Interstitial water chemistry at DSDP Leg 67 Holes

Interstitial water chemistry has proved to be a sensitive indicator for early diagenetic reactions, particularly those related to organic matter oxidation. Downhole chemical variations in the pore waters from Deep Sea Drilling Project Holes 496 and 497 on the Middle America Trench slope off Guatemala are anomalous because both salinity and chlorinity show strong decreases to half the values of seawater, and d18O values become positive (maximum of about +2.5% at the bottom of the holes). These observations are explained in terms of dilution of pore waters after retrieval as a result of decomposition of the gas hydrates before removal of pore waters by shipboard squeezing techniques. In all holes, except Hole 495 (drilled in pelagic sediments), decomposition of organic matter leads to rapid sulfate depletion and subsequent methane generation. Associated with methane generation are large increases in alkalinity and dissolved ammonia. The latter component causes ion exchange reactions with clay minerals, which results in maxima in magnesium and perhaps potassium. At greater depths, as yet unidentified reactions cause the removal of magnesium. Especially in the deeper Trench Sites 499 and 500, rapid variations in calcium, magnesium, and alkalinity occur in turbidite sequences.

Age determination of Southeast Atlantic sediment cores

Angola Basin and Cape Basin (southeast Atlantic) surface sediments and sediment cores show that maxima in the abundance of taraxerol (relative to other land-derived lipids) covary with maxima in the relative abundance of pollen from the mangrove tree genus Rhizophora and that in the surface sediments offshore maxima in the relative abundance of taraxerol occur at latitudes with abundant coastal mangrove forests. Together with the observation that Rhizophora mangle and Rhizophora racemosa leaves are extraordinarily rich in taraxerol, this strongly indicates that taraxerol can be used as a lipid biomarker for mangrove input to the SE Atlantic. The proxy-environment relations for taraxerol and Rhizophora pollen down-core show that increased taraxerol and Rhizophora pollen abundances occur during transgressions and periods with a humid climate. These environmental changes modify the coastal erosion and sedimentation patterns, enhancing the extent of the mangrove ecosystem and/or the transport of mangrove organic matter offshore. Analyses of mid-Pleistocene sediments show that interruption of the pattern of taraxerol maxima during precession minima occurs almost only during periods of low obliquity. This demonstrates the complex environmental response of the interaction between precession-related humidity cycles and obliquity-related sea-level changes on mangrove input.

Geochemistry of ODP Site 145-882

Measurements of benthic foraminiferal cadmium:calcium (Cd/Ca) have indicated that the glacial-interglacial change in deep North Pacific phosphate (PO4) concentration was minimal, which has been taken by some workers as a sign that the biological pump did not store more carbon in the deep glacial ocean. Here we present sedimentary redox-sensitive trace metal records from Ocean Drilling Program (ODP) Site 882 (NW subarctic Pacific, water depth 3244 m) to make inferences about changes in deep North Pacific oxygenation - and thus respired carbon storage - over the past 150,000 yr. These observations are complemented with biogenic barium and opal measurements as indicators for past organic carbon export to separate the influences of deep-water oxygen concentration and sedimentary organic carbon respiration on the redox state of the sediment. Our results suggest that the deep subarctic Pacific water mass was depleted in oxygen during glacial maxima, though it was not anoxic. We reconcile our results with the existing benthic foraminiferal Cd/Ca by invoking a decrease in the fraction of the deep ocean nutrient inventory that was preformed, rather than remineralized. This change would have corresponded to an increase in the deep Pacific storage of respired carbon, which would have lowered atmospheric carbon dioxide (CO2) by sequestering CO2 away from the atmosphere and by increasing ocean alkalinity through a transient dissolution event in the deep sea. The magnitude of change in preformed nutrients suggested by the North Pacific data would have accounted for a majority of the observed decrease in glacial atmospheric pCO2.

