Chemical composition and dated ages of detrital smectites in sediments at DSDP Legs 43, 48 and 50

Mineralogical, morphological and isotopic (Rb-Sr and K-Ar) determinations were made on some detrital smectites of Palaeocene and Cenomanian ages from DSDP. drillings in the Atlantic Ocean. These minerals are not inert in their depositional environment; authigenic laths grow on detrital sheets with sharp borders. This authigenesis could occur slightly after deposition in a closed system, for some of these smectites. It has been tentatively quantified by the Rb-Sr and K-Ar isotopic methods, which seem also well suited to evaluate the chemical extent of this authigenesis. At least, no preferential loss of 40Ar vs. 87Sr could be detected in the minerals, even in those which are smaller than 0.2 ?m.

Chemistry of interstitial waters of ODP Leg 112 samples

Two distinct hydrogeochemical regimes currently dominate the Peruvian continental margin. One, in shallower water (150-450 m) shelf to upper-slope regions, is characterized by interstitial waters with strong positive chloride gradients with depth. The maximum measured value of 1043 mM chloride at Site 680 at ITS corresponds to a degree of seawater evaporation of ~2 times. Major ion chemistry and strontioum isotopic composition of the interstitial waters suggest that a subsurface brine that has a marine origin and is of pre-early Miocene "age," profoundly influences the chemistry and diagenesis of this shelf environment. Site 684 at ~9°S must be closest to the source of this brine, which becomes diluted with seawater and/or interstitial water as it flows southward toward Site 686 at ~13?S (and probably beyond) at a rate of approximately 3 to 4 cm/yr, since early Miocene time. The other regime, in deep water (3000-5000 m) middle to lower-slope regions, is characterized by interstitial waters with steep negative and nonsteady-state chloride gradients with depth. The minimum measured value of 454 mM chloride, at Site 683 at ITS, corresponds to ~20% dilution of seawater chloride The most probably sources of these low-chloride fluids are gas hydrate dissociation and mineral (particularly clay) dehydration reactions. Fluid advection is consistent with (1) the extent of dilution shown in the chloride profiles, (2) the striking nonsteady-state depth profiles of chlorides at Sites 683 and 688 and of 87Sr/86Sr ratios at Site 685, and (3) the temperatures resulting from an average geothermal gradient of 50°C/km and required for clay mineral dehydration reactions. Strontium isotope data reveal two separate fluid regimes in this slope region: a more northerly one at Sites 683 and 685 that is influenced by fluids with a radiogenic continental strontium signature, and a southerly one at Sites 682 and 688 that is influenced by fluids with a nonradiogenic oceanic signatures. Stratigraphically controlled fluid migration seems to prevail in this margin. Because of its special tectonic setting, Site 679 at ITS is geochemically distinct. The interstitial waters are characterized by seawater chloride concentrations to -200 mbsf and deeper by a significantly lower chloride concentration of about two-thirds of the value in seawater, suggesting mixing with a meteoric water source. Regardless of the hydrogeochemical regime, the chemistry and isotopic compositions of the interstitial waters at all sites are markedly modified by diagenesis, particularly by calcite and dolomite crystallization.

Age model, stable isotopes, major element proportions and endmember unmixing results from four western tropical Atlantic cores

