Component composition and benthic foraminifera in sediments of ODP Leg 112

Indicators of surface-water productivity and bottom-water oxygenation have been studied for the age interval from the latest Pleistocene to the Holocene at three holes (679D, 680B, and 68IB) located in the center and at the edges of an upwelling cell at approximately 11°S on the Peruvian continental margin. Upwelling activity was maximal at this latitude during d18O Stages 1 (lower part), 3, the upper part of 5, the lower part of 6, and 7, as documented by high diatom abundance. During these time intervals, the bottom water was poorly oxygenated, as documented by low diversity benthic foraminiferal assemblages that are dominated by B. seminuda s.l. Both surface- and bottom-water-circulation patterns appear to have changed rapidly over short time intervals. Due to changes in surface circulation, the intensity of upwelling decreased, thereby decreasing the concentration of nutrients, and reducing the supply of organic matter to the bottom. Radiolarians became more abundant in the surface waters, and the bottom-water environment was less depleted in oxygen, allowing for the establishment of more diverse benthic foraminiferal assemblages. Surface-water productivity was probably minimal during the early part of d18O Stages 5 and 9, as indicated by the increased abundance of planktonic foraminifers and pteropods and their subsequent preservation.

Hydrogen, carbon, and oxygen isotope ratios of interstitial fluides of ODP Leg 104 holes

Carbon, hydrogen, and oxygen isotope ratios determined on 32 squeezed interstitial fluid samples show remarkable variations with depth. For the most part these variations are related to diagenetic and alteration reactions taking place in the sediments, and in the underlying basalts. delta13C SumCO2 depth distributions at Sites 642 and 643 are the result of mixing of original SumCO2 of the paleo bottom water with SumCO2 released by remineralization of organic matter. At Site 644, where sulfate exhaustion occurs, the processes of methanogenesis by CO2 reduction and anaerobic methanotrophy strongly influence the delta13C SumCO2 distribution. Hydrogen and oxygen isotopes roughly covary, and become enriched in 16O and1H with depth. This effect is most pronounced at Sites 642 and 643, possibly due to the influence of the directly underlying basalts. Isotope depletions at Site 644 are much lower, corresponding to the greater sediment depth to basement. The alternative, that the O, H isotope shifts are due primarily to autochthonous diagenetic and exchange reactions, is not supported by the data available.

Detriral flux of sediment cores in the southeast Indian Ocean

Because of a close relationship between detrital flux variations and magnetic susceptibility (MS) flux (MS cm**3 of bulk sediment multiplied by the linear sedimentation rate) variations in the southeast Indian basin of the southern ocean, MS flux profiles have been used to examine the spatial and temporal detrital flux changes in this basin during the last climatic cycle. Results indicate a general increase in detrital material input during the coldest periods, suggesting a widespread phenomenon, at least on the basin scale. Mineralogical data, geochemical data, and 87Sr/86Sr isotopic ratios have been used to determine the origin and transport mechanisms responsible for increased detrital flux during glacial periods. Mineralogical and geochemical data show that these glacial 'highs' are due to increases in both Kerguelen-Crozet volcanic and Antarctic detrital inputs. The 87Sr/86Sr isotopic composition of the >45-µm fraction indicates that the Kerguelen-Crozet province contributes to at least 50% of the coarse particule input to the west. This contribution decreases eastward to reach less than 10%. These tracers clearly indicate that the Crozet-Kerguelen province was a major source region of detrital in the western part of the basin during glacial times. In contrast, material of Antarctic origin is well represented in the whole basin (fine and coarse fractions). Because of the minor amount of coarse particles in the sediments, volcanic particles from Kerguelen and crustal particles from Antarctica have most probably been transported by the Antarctic bottom water current and/or the Circumpolar deepwater current during glacial periods as is the case today. Nevertheless, the presence of coarse particles even in low amount suggests also a transport by ice rafting (sea-ice and icebergs), originated from both Kerguelen and Antarctic sources. However, the relative importance of both hydrographic and ice-rafting modes of transport cannot be identified accurately with our data. During low sea level stands (glacial maximum periods), increasing instability and erosion of the continental platform and shallow plateaus could have resulted in a more efficient transfer of crustal and volcano-detrital material to the Southeast Indian basin. At the same time, extension of the grounded ice shelves over the continental margins and increase in the erosion rate of the Antarctic ice sheet could have induced a greater input of ice rafted detritus (IRD) to southern ocean basins. Enhancement of the circumpolar deepwater current strength might have also carried a more important flux of detrital material from Kerguelen. However, an increase in the bottom water flow is not necessarily required.

