Concentrations of organic carbon and organic matter isotopic compositions of sapropels and adjacent marls from ODP Hole 161-974B in the Tyrrhenian Basin (Table 1)

Multiple layers of sapropels occur widely in the sedimentary record of the Mediterranean Sea and record repetitions of paleoclimatic conditions that favored increased production and preservation of marine organic matter. A combination of hydrogen and carbon isotope analyses of Pleistocene sapropels from the Tyrrhenian Sea reveals new aspects of the factors leading to their deposition. Organic matter dD values that are significantly more negative in sapropels than in adjacent marls indicate a combination of dilution of surface waters by meteoric waters and increased burial of lipid-rich organic matter during periods of sapropel deposition. Organic d13C values in sapropels that are less negative than those in marls suggest periods of markedly elevated marine biological production. The opposite but concordant excursions of these two isotopic parameters imply that the sapropel layers formed from increased export of marine organic matter from the photic zone to the sea floor during periods of greater fluvial delivery of continental nutrients to the Mediterranean Sea. Furthermore, the isotopic evidence indicates that periods of wetter climate were widespread in southern Europe at the same times as in northern Africa.

(Table 1) Peak intensities and stable carbon and oxygen isotope ratios of various diagenetic carbonates of ODP Site 128-799

Abundant and various diagenetic carbonates were recovered from a 1084-m-thick, Quaternary to lower Miocene section at ODP Site 799 in the Japan Sea. Petrographic, XRD, SEM, EDS-chemical, and isotopic analyses revealed wide variations in occurrence and textural relations and complex mineralogy and chemistry. Diagenetic carbonates include calcite, calcium-rich rhodochrosite, iron- and manganese-rich magnesite, iron- and manganese-rich dolomite and ankerite, and iron- and manganeserich lansfordite (hydrous Mg-carbonate). Rhodochrosite commonly occurs as small, solid nodules and semi-indurated, thin layers in bioturbated, mottled sediments of Units I and II (late Miocene to Quaternary). Lansfordite occurs as unindurated nodules and layers in Unit II (late Miocene and Pliocene), whereas magnesite forms indurated beds a few centimeters thick in slightly bioturbated-to-faintly laminated sediments of Unit III (middle and late Miocene). Some rhodochrosite nodules have dark-colored, pyritic cores, and some pyrite-rhodochrosite nodules are overgrown by and included within magnesite beds. Dolomite and ankerite tend to form thick beds (>10 cm) in bedded to laminated sediments of Units III, IV, and V (early to late Miocene). Calcite occurs sporadically throughout the Site 799 sediments. The d18O values of carbonates and the interstitial waters, and the measured geothermal gradient indicate that almost all of the Site 799 carbonates are not in isotopic equilibrium with the ambient waters, but were precipitated in the past when the sediments were at shallower depths. Depths of precipitation obtained from the d18O of carbonates span from 310 to 510 mbsf for magnesite and from 60 to 580 mbsf for dolomite-ankerite. Rhodochrosite and calcite are estimated to have formed within sediments at depths shallower than 80 mbsf. Diagenetic history in the Site 799 sediments have been determined primarily by the environment of deposition; in particular, by the oxidation-reduction state of the bottom waters and the alkalinity level of the interstitial waters. Under the well-oxygenated bottom-water conditions in the late Miocene and Pliocene, manganese initially accumulated on the seafloor as hydrogenous oxides and subsequently was mobilized and reprecipitated as rhodochrosite within the shallow sulfate-reduction, sub-oxic zone. Precipitation of lansfordite occurred in the near-surface sediments with abundant organic carbon and an extremely high alkalinity during the latest Miocene and Pliocene. The lansfordite was transformed to magnesite upon burial in the depth interval 310 to 510 mbsf. Dolomite first precipitated at shallow depths in Mn-poor, anoxic, moderately biocalcareous sediments of early to late Miocene. With increasing temperature and depth, the dolomite recrystallized and reequilibrated with ambient waters at depths below about 400 mbsf.