We investigate changes in the delivery and oceanic transport of Amazon sediments related to terrestrial climate variations over the last 250 ka. We present high-resolution geochemical records from four marine sediment cores located between 5 and 12° N along the northern South American margin. The Amazon River is the sole source of terrigenous material for sites at 5 and 9° N, while the core at 12° N receives a mixture of Amazon and Orinoco detrital particles. Using an endmember unmixing model, we estimated the relative proportions of Amazon Andean material ("%-Andes", at 5 and 9° N) and of Amazon material ("%-Amazon", at 12° N) within the terrigenous fraction. The %-Andes and %-Amazon records exhibit significant precessional variations over the last 250 ka that are more pronounced during interglacials in comparison to glacial periods. High %-Andes values observed during periods of high austral summer insolation reflect the increased delivery of suspended sediments by Andean tributaries and enhanced Amazonian precipitation, in agreement with western Amazonian speleothem records. Increased Amazonian rainfall reflects the intensification of the South American monsoon in response to enhanced land-ocean thermal gradient and moisture convergence. However, low %-Amazon values obtained at 12° N during the same periods seem to contradict the increased delivery of Amazon sediments. We propose that reorganizations in surface ocean currents modulate the northwestward transport of Amazon material. In agreement with published records, the seasonal North Brazil Current retroflection is intensified (or prolonged in duration) during cold substages of the last 250 ka (which correspond to intervals of high DJF or low JJA insolation) and deflects eastward the Amazon sediment and freshwater plume.

Geochemistry of volcanic rocks from the Hikurangi and Manihiki Plateaus

Here we present the first radiometric age data and a comprehensive geochemical data set (including major and trace element and Sr-Nd-Pb-Hf isotope ratios) for samples from the Hikurangi Plateau basement and seamounts on and adjacent to the plateau obtained during the R/V Sonne 168 cruise, in addition to age and geochemical data from DSDP Site 317 on the Manihiki Plateau. The 40Ar/39Ar age and geochemical data show that the Hikurangi basement lavas (118-96 Ma) have surprisingly similar major and trace element and isotopic characteristics to the Ontong Java Plateau lavas (ca. 120 and 90 Ma), primarily the Kwaimbaita-type composition, whereas the Manihiki DSDP Site 317 lavas (117 Ma) have similar compositions to the Singgalo lavas on the Ontong Java Plateau. Alkalic, incompatible-element-enriched seamount lavas (99-87 Ma and 67 Ma) on the Hikurangi Plateau and adjacent to it (Kiore Seamount), however, were derived from a distinct high time-integrated U/Pb (HIMU)-type mantle source. The seamount lavas are similar in composition to similar-aged alkalic volcanism on New Zealand, indicating a second wide-spread event from a distinct source beginning ca. 20 Ma after the plateau-forming event. Tholeiitic lavas from two Osbourn seamounts on the abyssal plain adjacent to the northeast Hikurangi Plateau margin have extremely depleted incompatible element compositions, but incompatible element characteristics similar to the Hikurangi and Ontong Java Plateau lavas and enriched isotopic compositions intermediate between normal mid-ocean-ridge basalt (N-MORB) and the plateau basement. These younger (~52 Ma) seamounts may have formed through remelting of mafic cumulate rocks associated with the plateau formation. The similarity in age and geochemistry of the Hikurangi, Ontong Java and Manihiki Plateaus suggest derivation from a common mantle source. We propose that the Greater Ontong Java Event, during which ?1% of the Earth's surface was covered with volcanism, resulted from a thermo-chemical superplume/dome that stalled at the transition zone, similar to but larger than the structure imaged presently beneath the South Pacific superswell. The later alkalic volcanism on the Hikurangi Plateau and the Zealandia micro-continent may have been part of a second large-scale volcanic event that may have also triggered the final breakup stage of Gondwana, which resulted in the separation of Zealandia fragments from West Antarctica.

Palynological and geochemical data of sediment core GeoB3910-2 located offshore Northeast Brazil

High resolution palynological and geochemical data of sediment core GeoB 3910-2 (located offshore Northeast Brazil) spanning the period between 19 600 and 14 500 calibrated year bp (19.6-14.5 ka) show a land-cover change in the catchment area of local rivers in two steps related to changes in precipitation associated with Heinrich Event 1 (H1 stadial). At the end of the last glacial maximum, the landscape in semi-arid Northeast Brazil was dominated by a very dry type of caatinga vegetation, mainly composed of grasslands with some herbs and shrubs. After 18 ka, considerably more humid conditions are suggested by changes in the vegetation and by Corg and C/N data indicative of fluvial erosion. The caatinga became wetter and along lakes and rivers, sedges and gallery forest expanded. The most humid period was recorded between 16.5 and 15 ka, when humid gallery (and floodplain) forest and even small patches of mountainous Atlantic rain forest occurred together with dry forest, the latter being considered as a rather lush type of caatinga vegetation. During this humid phase erosion decreased as less lithogenic material and more organic terrestrial material were deposited on the continental slope of northern Brazil. After 15 ka arid conditions returned. During the humid second phase of the H1 stadial, a rich variety of landscapes existed in Northeast Brazil and during the drier periods small pockets of forest could probably survive in favorable spots, which would have increased the resilience of the forest to climate change.

