climate cycles. Global excursions to relatively unradiogenic 187Os/188Os during glacial intervals are consistent with decreased input of radiogenic continental material, reflecting cooler temperatures and reduced continental runoff. Modelling indicates that the shift to unradiogenic values during glacial intervals could be caused by an ~30% decrease in the global river flux, with an ~5% change in river composition. If the residence time of Os in the oceans is ~5 ka then the post-glacial recovery to present-day seawater values is consistent with a corresponding increase in the river flux of around 30%. However, if the residence time of Os is closer to 40 ka, as is suggested by the global river flux, then this demands either significant changes in both the riverine Os flux and composition of around 40% and 30%, respectively, that closely follow the oxygen isotope record, or else a short-lived post-glacial pulse of weathering some 75% greater than the steady-state flux. In either case, these results clearly indicate that climatic changes affect both the flux and composition of weathered material delivered to the oceans on glacial-interglacial timescales.

Isotopic ratios and geochemical composition of ODP Hole 176-735B minerals

The mineralogy and stable (O and C) and Sr isotopic compositions of low-temperature alteration phases were determined in Hole 735B gabbroic rocks in order to understand the processes of low-temperature alteration in this uplifted block of lower oceanic crust. Phyllosilicates include smectite (saponite, Mg montmorillonite, and nontronite), chlorite/smectite, chlorite, talc, and serpentine. Other phases include prehnite, albite, K-feldspar, analcite, natrolite, thompsonite, pyrite, and titanite. The low-grade mineral assemblages mainly represent zeolite facies and lower-temperature "seafloor weathering" processes. Phyllosilicates formed over a range of temperatures but may also reflect variable reaction progress. Alteration temperatures were probably somewhat greater below 1300 meters below seafloor. Mineralogy and isotopic data indicate that conditions were mostly reducing and that seawater solutions were rock dominated. Carbonates formed late from cold and generally oxidizing seawater solution, however, as seawater penetrated downward as the result of fracturing and faulting in the uppermost portion of the uplifted crustal block.

Late Cretaceous dinoflagellate cysts of ODP Hole 120-748C

At Ocean Drilling Program Hole 748C in the Southern Indian Ocean, a total of 171 Late Cretaceous dinoflagellate taxa were encountered in 38 productive samples from Cores 120-748C-27R through 120-748C-62R (407-740 mbsf). Four provisional dinoflagellate assemblage zones and five subzones were recognized based on the character of the dinoflagellate flora and the first/last occurrences of some key species. Isabelidinium korojonense and Nelsoniella aceras occur in Zone A together with Oligosphaeridium pulcherrimum and Trithyrodinium suspect urn. Zone B was delineated by the total range of Odontochitina cribropoda. Zone C was separated from Zone B by the presence of Satyrodinium haumuriense, and Zone D is dominated by new taxa. The dinocyst assemblages bear a strong affinity to Australian assemblages. Paleoenvironmental interpretations based mainly on dinocysts suggest that during the ?Santonian-Campanian to the Maestrichtian this portion of the Kerguelen Plateau was a shallow submerged plateau, similar to nearshore to offshore to upper slope environments with water depths of tens to hundreds of meters, but isolated from the major continents of the Southern Hemisphere. Starting perhaps in the late Cenomanian (Mohr and Gee, 1992, doi:10.2973/odp.proc.sr.120.196.1992), the Late Cretaceous transgression over the plateau reached its maximum during the late Campanian. The plateau may have been exposed above sea level and subjected to weathering during the latest Maestrichtian. The studied dinocyst assemblages characterized by species of Amphidiadema, Nelsoniella, Satyrodinium, and Xenikoon together with abundant Chatangiella (the large-size species) and Isabelidinium suggest that a South Indian Province (tentatively named the Helby suite) may have existed during the Campanian-Maestrichtian in comparison with the other four provinces of Lentin and Williams. One new genus, three new species, and two new subspecies of dinocysts are described.