Cenozoic oxygen isotopic values for benthic foraminifera from DSDP and ODP low and high latitude marine sediment cores

The climate during the Cenozoic era changed in several steps from ice-free poles and warm conditions to ice-covered poles and cold conditions. Since the 1950s, a body of information on ice volume and temperature changes has been built up predominantly on the basis of measurements of the oxygen isotopic composition of shells of benthic foraminifera collected from marine sediment cores. The statistical methodology of time series analysis has also evolved, allowing more information to be extracted from these records. Here we provide a comprehensive view of Cenozoic climate evolution by means of a coherent and systematic application of time series analytical tools to each record from a compilation spanning the interval from 4 to 61 Myr ago. We quantitatively describe several prominent features of the oxygen isotope record, taking into account the various sources of uncertainty (including measurement, proxy noise, and dating errors). The estimated transition times and amplitudes allow us to assess causal climatological-tectonic influences on the following known features of the Cenozoic oxygen isotopic record: Paleocene-Eocene Thermal Maximum, Eocene-Oligocene Transition, Oligocene-Miocene Boundary, and the Middle Miocene Climate Optimum. We further describe and causally interpret the following features: Paleocene-Eocene warming trend, the two-step, long-term Eocene cooling, and the changes within the most recent interval (Miocene-Pliocene). We review the scope and methods of constructing Cenozoic stacks of benthic oxygen isotope records and present two new latitudinal stacks, which capture besides global ice volume also bottom water temperatures at low (less than 30°) and high latitudes. This review concludes with an identification of future directions for data collection, statistical method development, and climate modeling.

Benthic foraminiferal communities at DSDP Sites 94-609 to 94-611

Benthic foraminiferal assemblages from northeast Atlantic DSDP Sites 609, 610, and 611 have been interpreted with reference to modern assemblages known to be linked with the overlying bottom-water masses. It is shown that the water masses in the late Miocene to Pleistocene were similar to those of today. The distribution of the water masses changed with time, however. Antarctic Bottom Water ("AABW"), which at present is restricted to the area south of the Azores, reached as far north as the Gibbs Fracture Zone in the early Pliocene. Increased production of North Atlantic Deep Water in the late Pliocene displaced the AABW to the south

Amino acid in Deep Sea Drilling Project cores

Several amino acid diagenetic reactions, which take place in the deep-sea sedimentary environment, were investigated, using various Deep Sea Drilling Project (DSDP) cores. Initially it was found that essentially all the amino acids in sediments are bound in peptide linkages; but, with increasing age, the peptide bonds undergo slow hydrolysis that results in an increasingly larger fraction of amino acids in the free state. The hydrolysis half-life in calcareous sediments was estimated to be ~1-2 million years, while in non-carbonate sediment the hydrolysis rate may be considerably slower. The amino acid compositions and the extent of racemization of several amino acids were determined in various fractions isolated from the sediments. These analyses demonstrated that the mechanism, kinetics, and rate of amino acid diagenesis are highly dependent upon the physical state (i.e., free, bound, etc.) in which the amino acids exist in the sedimentary environment. In the free state, serine and threonine were found to decompose primarily by a dehydration reaction, while in the bound state (residue or HCl-insoluble fraction) a reversible aldol-cleavage reaction is the main decomposition pathway of these amino acids. The change in amino acid composition of the residue fraction with time was suggested to be due to the hydrolysis of peptide bonds, while in foraminiferal tests the compositional changes over geological time are the result of various decomposition reactions. Reversible first-order racemization kinetics are not observed for free amino acids in sediments. The explanation for these anomalous kinetics involves a complex reaction series which includes the hydrolysis of peptide bonds and the very rapid racemization of free amino acids. The racemization rates of free amino acids in sediments were found to be many orders of magnitude faster than those predicted from elevated temperature experiments using free amino acids in aqueous solution. The racemization rate enhancement of free amino acids in sediments may be due to the catalysis of the reaction by trace metals. Reversible first-order kinetics are followed for amino acids in the residue fraction isolated from sediments; the rate of racemization in this fraction is slower than that predicted for protein-bound amino acids. Various applications of amino acid diagenetic reactions are discussed. Racemization and the decomposition reaction of serine and threonine can both be used, with certain limitations, to make rough age estimates of deep-sea sediments back to several million years. The extent of racemization in foraminiferal tests which have been dated by some other independent technique can be used to estimate geothermal gradients, and thus heat flows, and to evaluate the bottom water temperature history in certain oceanic areas.