Paleocoenographic investigations on sediment profile GeoB6008

Near-shore waters along the northwest African margin are characterized by coastal upwelling and represent one of the world's major upwelling regions. Sea surface temperature (SST) records from Moroccan sediment cores, extending back 2500 years, reveal anomalous and unprecedented cooling during the 20th century, which is consistent with increased upwelling. Upwelling-driven SSTs also vary out of phase with millennial-scale changes in Northern Hemisphere temperature anomalies (NHTAs) and show relatively warm conditions during the Little Ice Age and relatively cool conditions during the Medieval Warm Period. Together, these results suggest that coastal upwelling varies with NHTAs and that upwelling off northwest Africa may continue to intensify as global warming and atmospheric CO2 levels increase.

Study on the last deglaciation section of sediment core GeoB6211-2

The North Atlantic Ocean underwent an abrupt temperature increase of 9 °C at high latitudes within a couple of decades during the transition from Heinrich event 1 (H1) to the Bølling warm event, but the mechanism responsible for this warming remains uncertain. Here we address this issue, presenting high-resolution last deglaciation planktic and benthic foraminiferal records of temperature and oxygen isotopic composition of seawater (d18OSW) for the subtropical South Atlantic. We identify a warming of ~6.5 °C and an increase in d18Osw of 1.2 per mil at the permanent thermocline during the transition, and a simultaneous warming of ~3.5 °C with no significant change in d18Osw at intermediate depths. Most of the warming can be explained by tilting the South Atlantic east-west isopycnals from a flattened toward a steepened position associated with a collapsed (H1) and strong (Bølling) Atlantic meridional overturning circulation (AMOC). However, this zonal seesaw explains an increase of just 0.3 per mil in permanent thermocline d18Osw. Considering that d18Osw at the South Atlantic permanent thermocline is strongly influenced by the inflow of salty Indian Ocean upper waters, we suggest that a strengthening in the Agulhas leakage took place at the transition from H1 to the Bølling, and was responsible for the change in d18Osw recorded in our site. Our records high-light the important role played by Indian-Atlantic interocean exchange as the trigger for the resumption of the AMOC and the Bølling warm event. of the AMOC and the Bølling warm event.

Radiocarbon datings and temperature reconstructions of sediment core GeoB10038-4 off SW Sumatra

Surface and thermocline conditions of the eastern tropical Indian Ocean were reconstructed through the past glacial-interglacial cycle by using Mg/Ca and alkenone-paleothermometry, stable oxygen isotopes of calcite and seawater, and terrigenous fraction performed on sediment core GeoB 10038-4 off SW Sumatra (~6°S, 103°E, 1819 m water depth). Results show that annual mean surface and thermocline temperatures varied differently and independently, and suggest that surface temperatures have been responding to southern high-latitude climate, whereas the more variable thermocline temperatures were remotely controlled by changes in the thermocline temperatures of the North Indian Ocean. Except for glacial terminations, salinity proxies indicate that changing intensities of the boreal summer monsoon did not considerably affect annual mean conditions off Sumatra during the past 133,000 years. Our results do not show a glacial-interglacial pattern in the thermocline conditions and reject a linear response of the tropical Indian Ocean thermocline to mid- and high-latitude climate change. Alkenone-based surface temperature estimates varied in line with the terrigenous fraction of the sediment and the East Asian winter monsoon proxy records at the precession band suggestive of monsoon (sea level) to be the dominant control on alkenone temperatures in the eastern tropical Indian Ocean on sub-orbital (glacial-interglacial) timescales.