Age determination of sediment core W8709A-13

Northeast Pacific benthic foraminiferal d18O and d13 reveal repeated millennial-scale events of strong deep-sea ventilation (associated with nutrient depletion and/or high gas exchange) during stadial (cool, high ice volume) episodes from 10 to 60 ka, opposite the pattern in the deep North Atlantic. Two climate mechanisms may explain this pattern. North Pacific surface waters, chilled by atmospheric transmission from a cold North Atlantic and made saltier by reduced freshwater vapor transports, could have ventilated the deep Pacific from above. Alternatively, faster turnover of Pacific bottom and mid-depth waters, driven by Southern Ocean winds, may have compensated for suppressed North Atlantic Deep Water production during stadial intervals. During the Younger Dryas event (~11.6-13.0 cal ka), ventilation of the deep NE Pacific (~2700 m) lagged that in the Santa Barbara Basin (~450 m) by >500 years, suggesting that the NE Pacific was first ventilated at intermediate depth from above and then at greater depth from below. This apparent lag may reflect the adjustment time of global thermohaline circulation.

Alkenone stable carbon isotopes, carbonate stable carbon and oxygen isotopes, planktic foraminifera boron isotopes and atmospheric CO2 calculations and box model results from Ras il-Pellegrin section, Malta

The development of a permanent, stable ice sheet in East Antarctica happened during the middle Miocene, about 14 million years (Myr) ago. The middle Miocene therefore represents one of the distinct phases of rapid change in the transition from the "greenhouse" of the early Eocene to the "icehouse" of the present day. Carbonate carbon isotope records of the period immediately following the main stage of ice sheet development reveal a major perturbation in the carbon system, represented by the positive d13C excursion known as carbon maximum 6 ("M6"), which has traditionally been interpreted as reflecting increased burial of organic matter and atmospheric pCO2 drawdown. More recently, it has been suggested that the d13C excursion records a negative feedback resulting from the reduction of silicate weathering and an increase in atmospheric pCO2. Here we present high-resolution multi-proxy (alkenone carbon and foraminiferal boron isotope) records of atmospheric carbon dioxide and sea surface temperature across CM6. Similar to previously published records spanning this interval, our records document a world of generally low (~300 ppm) atmospheric pCO2 at a time generally accepted to be much warmer than today. Crucially, they also reveal a pCO2 decrease with associated cooling, which demonstrates that the carbon burial hypothesis for CM6 is feasible and could have acted as a positive feedback on global cooling.

(Table 1) Results of pore water analyses, including boron content and boron isotope ratios

Drilling a transect of holes across the Costa Rica forearc during ODP Leg 170 demonstrated the margin wedge to be of continental, non accretionary origin, which is intersected by permeable thrust faults. Pore waters from four drillholes, two of which penetrated the décollement zone and reached the underthrust lower plate sedimentary sequence of the Cocos Plate, were examined for boron contents and boron isotopic signatures. The combined results show dilution of the uppermost sedimentary cover of the forearc, with boron contents lower than half of the present-day seawater values. Pore fluid "refreshening" suggests that gas hydrate water has been mixed with the sediment interstitial water, without profoundly affecting the d11B values. Fault-related flux of a deeply generated fluid is inferred from high B concentration in the interval beneath the décollement, being released from the underthrust sequence with incipient burial. First-order fluid budget calculations over a cross-section across the Costa Rica forearc indicate that no significant fluid transfer from the lower to the upper plate is inferred from boron fluid profiles, at least within the frontal 40 km studied. Expulsed lower plate pore water, which is estimated to be 0.26-0.44 km3 per km trench, is conducted efficiently along and just beneath the décollement zone, indicating effective shear-enhanced compaction. In the upper plate forearc wedge, dewatering occurs as diffuse transport as well as channelled flow. A volume of approximately 2 km3 per km trench is expulsed due to compaction and, to a lesser extent, lateral shortening. Pore water chemistry is influenced by gas hydrate instability, so that it remains unknown whether deep processes like mineral dehydration or hydrocarbon formation may play a considerable role towards the hinterland.

Osmium concentrations and isotope ratios of ODP Hole 207-1260B and the Furlo section