(Tabls S1) Bulk geochemistry for sediment samples collected from the Cenomanian-Turonian boundary section at Pont d'Issole

Oceanic Anoxic Event 2 (OAE2), spanning the Cenomanian-Turonian boundary (CTB), represents one of the largest perturbations in the global carbon cycle in the last 100 Myr. The d13Ccarb, d13Corg, and d18O chemostratigraphy of a black shale-bearing CTB succession in the Vocontian Basin of France is described and correlated at high resolution to the European CTB reference section at Eastbourne, England, and to successions in Germany, the equatorial and midlatitude proto-North Atlantic, and the U.S. Western Interior Seaway (WIS). Delta13C (offset between d13Ccarb and d13Corg) is shown to be a good pCO2 proxy that is consistent with pCO2 records obtained using biomarker d13C data from Atlantic black shales and leaf stomata data from WIS sections. Boreal chalk d18O records show sea surface temperature (SST) changes that closely follow the Delta13C pCO2 proxy and confirm TEX86 results from deep ocean sites. Rising pCO2 and SST during the Late Cenomanian is attributed to volcanic degassing; pCO2 and SST maxima occurred at the onset of black shale deposition, followed by falling pCO2 and cooling due to carbon sequestration by marine organic productivity and preservation, and increased silicate weathering. A marked pCO2 minimum (~25% fall) occurred with a SST minimum (Plenus Cold Event) showing >4°C of cooling in ~40 kyr. Renewed increases in pCO2, SST, and d13C during latest Cenomanian black shale deposition suggest that a continuing volcanogenic CO2 flux overrode further drawdown effects. Maximum pCO2 and SST followed the end of OAE2, associated with a falling nutrient supply during the Early Turonian eustatic highstand.

North Atlantic late Miocene stable-isotope stratigraphy, biostratigraphy, and magnetostratigraphy

Upper Miocene foraminiferal nannofossil ooze and chalk from DSDP Hole 552A in the northeast Atlantic Ocean have been closely sampled for biostratigraphic, paleomagnetic, and stable-isotopic studies. Sampling at 10-cm intervals resulted in an uppermost Miocene isotope stratigraphy with a 1000- to 3000-yr. resolution. Covariance in benthic (Planulina wuellerstorfi) and planktonic (Globigerina bulloides) foraminiferal d18O records is taken as evidence for variability in continental ice volume. Our best estimate is that glacial maxima occurred at -5.0 and ~ 5.5 Ma and lasted no more than 20,000 yrs. These events probably lowered sea level by 60 m below the latest Miocene average. There is little oxygen-isotope evidence, however, for a prolonged glaciation during the last 2 m.y. of the late Miocene. High- and low-frequency variability in the d13C record of foraminifers is useful for correlation among North Atlantic DSDP Sites 408, 410, 522, 610, and 611, and for correlation with sites in other oceans. Similar d13C changes are seen in P. wuellerstorfi and G. bulloides, but the amplitude of the signal is always greater in G. bulloides. Variability in d13C common to both species probably reflects variability in the d13C of total CO2 in seawater. Major long-term features in the d13C record include a latest Miocene maximum (P. wuellerstorfi = 1.5 per mil ) in paleomagnetic Chron 7, an abrupt decrease in d13C at -6.2 Ma, and a slight increase at -5.5 Ma. The decrease in d13C at -6.2 Ma, which has been paleomagnetically dated only twice before, occurs in the upper reversed part of Chronozone 6 at Holes 552A and 611C, in excellent agreement with earlier studies. Cycles in d13C with a period of ~ 10 4 yrs. are interpreted as changes in seawater chemistry, which may have resulted from orbitally induced variability in continental biomass. Samples of P. wuellerstorfi younger than 6 Ma from throughout the North Atlantic have d13C near lo, on average ~ l per mil greater than samples of the same age in the Pacific Ocean. Thus, there is no evidence for cessation of North Atlantic Deep Water production resulting from the Messinian "salinity crisis." Biostratigraphic results indicate continuous sedimentation during the late Miocene after about -6.5 Ma at Hole 552A. Nannofossil biostratigraphy is complicated by the scarcity of low-latitude marker species, but middle and late Miocene Zones NN7 through NN11 are recognized. A hiatus is present at -6.5 Ma, on the basis of simultaneous first occurrences of Amaurolithusprimus, Amaurolithus delicatus, Amaurolithus amplificus, and Scyphosphaera globulata. The frequency and duration of older hiatuses increase downsection in Hole 552A, as suggested by calcareous nannofossil biostratigraphy and magnetostratigraphy. Paleomagnetic results at Hole 552A indicate a systematic pattern of inclination changes. Chronozone 6 was readily identified because of its characteristic nannoflora (sequential occurrences of species assigned to the genus Amaurolithus) and the d13C decrease in foraminifers, but its lower reversed interval is condensed. Only the lower normal interval of Chronozone 5 was recognized at Hole 552A; the upper normal interval and the lowest Gilbert sediment are not recognized, owing to low intensity of magnetization and to coring disturbance. Interpreting magnetic reversals below Chronozone 6 was difficult because of hiatuses, but a lower normally magnetized interval is probably Chronozone 7. Correlation between DSDP Hole 552A and other North Atlantic sites is demonstrated using coiling direction changes in the planktonic foraminifer Neogloboquadrina. At most sites this genus changed its coiling preference from dominantly right to dominantly left during the late Miocene. At Hole 552A this event probably occurred about 7 m.y. ago. At the same time, P. wuellerstorfi had maximum d13C values. A similar d13C maximum and coiling change occurred together in Chron 7 at Hole 611C, and at Hole 610E. In sediment younger than -5.5 Ma, the coiling of small Neogloboquadrina species is random, but the larger species N. atlantica retains preferential left coiling.

