Geochemistry of surface sediment samples from the equatorial Atlantic south of the Azores

In order to recognize the distribution of hydrothermal tracers south of the Azores, a series of cores has been sampled during the GEOFAR cruise. The distribution of the Mn concentrations shows that the hydrothermal influence is maximum within and to the north-west of the Lucky Strike segment. North of the East-Azores Fracture Zone the sediments are enriched in Ba which could be derived from different sources. The chemical composition of the interstitial water shows that water advection is limited. Mn, Cu, Ni fluxes evaluated in one site have increased during isotopic stages 4 and 2 and the deglaciation.

Geochemistry of basement carbonates from ODP Site 801 in the western Pacific Ocean

Many studies argue, based partly on Pb isotopic evidence, that recycled, subducted slabs reside in the mantle source of ocean island basalts (OIB) (Hofmann and White, 1982, doi:10.1016/0012-821X(82)90161-3; Weaver, 1991 doi:10.1016/0012-821X(91)90217-6; Lassiter, and Hauri, 1998, doi:10.1016/S0012-821X(98)00240-4). Such models, however, have remained largely untested against actual subduction zone inputs, due to the scarcity of comprehensive measurements of both radioactive parents (Th and U) and radiogenic daughter (Pb) in altered oceanic crust (AOC). Here, we discuss new, comprehensive measurements of U, Th, and Pb concentrations in the oldest AOC, ODP Site 801, and consider the effect of subducting this crust on the long-term Pb isotope evolution of the mantle. The upper 500 m of AOC at Site 801 shows >4-fold enrichment in U over pristine glass during seafloor alteration, but no net change to Pb or Th. Without subduction zone processing, ancient AOC would evolve to low 208Pb/206Pb compositions unobserved in the modern mantle (Hart and Staudigel, 1989 [Isotopic characterization and identification of recycled components, in: Crust/Mantle Recycling at Convergence Zones, Eds. S.R. Hart, L. Gqlen, NATO ASI Series. Series C: Mathematical and Physical Sciences 258, pp. 15-28, D. Reidel Publishing Company, Dordrecht-Boston, 1989]). Subduction, however, drives U-Th-Pb fractionation as AOC dehydrates in the earth's interior. Pacific arcs define mixing trends requiring 8-fold enrichment in Pb over U in AOC-derived fluid. A mass balance across the Mariana subduction zone shows that 44-75% of Pb but <10% of U is lost from AOC to the arc, and a further 10-23% of Pb and 19-40% of U is lost to the back-arc. Pb is lost shallow and U deep from subducted AOC, which may be a consequence of the stability of phases binding these elements during seafloor alteration: U in carbonate and Pb in sulfides. The upper end of these recycling estimates, which reflect maximum arc and back-arc growth rates, remove enough Pb and U from the slab to enable it to evolve rapidly (<<0.5 Ga) to sources suitable to explain the 208Pb/206Pb isotopic array of OIB, although these conditions fail to simultaneously satisfy the 207Pb/206Pb system. Lower growth rates would require additional U loss (29%) at depths beyond the zones of arc and back-arc magmagenesis, which would decrease upper mantle kappa (232Th/238U) over time, consistent with one solution to the "kappa conundrum" (Elliott et al., 1999, doi:10.1016/S0012-821X(99)00077-1). The net effects of alteration (doubling of l [238U/204Pb]) and subduction (doubling of omega [232Th/204Pb]) are sufficient to create the Pb isotopic signatures of oceanic basalts.

Oxygen and hydrogen isotope ratios of pore waters from ODP sites in the Mediterranean Sea

Pore fluids from two ODP sites at Eastern Mediterranean mud volcanoes have been analyzed for their Cl concentration and their delta18O and deltaD isotopic composition. The Cl data span a wide range of concentrations, from extremely depleted with respect to seawater (as low as 60 mM) at the crest of Milano dome (site 970) to strongly enriched (up to 5.4 M) at Napoli dome (site 971). Chloride enrichment is known to be due to dissolving Messinian evaporites, whereas the source of the low-Cl fluid is deduced from stable isotope data presented here. The isotopic composition of the endmember fluid is found to be +10? for delta18O and -32? for deltaD for low- as well as for high-Cl waters. From this signature it can be concluded that neither gas hydrates nor meteoric water play a significant role in the freshening of the pore water. Several other processes altering the delta18O/deltaD composition of pore waters are discussed and considered to be of only negligible influence. The process characterizing the isotopic composition of the fluid is found to be clay mineral dehydration (mainly smectite-illite transformation), corresponding to a depth range of 3.5-7 km and an elevated temperature of about 120-165°C. A quantitative estimate shows that this reaction is capable of producing the observed extreme Cl depletion.