Oceanic anoxic events (OAEs) were episodes of widespread marine anoxia during which large amounts of organic carbon were buried on the ocean floor under oxygen-deficient bottom waters (Schlanger and Jenkyns, 1976; Schlanger et al., 1987). OAE2, occurring at the Cenomanian/Turonian boundary (about 93.5 Myr ago) (Gradstein et al., 2004), is the most widespread and best defined OAE of the mid-Cretaceous. Although the enhanced burial of organic matter can be explained either through increased primary productivity or enhanced preservation scenarios (Schlanger and Jenkyns, 1976; Schlanger et al., 1987). the actual trigger mechanism, corresponding closely to the onset of these episodes of increased carbon sequestration, has not been clearly identified. It has been postulated that large-scale magmatic activity initially triggered OAE2 (Sinton and Duncan, 1997; Kerr, 1998, doi:10.1144/gsjgs.155.4.0619), but a direct proxy of magmatism preserved in the sedimentary record coinciding closely with the onset of OAE2 has not yet been found. Here we report seawater osmium isotope ratios in organic-rich sediments from two distant sites. We find that at both study sites the marine osmium isotope record changes abruptly just at or before the onset of OAE2. Using a simple two-component mixing equation, we calculate that over 97 per cent of the total osmium content in contemporaneous seawater at both sites is magmatic in origin, a ~30-50-fold increase relative to pre-OAE conditions. Furthermore, the magmatic osmium isotope signal appears slightly before the OAE2 -as indicated by carbon isotope ratios- suggesting a time-lag of up to ~23 kyr between magmatism and the onset of significant organic carbon burial, which may reflect the reaction time of the global ocean system. Our marine osmium isotope data are indicative of a widespread magmatic pulse at the onset of OAE2, which may have triggered the subsequent deposition of large amounts of organic matter.

(Table 1) Stable isotope record of Middle Cretaceous benthic foraminifera

Preservation of planktic foraminiferal calcite has received widespread attention in recent years, but the taphonomy of benthic foraminiferal calcite and its influence on the deep-sea palaeotemperature record have gone comparatively unreported. Numerical modeling indicates that the carbonate recrystallization histories of deep-sea sections are dominated by events in their early burial history, meaning that the degree of exchange between sediments and pore fluids during the early postburial phase holds the key to determining the palaeotemperature significance of diagenetic alteration of benthic foraminifera. Postburial sedimentation rate and lithology are likely to be important determinants of the paleoceanographic significance of this sediment-pore fluid interaction. Here we report an investigation of the impact of extreme change in sedimentation rate (a prolonged and widespread Upper Cretaceous hiatus in the North Atlantic Ocean) on the preservation and d18O of benthic foraminifera of Middle Cretaceous age (nannofossil zone NC10, uppermost Albian/lowermost Cenomanian, ~99 Ma ago) from multiple drill sites. At sites where this hiatus immediately overlies NC10, benthic foraminifera appear to display at least moderate preservation of the whole test. However, on closer inspection, these tests are shown to be extremely poorly preserved internally and yield d18O values substantially higher than those from contemporaneous better preserved benthic foraminifera at sites without an immediately overlying hiatus. These high d18O values are interpreted to indicate alteration close to the seafloor in cooler waters during the Late Cretaceous hiatus. Intersite differences in lithology modulate the diagenetic impact of this extreme change in sedimentation rate. Our results highlight the importance of thorough examination of benthic foraminiferal wall structures and lend support to the view that sedimentation rate and lithology are key factors controlling the paleoceanographic significance of diagenetic alteration of biogenic carbonates.

Öate Cretaceous to early Paleogene nutrient and paleoproductivity records of ODP Leg 171 sites

We evaluate phosphorus (P) and biogenic barium (bio-Ba) as nutrient burial and export productivity indicators for the Late Cretaceous and early Paleogene, combining these with calcium carbonate (CaCO3), organic carbon (C), and bulk CaCO3 C isotopes (d13C). Sample ages span 36-71 Ma (~1 sample/0.5 m.y.) for a depth transect of sites in the western North Atlantic (Blake Nose, Ocean Drilling Program Leg 171B, Sites 1052, 1051, and 1050). We use a multitracer approach including redox conditions to investigate export productivity surrounding the global Paleocene d13C maximum (~57 Ma). Reducing conditions render most of the bio-Ba record not useful for export productivity interpretations. P and organic C records indicate that regional nutrient and organic C burial were high at ~61 and ~69 Ma, and low during the Paleocene d13C maximum, a time of proposed global high relative organic C burial. Observed organic C burial changes at Blake Nose cannot explain this C isotope excursion.