Stable isotope ratios measured on carbonate tests from the Kara Sea

River discharge of Ob and Yenisei to the Kara Sea is highly variable on seasonal and interannual time scales. River water dominates the shallow bottom water near the river mouths, making it warmer and less saline but seasonally and interannually more changeable than bottom water on the deeper shelf. This hydrographic pattern shows up in measurements and modelling, and in stable isotope records (delta18O, delta13C) along the growth axis of bivalve shells and in multiple analyses of single benthic foraminiferal shells. Average isotope ratios increase, but sample-internal variability decreases with water depth and distance from river mouths. However, isotope records of bivalves and foraminifera of a sediment core from a former submarine channel of Yenisei River reveal a different pattern. The retreat of the river mouth from this site due to early Holocene sea level rise led to increasing average isotope values up core, but not to the expected decrease of the in-sample isotope variability. Southward advection of cold saline water along the palaeo-river channel probably obscured the hydrographic variability during the early Holocene. Later, when sediment filled the channel, the hydrographic variability at the core location remained low, because the shallowing proceeded synchronously with the retreat of the river mouth.

Oxygen and carbon isotopes from foraminifers and benthic foraminiferal abundance at DSDP Holes 71-511 and 71-512

An Eocene-Oligocene oxygen and carbon isotope history based on planktonic and benthic foraminifers from Deep Sea Drilling Project Leg 71 cores has been constructed for the Maurice Ewing Bank of the eastern Falkland Plateau, Southwest Atlantic Ocean. Specifically, the cores cover portions of the middle Eocene, upper Eocene, and lower Oligocene. Surface water isotopic temperatures postulated for the middle Eocene at Site 512 fluctuated within about four degrees but generally averaged about 9°C. Bottom isotopic temperatures at Site 512 (water depth, 1846 m) were generally a degree lower than surface water temperatures. Surface water isotopic temperatures at Site 511 initially averaged about 11°C during the late Eocene, but dropped to an average of 7°C in the early Oligocene. Bottom isotopic temperatures at Site 511 (water depth, 2589 m) generally record temperatures between 12.5°C and 8°C, similar to the range in the surface water isotopic temperatures. During the early Oligocene, bottom isotopic temperatures dropped sharply and averaged about 2°C (very close to present-day values). Surface water temperature values also decreased to an average of about 7°C, therefore leading to a significant divergence between surface and bottom water isotopic temperatures during the early Oligocene. Comparisons among Southern Ocean DSDP Sites 511, 512, and 277, and between these and other DSDP sites from central and northern latitudes (Sites 44, 167, 171, 292, 357, 398, 119, and 401) show that much of the Eocene was characterized by relatively warm temperatures until sometime in either the middle Eocene, late Eocene, or early Oligocene. At each site, conspicuous 18O enrichments occur in both the benthic and planktonic foraminifers over a relatively short period of time. Although a general trend toward a climatic deterioration is evident, the density of data points among the various studies is still too sparse to determine either synchrony or time-transgression between the major isotopic events. A close correlation could be made between the Site 511 oxygen isotope temperature curve and paleoclimatic trends derived independently from radiolarian studies. The sharp temperature drop and the divergence between bottom and surface water temperatures during the early Oligocene apparently reflect a major expansion of the antarctic water mass. The migration of the boundary between the subantarctic and antarctic water masses over the site at this time would account in part for the sharp temperature changes. Sharp changes of this nature would not necessarily be noted in other geographic areas, particularly those to the north which have different oceanographic regimes.

Stable carbon and oxygen isotope record of benthic foraminifera from Paleocene-Eocene sediments

A major change in Cenozoic deep-sea benthic foraminifera occurred in the Atlantic, Indian, and Pacific oceans near the Paleocene/Eocene boundary. Benthic foraminiferal abundance changes began at about 61.5 Ma at Pacific Deep Sea Drilling Project (DSDP) Site 577. A major extinction event followed at 58-57 Ma (between Zones P6a and P6b), and a series of first appearances continued until circa 55.5 Ma (Zone P6c). These faunal changes occurred during a 6°C warming of Pacific bottom water and may indicate that the primary cause was changing temperature. Other potential causes of the faunal turnover include global changes in surface ocean productivity and changing bottom water source regions. Comparison of benthic and planktonic delta13C records requires no change in the ratio of oceanic phosphorous to carbon during the late Paleocene to early Eocene, which weakens the case for (but does not disprove) a change in surface ocean productivity at this time. Interbasinal comparisons of benthic foraminiferal delta13C records document that water with high delta13C values filled the Cape Basin during the late Paleocene and possibly the early Eocene (circa 61-57 Ma), but apparently did not extend into the western basins of the Atlantic. This pattern suggests a supply of Antarctic source water for the Cape Basin and possible tectonic isolation of the western Atlantic basins during at least part of the late Paleocene. Carbon isotope comparisons show that bottom water supply to the Cape Basin was reduced in the early Eocene. Eolian grain size data suggest that a decrease in zonal wind intensity occurred at the end of the Paleocene. These late Paleocene climatic changes (bottom water warming and decreased wind intensity) correspond with evidence for an important global tectonic reorganization and extensive subaerial volcanism, which may have contributed to climatic warming through increased supply of CO2.