Sediment investigations in the Kara Sea

AMS-14C dated sediment cores from the Ob and Yenisei estuaries and the adjacent inner Kara Sea were investigated to determine the siliclastic and organic carbon fluxes and their relationship to paleoenvironmental changes. The variability of sediment fluxes during Holocene times is related to the post-glacial sea-level rise and changes in river discharge and coastal erosion input. Whereas during the late/middle Holocene most of the terrigenous sediments were deposited in the estuaries and the areas directly off the estuaries, huge amounts of sediments accumulated on the Kara Sea shelf farther north during the early Holocene before about 9 Cal. kyrs. BP. The maximum accumulation at that time is related to the lowered sea level, increased coastal erosion, and increased river discharge due to the final stage of mountain deglaciation of the Putoran Massif. Increased supply of Yenisei-derived material indicated by peak magnetic susceptibility values probably occurred in climate-related pulses culminating near 11, 10, and 9 Cal. kyrs. BP. As sea level rose, the main Holocene depocenter migrated southward. Based on hydrogen index values and n-alkanes, the organic matter is predominantly of terrigenous origin. Maximum accumulation rates of 1.5 to more than 6 g/cm**2/y occurred in the early Holocene sediments, suggesting more humid climatic conditions with an increased vegetation cover in the source area at that time. In general, high organic carbon accumulation rates characterize the estuaries and the inner Kara Sea as important sink for terrigenous organic carbon. A high-resolution record of Holocene variability of magnetic susceptibility (MS) in an AMS14C-dated sediment core from the northern Yenisei estuary may indicate natural variability of Arctic climate change and river discharge on a centennial to millenial time scale. Short-term maxima in MS probably related to warmer climate, enhanced precipitation, intensified weathering/erosion and increased river discharge, display a frequency of about 300 to 700 years.

Strontium isotopic composition and chronology of sediments from DSDP Site 90-588

We report 261 strontium isotopic analyses of well-preserved planktonic foraminifers from three Deep Sea Drilling Project Sites (519, 588, and 607). These samples cover the period from 24 Ma to present with an average of approximately one sample per 100 ka. The combination of high sample density and uniformity of analytical procedures has produced a well-defined record of changes in the 87Sr/86Sr of seawater during the Neogene. The record can be viewed as a series of essentially linear segments with slopes ranging from as high as 0.00006/m.y. to as low as 0/m.y. The times associated with major inflections in the curve do not appear to correspond to simple geologic phenomena such as eustatic cycles, but are probably controlled by a combination of tectonic and climatic factors that influenced the abundance and isotopic composition of terrestrial strontium input to the oceans. The strontium isotopic data are consistent with a progressive increase in the chemical weathering rates of the continents during the Neogene, probably related to repeated glaciations, increased exposure of continents by lowered sea level, and increased continental relief resulting from high rates of tectonic uplift.

Ba/Ca ratios in Neogloboquadrina pachyderma of sedimet core 94B17

Down-core samples of the planktonic foraminifer Neogloboquadrina pachyderma sinistral from the Mendeleyev Ridge in the western Arctic Ocean have been analyzed for Ba/Ca and d18O. The apparent distribution coefficient for N. pachyderma sin. is estimated at DBa = 0.22 ± 0.02. A meltwater event is identified at around 11.8 14C kyr BP and is coincident with elevated Ba/Ca ratios. The barium enrichment is believed to be the result of enhanced weathering and erosion following glaciation. Additionally, barium may have desorbed from shelf sediments as sea level rose. Changes in Ba/Ca correlate with the retreat of the Laurentide Ice Sheet and the evolution of the Mackenzie River drainage basin. Therefore maximum Ba/Ca in Arctic surface waters at 11.8 ka may be indicative of an increase in the export of freshwater from the Arctic to the North Atlantic, potentially contributing to the onset of the Younger Dryas. This work suggests that Ba/Ca in planktonic foraminifera may be a useful indicator of the timing and processes associated with deglaciation.