Biogeochemical investigations on sediment core MD04-2876

Modern seawater profiles of oxygen, nitrate deficit, and nitrogen isotopes reveal the spatial decoupling of summer monsoon-related productivity and denitrification maxima in the Arabian Sea (AS) and raise the possibility that winter monsoon and/or ventilation play a crucial role in modulating denitrification in the northeastern AS, both today and through the past. A new high-resolution 50-ka record of d15N from the Pakistan margin is compared to five other denitrification records distributed across the AS. This regional comparison unveils the persistence of east-west heterogeneities in denitrification intensity across millennial-scale climate shifts and throughout the Holocene. The oxygen minimum zone (OMZ) experienced east-west swings across Termination I and throughout the Holocene. Probable causes are (1) changes in ventilation due to millennial-scale variations in Antarctic Intermediate Water formation and (2) postglacial reorganization of intermediate circulation in the northeastern AS following sea level rise. Whereas denitrification in the world's OMZs, including the western AS, gradually declined following the deglacial maximum (10-9 ka BP), the northeastern AS record clearly witnesses increasing denitrification from about 8 ka BP. This would have impacted the global Holocene climate through sustained N2O production and marine nitrogen loss.

Age model for ODP Leg 175 sites

Upwelling along the western coast of Africa south of the equator may be partitioned into three major areas, each having its own dynamics and history: (1) the eastern equatorial region, comprising the Congo Fan and the area of Mid-Angola; (2) the Namibia upwelling system, extending from the Walvis Ridge to Lüderitz; and (3) the Cape Province region, where upwelling is subdued. The highest nutrient contents in thermocline waters are in the northern region, the lowest in the southern one. Wind effects are at a maximum near the southern end of the Namibia upwelling system, and maximum productivity occurs near Walvis Bay, where the product between upwelling rate and nutrient content of upwelled waters is at a maximum. In the Congo/Angola region, opal tends to follow organic carbon quite closely in the Quaternary record. However, organic carbon has a strong precessional component, while opal does not. Despite relatively low opal content, sediments off Angola show the same patterns as those off the Congo; thus, they are part of the same regime. The spectrum shows nonlinear interference patterns between high- and low-latitude forcing, presumably tied to thermocline fertility and wind. On Walvis Ridge, as in the Congo-Angola region, the organic matter record behaves normally; that is, supply is high during glacial periods. In contrast, interglacial periods are favorable for opal deposition. The pattern suggests reduction in silicate content of the thermocline during glacial periods. The reversed phase (opal abundant during interglacials) persists during the entire Pleistocene and can be demonstrated deep into the Pliocene, not just on Walvis Ridge but all the way to the Oranje River and off the Cape Province. From comparison with other regions, it appears that silicate is diminished in the global thermocline, on average, whenever winds become strong enough to substantially shorten the residence time of silicate in upper waters (Walvis Hypothesis, solving the Walvis Paradox of reversed phase in opal deposition). The central discovery during Leg 175 was the documentation of a late Pliocene opal maximum for the entire Namibia upwelling system (early Matuyama Diatom Maximum [MDM]). The maximum is centered on the period between the end of the Gauss Chron and the beginning