Coral Sr/Ca records from Bonaire Holocene corals

Proxy reconstructions of tropical Atlantic sea surface temperature (SST) that extend beyond the period of instrumental observations have primarily focused on centennial to millennial variability rather than on seasonal to multidecadal variability. Here we present monthly-resolved records of Sr/Ca (a proxy of SST) from fossil annually-banded Diploria strigosa corals from Bonaire (southern Caribbean Sea). The individual corals provide time-windows of up to 68 years length, and the total number of 295 years of record allows for assessing the natural range of seasonal to multidecadal SST variability in the western tropical Atlantic during snapshots of the mid- to late Holocene. Comparable to modern climate, the coral Sr/Ca records reveal that mid- to late Holocene SST was characterised by clear seasonal cycles, persistent quasi-biennial and prominent interannual as well as inter- to multidecadal-scale variability. However, the magnitude of SST variations on these timescales has varied over the last 6.2 ka. The coral records show increased seasonality during the mid-Holocene consistent with climate model simulations indicating that southern Caribbean SST seasonality is induced by insolation changes on orbital timescales, whereas internal dynamics of the climate system play an important role on shorter timescales. Interannual SST variability is linked to ocean-atmosphere interactions of Atlantic and Pacific origin. Pronounced interannual variability in the western tropical Atlantic is indicated by a 2.35 ka coral, possibly related to a strengthening of the variability of the El Niño/Southern Oscillation throughout the Holocene. Prominent inter- to multidecadal SST variability is evident in the coral records and slightly more pronounced in the mid-Holocene. We finally argue that our coral data provide a target for studying Holocene climate variability on seasonal and interannual to multidecadal timescales, when using further numerical models and high-resolution proxy data.

Neodymium isotope signature of Holocene corals

The neodymium isotopic composition of marine precipitates is increasingly recognized as a powerful tool for identifying changes in ocean circulation and mixing on million year to millennial timescales. Unlike nutrient proxies such as ?13C or Cd/Ca, Nd isotopes are not thought to be altered in any significant way by biological processes, and thus they can serve as a quasi-conservative water mass tracer. However, the application of Nd isotopes in understanding the role of thermohaline circulation in rapid climate change is currently hindered by the lack of direct constraints on the signature of the North Atlantic end-member through time. Here we present the first results of Nd isotopes measured in U-Th-dated deep-sea corals from the New England seamounts in the northwest Atlantic Ocean. Our data are consistent with the conclusion that the Nd isotopic composition of North Atlantic deep and intermediate water has remained nearly constant through the last glacial cycle. The results address long-standing concerns that there may have been significant changes in the Nd isotopic composition of the North Atlantic end-member during this interval and substantiate the applicability of this novel tracer on millennial timescales for paleoceanography research.