X-ray fluorescence scanning of discrete samples on the Schwalbenberg II loess-paleosol sequence, raw data, magnetic susceptibility, organic carbon and U-ratio as grainsize index

The Schwalbenberg II loess-paleosol sequence (LPS) denotes a key site for Marine Isotope Stage (MIS 3) in Western Europe owing to eight succeeding cambisols, which primarily constitute the Ahrgau Subformation. Therefore, this LPS qualifies as a test candidate for the potential of temporal high-resolution geochemical data obtained X-ray fluorescence (XRF) scanning of discrete samplesproviding a fast and non-destructive tool for determining the element composition. The geochemical data is first contextualized to existing proxy data such as magnetic susceptibility (MS) and organic carbon (Corg) and then aggregated to element log ratios characteristic for weathering intensity [LOG (Ca/Sr), LOG (Rb/Sr), LOG (Ba/Sr), LOG (Rb/K)] and dust provenance [LOG (Ti/Zr), LOG (Ti/Al), LOG (Si/Al)]. Generally, an interpretation of rock magnetic particles is challenged in western Europe, where not only magnetic enhancement but also depletion plays a role. Our data indicates leaching and top-soil erosion induced MS depletion at the Schwalbenberg II LPS. Besides weathering, LOG (Ca/Sr) is susceptible for secondary calcification. Thus, also LOG (Rb/Sr) and LOG (Ba/Sr) are shown to be influenced by calcification dynamics. Consequently, LOG (Rb/K) seems to be the most suitable weathering index identifying the Sinzig Soils S1 and S2 as the most pronounced paleosols for this site. Sinzig Soil S3 is enclosed by gelic gleysols and in contrast to S1 and S2 only initially weathered pointing to colder climate conditions. Also the Remagen Soils are characterized by subtle to moderate positive excursions in the weathering indices. Comparing the Schwalbenberg II LPS with the nearby Eifel Lake Sediment Archive (ELSA) and other more distant German, Austrian and Czech LPS while discussing time and climate as limiting factors for pedogenesis, we suggest that the lithologically determined paleosols are in-situ soil formations. The provenance indices document a Zr-enrichment at the transition from the Ahrgau to the Hesbaye Subformation. This is explained by a conceptual model incorporating multiple sediment recycling and sorting effects in eolian and fluvial domains.

Stable isotopes, sedimentology and geochemical analyses of Middle Eocene to early Miocene sediments of ODP Site 177-1090

During Leg 177 of the Ocean Drilling Program (ODP), a well-preserved middle Eocene to lower Miocene sediment record was recovered at Site 1090 on the Agulhas Ridge in the Atlantic sector of the Southern Ocean. This new sediment record shows evidence of a hitherto unknown late Eocene opal pulse. Lithological variations, compositional data, mass-accumulation rates of biogenic and lithogenic sediment constituents, grain-size distributions, geochemistry, and clay mineralogy are used to gain insights into mid-Cenozoic environmental changes and to explore the circumstances of the late Eocene opal pulse in terms of reorganizations in ocean circulation. The base of the section is composed of middle Eocene nannofossil oozes mixed with red clays enriched in authigenic clinoptilolite and smectite, deposited at low sedimentation rates (LE 2 cm/ka). It indicates reduced terrigenous sediment input and moderate biological productivity during this preglacial warm climatic stage. The basal strata are overlain by an extended succession (100 m, 4 cm/ka) of biosiliceous oozes and muds, comprising the upper middle Eocene, the entire late Eocene, and the lowermost early Oligocene. The opal pulse occurred between 37.5 and 33.5 Ma and documents the development of upwelling cells along topographic highs, and the utilization of a marine nutrient- and silica reservoir established during the pre-late Eocene through enhanced submarine hydrothermal activity and the introduction of terrigenous solutions from chemical weathering on adjacent continents. This palaeoceanographic overturn probably was initiated through the onset of increased meridional ocean circulation, caused by the diversion of the Indian equatorial current to the south. The opal pulse was accompanied by increased influxes of terrigenous detritus from southern African sources (illite), mediated by enhanced ocean particle advection in response to modified ocean circulation. The opal pulse ended because of frontal shifts to the south around the Eocene/Oligocene boundary, possibly in response to the opening of the Drake Passage and the incipient establishment of the Antarctic Circumpolar Current. Condensed sediments and a hiatus within the early Oligocene part of the section possibly point to an invigoration of the deep-reaching Antarctic Circumpolar Current. The mid-Oligocene to lower Miocene section on long time scale exhibits less pronounced lithological variations than the older section and points to relatively stable palaeoceanographic conditions after the dramatic changes in the late Eocene to early Oligocene.