of the Olduvai Chron. A rather sharp increase in both organic matter deposition and opal deposition occurs near 3 Ma in the middle of the Gauss Chron, in association with a series of major cooling steps. As concerns organic matter, high production persists at least to 1 Ma, when there are large changes in variability, heralding subsequent pulsed production periods. From 3 to 2 Ma, organic matter and opal deposition run more or less parallel, but after 2 Ma opal goes out of phase with organic matter. Apparently, this is the point when silicate becomes limiting to opal production. Thus, the MDM conundrum is solved by linking planetary cooling to increased mixing and upwelling (ramping up to the MDM) and a general removal of silicate from the upper ocean through excess precipitation over global supply (ramping down from the MDM). The hypothesis concerning the origin of the Namibia opal acme or MDM is fundamentally the same as the Walvis Hypothesis, stating that glacial conditions result in removal of silicate from the thermocline (and quite likely from the ocean as a whole, given enough time). The Namibia opal acme, and other opal maxima in the latest Neogene in other regions of the ocean, marks the interval when a cooling ocean selectively removes the abundant silicate inherited from a warm ocean. When the excess silicate is removed, the process ceases. According to the data gathered during Leg 175, major upwelling started in the late part of the late Miocene. Presumably, this process contributed to the drawing down of carbon dioxide from the atmosphere, helping to prepare the way for Northern Hemisphere glaciation.

Sediment, isotopic and geochemical record during Marine Isotope Stages 29 to 34 of IODP Site 339-U1387

Centennial-to-millennial scale records from IODP Site U1387, drilled during IODP Expedition 339 into the Faro Drift at 558 m water depth, now allow evaluating the climatic history of the upper core of the Mediterranean Outflow (MOW) and of the surface waters in the northern Gulf of Cadiz during the early Pleistocene. This study focuses on the period from Marine Isotope Stage (MIS) 29 to 34, i.e. the interval surrounding extreme interglacial MIS 31. Conditions in the upper MOW reflect obliquity, precession and millennial-scale variations. The benthic d18O signal follows obliquity with the exception of an additional, smaller d18O peak that marks the MIS 32/31 transition. Insolation maxima (precession minima) led to poor ventilation and a sluggish upper MOW core, whereas insolation minima were associated with enhanced ventilation and often also increased bottom current velocity. Millennial-scale periods of colder sea-surface temperatures (SST) were associated with short-term maxima in flow velocity and better ventilation, reminiscent of conditions known from MIS 3. A prominent contourite layer, coinciding with insolation cycle 100, was formed during MIS 31 and represents one of the few contourites developing within an interglacial period. MIS 31 surface water conditions were characterized by an extended period (1065-1091 ka) of warm SST, but SST were not much warmer than during MIS 33. Interglacial to glacial transitions experienced 2 to 3 stadial/interstadial cycles, just like their mid-to-late Pleistocene counterparts. Glacial MIS 30 and 32 recorded periods of extremely cold (< 12°C) SST that in their climatic impact were comparable to the Heinrich events of the mid and late Pleistocene. Glacial MIS 34, on the other hand, was a relative warm glacial period off southern Portugal. Overall, surface water and MOW conditions at Site U1387 show strong congruence with Mediterranean climate, whereas millennial-scale variations are closely linked to North Atlantic circulation changes.