Paleomagnetic and rock magnetic data from IODP Site U1308

Integrated Ocean Drilling Program (IODP) Site U1308 (central North Atlantic) records paleomagnetic directional and relative paleointensity (RPI) variations for the last 1.5 Myr, in 110 m of the sediment sequence at a mean sedimentation rate of 7.3 cm/kyr. A detailed benthic oxygen isotope record was combined with RPI to produce an integrated, high-resolution magneto-isotopic stratigraphy for Site U1308. Apart from the well-known polarity reversals in this interval, the Punaruu excursion is recorded at 1092 ka and the Cobb Mountain Subchron in the 1182-1208 ka interval. The paleointensity proxies are determined as slopes of NRM versus ARM and NRM versus ARMAQ (ARM acquisition) with linear correlation coefficients to monitor the quality of the linear fit. The RPI record for Site U1308 is compared with the three other paleointensity records (one from the Western Equatorial Pacific and two from the North Atlantic) that cover the same time interval and have accompanying oxygen isotope records. The Match protocol of Lisiecki and Lisiecki (2002) is used to optimize the correlation of paleointensity records. Beginning with the original (published) age models for each record, the Match routine is used to optimize the RPI correlations to Site U1308, with checks to ensure compatibility with oxygen isotope records. Squared wavelet coherence (WTC) indicates significant improvement in RPI (and oxygen isotope) correlations after matching each RPI record to Site U1308, particularly for periods > 10 kyr. The level of coherence for the Atlantic RPI records and the lower resolution Pacific record implies synchronous global variability (at scales > 10 kyr) that can be attributed to the axial dipole geomagnetic field.

Strontium, oxygen and hydrogen isotope ratios of basalts from DSDP Hole 504B

DSDP Hole 504B was drilled into 6 Ma crust, about 200 km south of the Costa Rica Rift, Galapagos Spreading Center, penetrating 1.35 km into a section that can be divided into four zones-Zone I: oxic submarine weathering; Zone II: anoxic alteration; Zones III and IV: hydrothermal alteration to greenschist facies. In Zone III there is intense veining of pillow basalts. Zone IV consists of altered sheeted dikes. Isotopic geochemical signatures in relation to the alteration zones are recorded in Hole 504B, as follows: Zone Depth(m) Average87Sr/86Sr Average delta18O (?) Average deltaD (?) I 275-550 0.7032 7.3 -63 II 550-890 0.7029 6.5 -45 III 890-1050 0.7035 5.6 -31 IV 1050-1350 0.7032 5.5 -36 Alteration temperatures are as low as 10°C in Zones I and II based on oxygen isotope fractionation. Strontium isotopic data indicate that a circulation of seawater is much more restricted in Zone II than in Zone I. Fluid inclusion measurements of vein quartz indicate the alteration temperature was mainly 300 +/- 20°C in Zones III and IV, which is consistent with secondary mineral assemblages. The strontium, oxygen, and hydrogen isotopic compositions of hydrothermal fluids which were responsible for the greenschist facies alteration in Zones III and IV are estimated to be 0.7037, 2?, and 3?, respectively. Strontium and oxygen isotope data indicate that completely altered portions of greenstones and vein minerals were in equilibrium with modified seawater under low water/rock ratios (in weight) of about 1.6. This value is close to that of the end-member hydrothermal fluids issuing at 21°N EPR. Basement rocks are not completely hydrothermally altered. About 32% of the greenstones in Zones III and IV have escaped alteration. Thus 1 g of fresh basalt including the 32% unaltered portion are required in order to make 1 g of end-member solution from fresh seawater in water-rock reactions.

Stable carbon and oxygen isotope record od IODP Hole 306-U1313

The Mid-Pleistocene transition (MPT) was the time when quasi-periodic (? 100 kyr), high-amplitude glacial variability developed in the absence of any significant change in the character of orbital forcing, leading to the establishment of the characteristic pattern of late Pleistocene climate variability. It has long been known that the interval around 900 ka stands out as a critical point of the MPT, when major glaciations started occurring most notably in the northern hemisphere. Here we examine the record of climatic conditions during this significant interval, using high-resolution stable isotope records from benthic and planktonic foraminifera from a sediment core in the North Atlantic (Integrated Ocean Drilling Program Expedition 306, Site U1313). We have considered the time interval from late in Marine Isotope Stage (MIS) 23 to MIS 20 (910 to 790 ka). Our data indicate that interglacial MIS 21 was a climatically unstable period and was broken into four interstadial periods, which have been identified and correlated across the North Atlantic region. These extra peaks tend to contradict previous studies that interpreted the MIS 21 variability as consisting essentially of a linear response to cyclical changes in orbital parameters. Cooling events in the surface record during MIS 21 were associated with low benthic carbon isotope excursions, suggesting a coupling between surface temperature changes and the strength of the Atlantic meridional overturning circulation. Time series analysis performed on the whole interval indicates that benthic and planktonic oxygen isotopes have significant concentrations of spectral power centered on periods of 10.7 kyr and 6 kyr, which is in agreement with the second and forth harmonic of precession. The excellent correspondence between the foraminifera d18O records and insolation variations at the Equator in March and September suggests that a mechanism related to low-latitude precession variations, advected to the high latitudes by tropical convective processes, might have generated such a response. This scenario accounts for the presence of oscillations at frequencies equal to precession harmonics at Site U1313, as well as the occurrence of higher amplitude oscillations between the MIS22/21 transition and most of MIS 21, times of enhanced insolation variability.