Chemical composition of the red bed layer in DSDP Hole 38-336

Clay minerals were studied in samples from the Eocene red bed layer of DSDP Hole 336. It is shown that composition and distribution of clay minerals have zoning, which is usually typical for the terrestrial crust of chemical weathering of basic rocks.

Mineral quantification of a Jordan Cretaceous outcrop (Section GM3, Ghawr Al Mazar, Ghor al Mazrar)

Cyclic fluctuations in global sea level during epochs of warm greenhouse climate have remained enigmatic, because absence or subordinate presence of polar ice during these periods precludes an explanation by glacio-eustatic forcing. An alternative concept suggests that the water-bearing potential of groundwater aquifers is equal to that of ice caps and that changes in the dynamic balance of aquifer charge versus discharge, as a function of the temperature-related intensity of the hydrological cycle, may have driven eustasy during warm climates. However, this idea has long been neglected for two reasons: 1) the large storage potential of subsurface aquifers was confused with the much smaller capacity of rivers and lakes and 2) empirical data were missing that document past variations in the hydrological cycle in relation to eustasy. In the present study we present the first empirical evidence for changes in precipitation, continental weathering intensity and evaporation that correlate with astronomically (long obliquity) forced sea-level cycles during the warmest period of the Cretaceous (Cenomanian-Turonian). We compare sequence-stratigraphic data with changes in the terrigenous mineral assemblage in a low-latitude marine sedimentary sequence from the equatorial humid belt at the South-Tethyan margin (Levant carbonate platform, Jordan), thereby avoiding uncertainties from land-ocean correlations. Our data indicate covariance between cycles in weathering and sea level: predominantly chemical weathering under wet climate conditions is reflected by dominance of weathering products (clays) in deposits that represent sea-level fall (aquifer charge > discharge). Conversely, preservation of weathering-sensitive minerals (feldspars, epidote and pyroxenes) in transgressive sediments reflects decreased continental weathering due to dryer climate (aquifer discharge > charge). Based on our results we suggest that aquifer-eustasy represents a viable alternative to glacio-eustasy as a driver of cyclic 3rd-order sea-level fluctuations during the middle Cretaceous greenhouse climate, and it may have been a pervasive process throughout Earth history.

Lead isotopes inthe Eastern Equatorial Pacific

The influence of atmospheric dust on climate and biogeochemical cycles in the oceans is well understood but poorly quantified. Glacial atmospheric dust loads were generally greater than those during the Holocene, as shown, for example, by the covariation of dust fluxes in the Equatorial Pacific and Antarctic ice cores. Nevertheless, it remains unclear whether these increases in dust flux were associated with changes in sources of dust, which would in turn suggest variations in wind patterns, climate or paleo-environment. Such questions can be answered using radiogenic isotope tracers of dust provenance. Here, we present a 160-kyr high-precision lead isotope time-series of dust input to the Eastern Equatorial Pacific (EEP) from core ODP Leg 138, Site 849 (0°11.59' N, 110°31.18' W). The Pb isotope record, combined with Nd isotope data, rules out contributions from Northern Hemisphere dust sources, north of the Intertropical Convergence Zone, such as Asia or North Africa/Sahara; similarly, eolian sources in Australia, Central America, the Northern Andes and Patagonia appear insignificant based upon the radiogenic isotope data. Fluctuations in Pb isotope ratios throughout the last 160 kyr show, instead, that South America remained the prevailing source of dusts to the EEP. There are two distinct South American Pb isotope end-members, constrained to be located in the south Central Volcanic Zone (CVZ, 22° S - 27.5° S) and the South Volcanic Zone (SVZ, 33° S - 43° S), with the former most likely originating in the Atacama Desert. Dust availability in the SVZ appears to be related to the weathering of volcanic deposits and the development of ash-derived Andosols, and influenced by local factors that might include vegetation cover. Variations in the dust fluxes from the two sources are in phase with both the dust flux and temperature records from Antarctican ice cores. We show that the forcing of dust provenance over time in the EEP overall is influenced by high-southerly-latitude climate conditions, leading to changes in the latitudinal position and strength of the South Westerlies as well as the coastal winds that blow northward along the Chilean margin. The net result is a modulation of dust emission from the Atacama Desert and the SVZ via a northward migration of the South Westerlies during cold periods and southward retreat during glacial terminations.