Compositional and isotopic data on core MD84641

The organic carbon isotopic record of the sapropels(S1 and S3-S10) and intercalated marl oozes has been determined in a 12-m piston core from the eastern Mediterranean. The d13C_organic values are systematically lighter (mean=-21.0±0.82 per mil) in all sapropels and heavier (mean=-18.8±1.07 per mil) in the marl oozes. These differences are not due to variable marine and terrestrial organic matter mixtures because all values are heavier than modern plankton in the Mediterranean, there is no relationship between the C_organic/N ratios and the isotopic values, and published information on the abundance and distribution of organic biomarkers shows that terrestrial material constitutes a minor fraction of the total organic matter. Temperature effects on isotope fractionation are also discounted because the change in d13C_organic values between glacial and interglacial horizons is in the opposite sense. Diagenesis, which can produce relatively small changes in the carbon isotopic composition of sedimentary organic matter under certain circumstances, is unlikely to have caused the observed differences because this mechanism would cause an enrichmet in 12C, implying that all values were even heavier originally, and there is no secular trend in the d13C_organic record. The observed differences in d13C_organic between the two lithologies are probably produced by changes in the isotopic composition and the concentration of dissolved CO2. First, freshwater flooding during the formation of the sapropels caused the isotopic composition of the dissolved inorganic carbon in the surface waters of the Mediterranean to become lighter because of the 13C deficiency in fresh waters. Hence photosynthesis would have produced isotopically lighter organic material. Second, changes in atmospheric pCO2 between glacial and interglacial periods, as shown by the Vostok ice core, caused marked changes in the concentration of free dissolved CO2 in the mixed layer; lower values during glacial maxima caused a smaller fractionation of the carbon isotopes by phytoplankton, whereas levels were less limiting during the interglacials. Concentrations of dissolved CO2 could also have been much higher during the deposition of the sapropels because of the supply of regenerated CO2 to the mixed layer by upwelling, and this could have further lightened the d13C_organic values in the sapropels themselves. Carbon isotope records may provide an alternative method for estimating atmospheric pCO2 levels over longer time periods than can be obtained from ice cores.

Log-ratio of silica to aluminium counts (ln(Si/Al)) from ODP site 108-658

Growing evidence suggests that the low atmospheric CO2 concentration of the ice ages resulted from enhanced storage of CO2 in the ocean interior, largely as a result of changes in the Southern Ocean1. Early in the most recent deglaciation, a reduction in North Atlantic overturning circulation seems to have driven CO2 release from the Southern Ocean**2, 3, 4, 5, but the mechanism connecting the North Atlantic and the Southern Ocean remains unclear. Biogenic opal export in the low-latitude ocean relies on silicate from the underlying thermocline, the concentration of which is affected by the circulation of the ocean interior. Here we report a record of biogenic opal export from a coastal upwelling system off the coast of northwest Africa that shows pronounced opal maxima during each glacial termination over the past 550,000 years. These opal peaks are consistent with a strong deglacial reduction in the formation of silicate-poor glacial North Atlantic intermediate water**2 (GNAIW). The loss of GNAIW allowed mixing with underlying silicate-rich deep water to increase the silicate supply to the surface ocean. An increase in westerly-wind-driven upwelling in the Southern Ocean in response to the North Atlantic change has been proposed to drive the deglacial rise in atmospheric CO2 (refs 3, 4). However, such a circulation change would have accelerated the formation of Antarctic intermediate water and sub-Antarctic mode water, which today have as little silicate as North Atlantic Deep Water and would have thus maintained low silicate concentrations in the Atlantic thermocline. The deglacial opal maxima reported here suggest an alternative mechanism for the deglacial CO2 release**5, 6. Just as the reduction in GNAIW led to upward silicate transport, it should also have allowed the downward mixing of warm, low-density surface water to reach into the deep ocean. The resulting decrease in the density of the deep Atlantic relative to the Southern Ocean surface promoted Antarctic overturning, which released CO2 to the atmosphere.

Parasound profiles and multibeam surveys in the Arctic Ocean

During the Pleistocene glaciations, Arctic ice sheets on western Eurasia, Greenland and North America terminated at their continental margins. In contrast, the exposed continental shelves in the Beringian region of Siberia are thought to have been covered by a tundra landscape. Evidence of grounded ice on seafloor ridges and plateaux off the coast of the Beringian margin, at depths of up to 1,000 m, have generally been attributed to ice shelves or giant icebergs that spread oceanwards during glacial maxima. Here we identify marine glaciogenic landforms visible in seismic profiles and detailed bathymetric maps along the East Siberian continental margin. We interpret these features, which occur in present water depths of up to 1,200 m, as traces from grounding events of ice sheets and ice shelves. We conclude that the Siberian Shelf edge and parts of the Arctic Ocean were covered by ice sheets of about 1 km in thickness during several Pleistocene glaciations before the most recent glacial period, which must have had a significant influence on albedo and oceanic and atmospheric circulation.