Noble gases in submarine pillow volcanic glasses

Fifteen submarine glasses from the East Pacific Rise (CYAMEX), the Kyushu-Palau Ridge (DSDP Leg 59) and the Nauru Basin (DSDP Leg 61) were analysed for noble gas contents and isotopic ratios. Both the East Pacific Rise and Kyushu-Palau Ridge samples showed Ne excess relative to Ar and a monotonic decrease from Xe to Ar when compared with air noble gas abundance. This characteristic noble gas abundance pattern (type 2, classified by Ozima and Alexander) is interpreted to be due to a two-stage degassing from a noble gas reservoir with originally atmospheric abundance. In the Kyushu-Palau Ridge sample, noble gases are nearly ten times more abundant than in the East Pacific Rise samples. This may be attributed to an oceanic crust contamination in the former mantle source. There is no correlation between the He content and that of the other noble gas in the CYAMEX samples. This suggests that He was derived from a larger region, independent from the other noble gases. Except where radiogenic isotopes are involved, all other noble gas isotopic ratios were indistinguishable from air noble gas isotopic ratios. The 3He/4He in the East Pacific Rise shows a remarkably uniform ratio of (1.21 +/- 0.07)*10**-5, while the40Ar/36Ar ranges from 700 to 5600.

Organic matter and trace element concentrations in sapropels from ODP Leg 160 sites

A distinct Pliocene eastern Mediterranean sapropel (i-282), recovered from three Ocean Drilling Program (ODP) Leg 160 Sites, has been investigated for its organic and inorganic composition. This sapropel is characterized by high organic carbon (Corg) and trace element contents, and the presence of isorenieratene derivatives. The latter suggests that the base of the photic zone was sulphidic during formation of the sapropel. Combined with evidence of bottom water anoxia (preservation of laminae, high redox-sensitive trace element contents, and the abundance and isotopic composition of pyrite) this leads to the tentative conclusion that almost the entire water column may have been anoxic. This anoxia resulted from high productivity and not from stagnation, because an approximation of the trace element budget during sapropel formation shows that water exchange with the western Mediterranean is needed. Entire water column anoxia has been suggested earlier for several black shales. With regard to the depositional environment and the Corg content, however, only the Cenomanian=Turonian Boundary Event (CTBE) black shales appear to be comparable to this sapropel. The proposed trace element removal mechanism of scavenging and (co-)precipitation in an anoxic water column, is thought to be similar for both types of deposits. The ultimate trace element source for the sapropel, however, is seawater, whereas it is hydrothermal and fluvial input for CTBE black shales (because they have a larger temporal and spatial distribution). Nonetheless, the Corg-rich eastern Mediterranean Pliocene sapropel discussed here may be considered to be a younger analogue of CTBE black shales.

Chemical and isotope composition of poor fluid from gas-hydrate samples of ODP Site 146-892