Geochemistry of ODP Leg 125 peridotites

Ocean Drilling Program Leg 125 recovered serpentined harzburgites and dunites from a total of jive sites on the crests and flanks of two serpen finite seamounts, Conical Seamount in the Mariana forearc and Torishima Forearc Seamount in the Izu-Bonin forearc. These are some of the first extant forearc peridotites reported in the literature and they provide a window into oceanic, supra-subduction zone (SSZ) mantle processes. Harzbutrgites from both seamounts are very refractory with low modal clinopyroxene (<4%), chrome-rich spinels (cx-number = 0.40-0.80), very low incompatible element contents, and (with the exception of amphibole-bearing samples) U-shaped rare earth element (REE) profiles with positive Eu anomalies. Both sets of peridotites have olivine-spinel equilibration temperatures that are low compared with abyssal peridotites, possibly because of water-assisted diffusional equilibration in the SSZ environment However, other features indicate that the harzburgites from the two seamounts have very different origins. Harzburgites from Conical Seamount are characterized by calculated oxygen fugacities between FMQ (fayalite- magnetite- quartz) - 1.1 (log units) and FMQ + 0.4 which overlap those of mid-ocean ridge basalt (MORB) peridotites. Dunites from Conical Seamotmt contain small amounts of clinopyroxene, orthopyroxene and amphibole and are light REE (LREE) enriched. Moreover; they are considerably more oxidized than the harzburgites to which they are spatially related, with calculated oxygen fugacities of FMQ -0.2 toFMQ + 1.2. Using textural and geochemical evidence, we interpret these harzburgites as residual MORB mantle (from 15 to 20 % fractional melting) which has subsequently been modified by interaction with boninitic melt ivithin the mantle wedge, and these dunites as zones of focusing of this melt in which pyroxene has preferentially been dissolved from the harzbutgite protolith. In contrast, harzburgites from Torishima Forearc Seamount give calculated oxygen fugacities between FMQ + 0.8 and FMQ + l.6, similar to those calculated for other subduction-zone related peridotites and similar to those calculated for the dunites (FMQ + 1.2 to FMQ + 1.8) from the same seamount. In this case, we interpret both the harzburgites and dunites as linked to mantle melting (20-25 % fractional melting) in a supra-subduction zone environment The results thus indicate that the forearc is underlain by at least two types of mantle lithosphere, one being trapped or accreted oceanic lithosphere, the other being lithosphere formed by subduction-related melting. They also demonstrate that both types of mantle lithosphere may have undergone extensive interaction with subduction-derived magmas.

Osmium, and stable carbon and oxygen isotope record accross the PETM

In the latest Paleocene an abrupt shift to more negative d13C values has been documented at numerous marine and terrestrial sites (Bralower et al., 1997, doi:10.1130/0091-7613(1997)025<0963:HRROTL>2.3.CO;2; Cramer et al., 1999; Kaiho et al., 1996, doi:10.1029/96PA01021; Kennett and Stott, 1991, doi:10.1038/353225a0; Koch et al., 1992, doi:10.1038/358319a0; Stott et al., 1996; Thomas and Shackleton, 1996, doi:10.1144/GSL.SP.1996.101.01.20; Zachos et al., 1993). This carbon isotope event (CIE) is coincident with oxygen isotope data that indicate warming of surface waters at high latitudes of nearly 4°-6°C (Kennett and Stott, 1991, doi:10.1038/353225a0) and more moderate warming in the subtropics (Thomas et al., 1999, doi:10.1029/1999PA900031). Here we report 187Os/188Os isotope records from the North Atlantic and Indian Oceans which demonstrate a >10% increase in the 187Os/188Os ratio of seawater coincident with the late Paleocene CIE. This excursion to higher 187Os/188Os ratios is consistent with a global increase in weathering rates. The inference of increased chemical weathering during this interval of unusual warmth is significant because it provides empirical evidence supporting the operation of a feedback between chemical weathering rates and warm global climate, which acts to stabilize Earth's climate (Walker et al., 1981). Estimates of the duration of late Paleocene CIE (Bains et al., 1999, doi:10.1126/science.285.5428.724; Bralower et al., 1997, doi:10.1130/0091-7613(1997)025<0963:HRROTL>2.3.CO;2; Norris and Röhl, 1999, doi:10.1038/44545; Röhl et al., 2000, doi:10.1130/0091-7613(2000)28<927:NCFTLP>2.0.CO;2) in conjunction with the Os isotope data imply that intensified chemical weathering in response to warm, humid climates can occur on timescales of 104-105 years. This interpretation requires that the late Paleocene thermal maximum Os isotope excursion be produced mainly by increased Os flux to the ocean rather than a transient excursion to higher 187Os/188Os ratios in river runoff. Although we argue that the former is more likely than the latter, we cannot rule out significant changes in the 187Os/188Os ratio of rivers.