Mineralogy, isotopic composition of oxygen, hydrogen and carbon, and oxygen isotopic temperature of deep-sea silica and coexisting carbonates (Table 1)

Water extracted from opal-CT ("porcellanite", "cristobalite"), granular microcrystalline quartz (chert), and pure fibrous quartz (chalcedony) in cherts from the JOIDES Deep Sea Drilling Project is 56? to 87? depleted in deuterium relative to the water in which the silica formed. This large fractionation is similar in magnitude and sign to that observed for hydroxyl in clay minerals and suggests that water extracted from these forms of silica has been derived from hydroxyl groups within the silica. Delta18O-values for opal-CT at sites 61, 64, 70B and 149 vary from 34.3? to 37.2? and show no direct correlation with depth of burial. Granular microcrystaUine quartz in these cores is 0.5 ? depleted in 18O relative to coexisting opal-CT at sediment depths of 100 m and the depletion increases to 2? for sediments buried below 384 m. These relationships suggest that opal-CT forms before significant burial while granular microcrystalline quartz forms during deeper burial at warmer temperatures. The temperature at which opal-CT forms is thus probably approximately equal to the temperature of the overlying bottom water. Isotopic temperatures deduced for opal-CT formation are preliminary and very approximate, but yield Eocene deep-water temperatures of 5-13°C, and 6°C for the upper Cretaceous sample. Pure euhedral quartz crystals lining a cavity in opal-CT at 388 m in core 8-70B-4-CC have a ~delta18O value of +29.8? and probably formed near maximum burial. The isotopic temperature is approximately 32 ° C.

Amino acid racemization for several DSDP samples (Table 1)

Kinetic parameters for the epimerization of isoleucine in multispecific foraminiferal asemblages were used to establish the effects of burial depth and the geothermal gradient on the extent of reaction. It was observed that with a little as thirty meters of burial in a normal thermal regime there were differences between the extent of epimerization measured and that which would have been predicted for thermal equilibrium with bottom water temperatures. As would be expected, these differences are greatest when the heat flow (the geothermal gradient) and/or the sedimentation rates are highest. These effects were observed in most of the DSDP samples studied, and have been used to estimate the average heat flux since the time of sample deposition. Occasional anomalous effects were observed which could not be related to past or present heat flux. These were determined to be due to such geologic occurrences as slumping and reworking or to recent sample contamination. Other problems emerged related to bottom water temperatures including changes over geologic time which are unknown and could not be deduced. Thus, the presence of epimerization anomalies in DSDP cores as noted above limits the effectiveness of amino acid geochronology in such cores, unless these anomalies can be recognized as ab initio.

Bulk and amino acid parameters of core SO188-342KL from the Northern Bay of Bengal for the last 18 ka

The Northern Bay of Bengal (NBoB) is a globally important region for deep-sea organic matter (OM) deposition due to massive fluvial discharge from the Ganges-Brahmaputra-Meghna (G-B-M) rivers and moderate to high surface productivity. Previous studies have focused on carbon burial in turbiditic sediments of the Bengal Fan. However, little is known about the storage of carbon in pelagic and hemipelagic sediments of the Bay of Bengal over millennial time scales. This study presents a comprehensive history of OM origin and fate as well as a quantification of carbon sediment storage in the Eastern Bengal Slope (EBS) during the last 18 ka. Bulk organic proxies (TOC, TIC, TN, d13CTOC, d15NTN) and content and composition of total hydrolysable amino acids (THAA) in a sediment core (SO188-342KL) from the EBS were analyzed. Three periods of high OM accumulation were identified: the Late Glacial (LG), the Bölling/Alleröd (B/A), and the Early Holocene Climatic Optimum (EHCO). Lower eustatic sea level before 15 ka BP allowed a closer connection between the EBS and the fluvial debouch, favoring high terrestrial OM input to the core site. This connection was progressively lost between 15 and 7 ka BP as sea level rose to its present height and terrestrial OM input decreased considerably. Export and preservation of marine OM was stimulated during periods of summer monsoon intensification (B/A and EHCO) as a consequence of higher surface productivity enhanced by cyclonic-eddy nutrient pumping and fluvial nutrient delivery into the photic zone. Changes in the THAA composition indicate that the marine plankton community structure shifted from calcareous-dominated before 13 ka BP to siliceous-dominated afterwards. They also indicate that the relative proportion of marine versus terrestrial OM deposited at site 342KL was primarily driven by relative sea level and enlarged during the Holocene. The ballasting effect of lithogenic particles during periods of high coastal proximity and/or enhanced fluvial discharge promoted the export and preservation of OM. The high organic carbon accumulation rates in the EBS during the LG (18-17 ka BP) were 5-fold higher than at present and comparable to those of glacial upwelling areas. Despite the differences in sediment and OM transport and storage among the Western and Eastern sectors of the NBoB, this region remains important for global carbon sequestration during sea level low-stands. In addition, the summer monsoon was a key promotor of terrestrial and marine OM export to the deep-ocean, highlighting its relevance as regulator of the global carbon budget.