Foraminiferal abundance, carbonat concentration and dissolution index of sediment core W9903B-51GC

In order to investigate the paleoceanographic record of dissolution of calcium carbonate (CaCO3) in the central equatorial Pacific Ocean, we have studied the relationship between three indices of foraminiferal dissolution and the concentration and accumulation of CaCO3, opal, and Corg in Core WEC8803B-GC51 (1.3°N, 133.6°W; 4410 m). This core spans the past 413 kyr of deposition and moved in and out of the lysoclinal transition zone during glacial-interglacial cycles of CaCO3 production and dissolution. The record of dissolution intensity provided by foraminiferal fragmentation, the proportion of benthic foraminifera, and the foraminiferal dissolution index consistently indicates that the past corrosion of pelagic CaCO3 in the central equatorial Pacific does not vary with the observed sedimentary concentration of CaCO3. Although there is a weak low-frequency variation (~100 kyr) in dissolution intensity, it is unrelated to sedimentary CaCO3 concentration. There are many shorter-lived episodes where high CaCO3 concentration is coincident with poor foraminiferal preservation, and where, conversely, low CaCO3 concentration is coincident with superb foraminiferal preservation. Spectral analyses indicate that dissolution maxima consistently lagged glacial maxima (manifest by the SPECMAP delta18O stack) in the 100-kyr orbital band. Additionally, there is no relationship between dissolution and the accumulation of biogenic opal or Corg or between dissolution and the burial ratio of Corg/CINorg (calculated from Corg and CaCO3). Because previous studies of this core strongly suggest that surface water productivity varied closely with CaCO3 accumulation, both the mechanistic decoupling of carbonate dissolution from CaCO3 concentration (and from biogenic accumulation) and the substantial phase shift between dissolution and global glacial periodicity effectively obscure any simple link between export production, CaCO3 concentration, and dissolution of sedimentary CaCO3.

Age determination of sediment cores from the continental shelf and slope off North-West Africa

Three sediment cores from the continental shelf and slope off NW Africa (Banc d'Arguin; 52 m, 665 m and 973 m water depth) have been investigated by means of a coarse fraction analysis. The two shallower cores have been deposited during less than 10,000 years, the deeper one during the last 36,000 years. The Holocene sedimentation ( 4000 years) in the deeper part of core 79 the edge of the Banc d'Arguin is strongly influenced by reworking of Late Glacial dune sands and biogenic particles from shallower ware (<40 m), as well as eroding current influence. A decrease in grain size of silicate material and a decrease in lateral supply, correlated to a doubling of accumulation rates in the upper part of the core, indicates a more autochthonous sedimentation with less sorting influence in the youngest Holocene. The depth of provenance of the allochttonous material can be assumed in 100-300 m water depth as indicated by various biogenous particles. Small amounts of shallow water particles in the autochthonous layers indicate a supplay from shallow water, which probably occured b ythe mechanism of "particle by particle supply". None of the three cores indicates upwelling influence, although occanographers found intense upwelling in the area of the Banc d'Arguin. The Holocene climate in that area probably has been arid, small variations in terrigenous matter composition and grain size in the Early Holocene might be due to decreased wind strength or to an increase in rain fall. The Peak Glacial section (14,000-22,000 y. B.P.) of the deepest core 88 indicates a very much intensified eolian silt supply and an additional bottom supply of quartz sand In the interval 22,000-36,000 y. B.P. wind strength decreased, but probably no increase in humidity occurred. So this area in about 19° 40' N had an arid climate in the Late Holocene and in the Peak Glacial. The fragmentation of planktonic foraminifers and the abundance of aragonitic tests of pteropods in core 88 indicate an Early Holocene (8330 y. B.P.) preservation spike. Two minima in fragmentation correlated to maxima in pteropod content at about 15,700 and 21,000 y. B.P. are correlated to maxima in shallow water supply and thus do not reflect preservation conditions, but only lateral supply from the carbonate dissolution minimum zone in about 300 m water depth.