87Sr/86Sr ratios of planktonic foraminifers and interstitial waters at DSDP Hole 90-593

Detailed profiles of the Sr isotopic compositions of fossil planktonic foraminifers and interstitial waters have been measured from DSDP Site 593 to determine the Sr isotopic composition of seawater during the last 40 m.y. Foraminiferal recrystallization was assessed through scanning electron microscopy (SEM) and Sr/Ca ratios. Foraminifers were shown to be well preserved. Results document that the seawater 87Sr/86Sr has increased continuously but not uniformly, since the latest Eocene.

K-Ar dating of altered deep-sea igneous rocks from DSDP Legs 2, 34, and 35

In an attempt to establish criteria for obtaining reliable K-Ar dates, conventional K-Ar studies of several Deep Sea Drilling Project sites were undertaken. K-Ar dates of these rocks may be subject to inaccuracies as the result of sea-water alteration. Inaccuracies may also result from the presence of excess radiogenic 40Ar trapped in rapidly cooled rocks at the time of their formation. The results obtained for DSDP Leg 34 basalts indicate that lowering of K-Ar dates, which is related to potassium addition by weathering, is a major cause of uncertainty in obtaining reliable K-Ar dates for deep-sea rocks. It could not be determined if the potassium addition to the basalts occurred at the time of formation, t_o, or continuously from t_o to the present. Calculations show that sediment cover is not a significant barrier to the diffusion of potassium into the basalt. 40Ar loss contributes, at least in part, to the lowering of the K-Ar date in rocks that have added potassium. The meaning of the K-Ar results obtained for DSDP Legs 35 and 2 basalts could not be unambiguously established. Because of the problems involved, caution must be used in interpreting the meaning of conventional K-Ar dates for deep-sea rocks.

Geochemistry of ODP Hole 183-1137A basalts

The Kerguelen Plateau and Broken Ridge in the southern Indian Ocean together represent one of the most voluminous large igneous provinces (LIPs) ever emplaced on Earth. A scientific objective of Ocean Drilling Program (ODP) Leg 183 was to constrain the post-melting magma evolution of Kerguelen Plateau magmas. In an effort to better understand this evolution, isotopic and trace element analysis of individual plagioclase crystals hosted within two Kerguelen Plateau basalts recovered from Elan Bank were undertaken. Previous whole-rock studies established that the two host basalts investigated in this study are samples of crustally contaminated (lower group) and relatively uncontaminated (upper group) basalt. Plagioclase phenocrysts from the uncontaminated basalt are dominantly normal zoned and exhibit a 87Sr/86SrI range of 0.704845-0.704985, which overlaps uncontaminated group whole-rock values previously reported. Plagioclase crystals from the contaminated basalt are dominantly reverse zoned and exhibit a 87Sr/86SrI range of 0.705510-0.705735, which all lie within contaminated group whole-rock values previously reported. There are no systematic within crystal core to rim variations in 87Sr/86SrI from either group, with the exception that contaminated group crystal rims have overall less radiogenic 87Sr/86SrI than other zones. These observations indicate that crustal assimilation occurred before the formation of Unit 10 plagioclase phenocrysts, which is supported by parent magma trace element abundance data inverted using carefully calculated partition coefficients. Trace element diffusion modeling indicates that the upper group basalt (Unit 4) experienced a more vigorous eruptive flux than the lower group basalt (Unit 10). We suggest that plagioclase phenocrysts in both the upper and lower group basalts originated from the shallowest section of what was likely a complex magma chamber system. We contend that the magmatic system contained regions of extensive plagioclase-dominated crystal mush. Crustal assimilation was not a significant ongoing process in this portion of the Elan Bank magmatic system. Both basalts exhibit compelling evidence for remobilization and partial resorption of crystalline debris (e.g., reverse zoned crystals, glomerocrysts). We suggest Unit 4 and 10 magmas ascended different sections of the Elan Bank magma system, where the Unit 10 magmas ascended a section of the magma system that penetrated a stranded fragment of continental crust.