(Table 1) Chemical and isotopic composition of pore fluids in cores TGC-1 and TGC-6

The role of sediment diagenesis in the marine cycles of Li and B is poorly understood. Because Li and B are easily mobilized during burial and are consumed in authigenic clay mineral formation, their abundance in marine pore waters varies considerably. Exchange with the overlying ocean through diffusive fluxes should thus be common. Nevertheless, only a minor Li sink associated with the low-temperature alteration of volcanic ash has been observed. We describe a low-temperature diagenetic environment in the Black Sea dominated by the alteration of detrital plagioclase feldspars. Fluids expelled from the Odessa mud volcano in the Sorokin Trough originate from shallow (~100-400 m deep) sediments which are poor in volcanic materials but rich in anorthite. These fluids are depleted in Na+, K+, Li+, B, and 18O and enriched in Ca2+ and Sr2+, indicating that anorthite is dissolving and authigenic clays are forming. Using a simple chemical model, we calculate the pH and the partial pressure of CO2 (PCO2) in fluids associated with this alteration process. Our results show that the pH of these fluids is up to 1.5 pH units lower than in most deep marine sediments and that PCO2 levels are up to several hundred times higher than in the atmosphere. These conditions are similar to those which favor the weathering of silicate minerals in subaerial soil environments. We propose that in Black Sea sediments enhanced organic matter preservation favors CO2 production through methanogenesis and results in a low pore water pH, compared to most deep sea sediments. As a result, silicate mineral weathering, which is a sluggish process in most marine diagenetic environments, proceeds rapidly in Black Sea sediments. There is a potential for organic matter-rich continental shelf environments to host this type of diagenesis. Should such environments be widespread, this new Li and B sink could help balance the marine Li and Li isotope budgets but would imply an apparent imbalance in the B cycle.

(Table 1) Diatom mats from ODP Leg 177 Sites in the Southern Ocean, Atlantic Sector

The interaction between biogenic silica export and burial, paleoceanography, diatom species succession and mats formation was examined based on relative abundances data of Plio/Pleistocene diatoms from six cores recovered during ODP Leg 177 on a transect across the Antarctic Circumpolar Current (ACC) in the Atlantic sector of the Southern Ocean. Fragilariopsis kerguelensis, Actinocyclus ingens and species of the genus Thalassiothrix were the main contributors to the diatom assemblages. Three main steps marked the development of the silica system in the Southern Ocean: Step 1 (at ca. 2.77 Ma), establishment of increased biogenic silica burial in the Antarctic Circumpolar Current area, following the large-scale oceanic reorganization connected to the increased northern hemisphere glaciation; Step 2 (at ca. 1.93 Ma), the Antarctic Polar Front becomes the main biogenic silica sink, diatom mats are widespread, and are also found slightly to the north and south of the APF; Step 3 (at ca. 0.63 Ma), with the strong drop in abundance (and later extinction at 0.38 Ma) of A. ingens and the rise to dominance of F. kerguelensis, the system enters a glacial-interglacial mode, with diatom mats occurring during interglacials at the APF and in the Antarctic Zone, but disappearing north of it.

Pelagic phosphorus accumulation in the Pacific Ocean

As a limiting nutrient to marine life, phosphorus (P) is an effective tracer of today's marine productivity. The distribution of P in marine sediments likewise tracks the history of marine productivity because of its relative insolubility in seawater. CaCO3, biogenic opal, terrigenous sediment, and total P have been measured in cores from nine Pacific sites (Deep Sea Drilling Project (DSDP) 65, 66, 310, 77, 62, 572, 463, 586, and GPC-3) and one subantarctic (DSDP 266) site. These sites were specifically chosen to provide information on biota burial flux changes with time for sedimentary sinks that represent key oceanographic variables, i.e., rate of upwelling, water depth, and carbonate dissolution gradient. The accumulation rates of these components for the last 10 Ma were then calculated from determined core age versus depth plots, core bulk density, and porosity data. The accumulation of P weakly correlates with that of CaCO3, moderately with that of total sediment, and very strongly with carbonate-free accumulation. Two prominent peaks for all components occur at 2-3 Ma and 5-6 Ma, and record the chemical loading of dissolved CaCO3, SiO2, and P from glacially emergent continental shelves. These results indicate that continental shelf phosphorites form during interglacially high sea levels and correspond to low deep-sea P accumulation rates, whereas glacially lowered sea levels allow for shelf bypassing and greater deep-sea P accumulation rates.