Although the presence of extensive gas hydrate on the Cascadia margin, offshore from the western U.S. and Canada, has been inferred from marine seismic records and pore water chemistry, solid gas hydrate has only been found at one location. At Ocean Drilling Program (ODP) Site 892, offshore from central Oregon, gas hydrate was recovered close to the sediment-water interface at 2-19 m below the seafloor (mbsf) at 670 m water depth. The gas hydrate occurs as elongated platy crystals or crystal aggregates, mostly disseminated irregularly, with higher concentrations occurring in discrete zones, thin layers, and/or veinlets parallel or oblique to the bedding. A 2- to 3-cm thick massive gas hydrate layer, parallel to bedding, was recovered at ~17 mbsf. Gas from a sample of this layer was composed of both CH4 and H2S. This sample is the first mixed-gas hydrate of CH4-H2S documented in ODP; it also contains ethane and minor amounts of CO2. Measured temperatures of the recovered core ranged from 2 to -1.8°C and are 6 to 8 degrees lower than in-situ temperatures. These temperature anomalies were caused by the partial dissociation of the CH4-H2S hydrate during recovery without a pressure core sampler. During this dissociation, toxic levels of H2S (delta34S, +27.4?) were released. The delta13C values of the CH4 in the gas hydrate, -64.5 to -67.5? (PDB), together with deltaD values of -197 to -199? (SMOW) indicate a primarily microbial source for the CH4. The delta18O value of the hydrate H2O is +2.9? (SMOW), comparable with the experimental fractionation factor for sea-ice. The unusual composition (CH4-H2S) and depth distribution (2-19 mbsf) of this gas hydrate indicate mixing between a methane-rich fluid with a pore fluid enriched in sulfide; at this site the former is advecting along an inclined fault into the active sulfate reduction zone. The facts that the CH4-H2S hydrate is primarily confined to the present day active sulfate reduction zone (2-19 mbsf), and that from here down to the BSR depth (19-68 mbsf) the gas hydrate inferred to exist is a >=99% CH4 hydrate, suggest that the mixing of CH4 and H2S is a geologically young process. Because the existence of a mixed CH4-H2S hydrate is indicative of moderate to intense advection of a methane-rich fluid into a near surface active sulfate reduction zone, tectonically active (faulted) margins with organic-rich sediments and moderate to high sedimentation rates are the most likely regions of occurrence. The extension of such a mixed hydrate below the sulfate reduction zone should reflect the time-span of methane advection into the sulfate reduction zone.

Boron concentrations and isotope ratios of authigenic carbonates from the Oregon margin

Boron contents and boron, carbon and oxygen stable isotopes were determined for authigenic carbonates recovered from Ocean Drilling Program Leg 146, Oregon margin. Carbonate precipitates are the most widespread authigenic phase in the shallow accretionary wedge and carry chemical information about long-term variations in pore fluid origin and flow paths in the Cascadia subduction zone. Drilling the first ridge (toe area including the frontal thrust) and the second ridge (or Hydrate Ridge) of the prism demonstrated different fluid regimes, with higher B contents in the authigenic precipitates at the toe. The delta11B of 18 authigenic precipitates analysed ranges from 13.9 per mil to as high as 39.8 per mil, extending the upper range of previously reported carbonate delta11B values considerably. When related to the delta11B ratio of their parent solutions, these data are characteristic of fluid-related processes in accretionary prisms. Together with delta13C and delta18O, delta11B ratios of the carbonate concretions, nodules and crusts allow one to distinguish between precipitation influenced by (i) seawater, (ii) fluid reservoirs at different depth levels within the accretionary prism and (iii) cage water from dissociated gas hydrates, the latter possibly indicating a fluctuation of the bottom simulating reflector during most recent Earth's history. From this first systematic boron study on authigenic precipitates from an accretionary prism it is suggested that B contents of such carbonate crusts and concretions exceed those reported for other marine carbonates. Given the abundance of such precipitates at convergent margins, they represent a significant B sink in geochemical cycling. Isotopic compositions of the parent fluids to the carbonates mirror B chemistry of modern pore waters from convergent margins. The precipitates carry information of different subduction-related fluid processes over a certain period of time, and hence are a crucial tracer in the investigation of palaeo-fluid flow.

Alkenone accumulation and SST reconstruction for the Benguela upwelling zone

A feature of Pliocene climate is the occurrence of "permanent El Niño-like" or "El Padre" conditions in the Pacific Ocean. From the analysis of sediment cores in the modern northern Benguela upwelling, we show that the mean oceanographic state off Southwest Africa during the warm Pliocene epoch was also analogous to that of a persistent Benguela "El Niño". At present these events occur when massive southward flows of warm and nutrient-poor waters extend along the coasts of Angola and Namibia, with dramatic effects on regional marine ecosystems and rainfall. We propose that the persistent warmth across the Pliocene in the Benguela upwelling ended synchronously with the narrowing of the Indonesian seaway, and the early intensification of the Northern Hemisphere Glaciations around 3.0-3.5 Ma. The emergence of obliquity-related cycles in the Benguela sea surface temperatures (SST) after 3 Ma highlights the development of strengthened links to high latitude orbital forcing. The subsequent evolution of the Benguela upwelling system was characterized by the progressive intensification of the meridional SST gradients, and the emergence of the 100 ky cycle, until the modern mean conditions were set at the end of the Mid Pleistocene transition, around 0.6 Ma. These findings support the notion that the interplay of changes in the depth of the global thermocline, atmospheric circulation and tectonics preconditioned the climate system for the end of the warm Pliocene epoch and the subsequent intensification of the ice ages.