Late Cretaceous benthic foraminiferal assemblages from Demerara Rise, western tropical Atlantic

This paper is based on Santonian-Campanian sediments of Ocean Drilling Program Sites 1257 (2951 mbsl) and 1259 (2353 mbsl) from Demerara Rise (Leg 207, western tropical Atlantic, off Surinam). According to its position, Demerara Rise should have been influenced by the early opening of the Equatorial Atlantic Gateway and the establishment of a bottom-water connection between the central and South Atlantic Oceans during the Late Cretaceous. The investigated benthic foraminiferal faunas demonstrate strong fluctuations in bottom-water oxygenation and organic-matter flux to the sea-floor. The Santonian-earliest Campanian interval is characterised by laminated black shales without benthic foraminifera in the lowermost part, followed by an increasing number of benthic foraminifera. These are indicative of anoxic to dysoxic bottom waters, high organic-matter fluxes and a position within the oxygen minimum zone. At the shallower Site 1259, benthic foraminifera occurred earlier (Santonian) than at the deeper Site 1257 (Early Campanian). This suggests that the shallower site was characterised by fluctuations in the oxygen minimum zone and that a re-oxygenation of the sea-floor started considerably earlier at shallower water-depths. We speculate that this re-oxygenation was related to the ongoing opening of the Equatorial Atlantic Gateway. A condensed glauconitic chalk interval of Early Campanian age (Nannofossil Zone CC18 of Sissingh) overlies the laminated shales at both sites. This interval contains benthic foraminiferal faunas reflecting increasing bottom-water oxygenation and reduced organic-matter flux. This glauconitic chalk is strongly condensed and contains most of the Lower and mid-Campanian. Benthic foraminiferal species indicative of well-oxygenated and more oligotrophic environments characterise the overlying mid- to Upper Campanian nannofossil chalk. During deposition of the nannofossil chalk, a permanent deep-water connection between the central and South Atlantic Oceans is proposed, leading to ventilated and well-oxygenated bottom waters. If this speculation is true, the establishment of a permanent deep-water connection between the central and South Atlantic Oceans terminated Oceanic Anoxic Event 3 "black shale" formation in the central and South Atlantic marginal basins during the Early Campanian (Nannofossil Zone CC18) and led to well-oxygenated bottom waters in the entire Atlantic Ocean during the Late Campanian (at least from Nannofossil Zone CC22 onwards).

Elemental and stable isotopic composition of some metalliferous and pelagic sediments at DSDP Leg 70 Holes

Nontronite, the main metalliferous phase of the Galapagos mounds, occurs at subsurface depths of about 2 to 20 meters; Mn-oxide material is limited to the upper 2 meters of the mounds. The nontronite forms intervals of up to a few meters' thickness, consisting essentially of 100% nontronite granules, which alternate with intervals of normal pelagic sediment. Electron microprobe analyses of nontronite granules from different core samples indicate that: (1) there is little difference in major element composition between nontronites from varying locations within the mounds, with adjacent granules from a given sample having very similar compositions; (2) individual granules show little internal variation in composition. This indicates that the granules are composed of a single mineral of essentially constant composition, consistent with relatively uniform conditions of Eh and composition during nontronite formation. Mn-oxide crusts have very low Fe contents, a feature characteristic of rapidly deposited Mn-oxide crusts formed under hydrothermal influences. The rare-earth element (REE) abundances of the nontronites are generally extremely low, totalling less than several ppm. Two samples have the negatively Ce anomaly typical of authigenic precipitates formed relatively rapidly from seawater. A Mn-oxide crust sample has low REE contents, typical of Mn-oxide crusts formed under hydrothermal influences, but no negative Ce anomaly. A sample of unusual Mn-Fe-oxide mud has relatively high REE concentrations and a seawater-type pattern; both of these features are also found for metalliferous sediments from the East Pacific Rise. The oxygen and hydrogen isotopic composition of the nontronites define a restricted field within a d18O-dD plot. In manganiferous sediments, d18O and dD appear to decrease with increase in the Mn-oxide content of the sediment. From the d18O values of the nontronites, formation temperatures in the range of about 20-30°C have been estimated. By comparison, temperatures of up to 11.5 °C at a 9-meter depth have been directly measured within the mounds (Corliss et al., 1979), and heat-flow data suggest present basement/sediment interface temperatures of 15-25°C. In a plot of Fe + Mn vs. d18O, the Mn-oxide crust and Mn-Fe-ooze plot near the tie-lines for authigenic Mn nodules and silicate phases, implying that they have formed in isotopic equilibrium with seawater at or close to bottom-water temperatures.

Geochemistry of Baltic Sea sediments

The Baltic Sea has experienced three major intervals of bottom water hypoxia following the intrusion of seawater ca. 8 kyrs ago. These intervals occurred during the Holocene Thermal Maximum (HTM), Medieval Climate Anomaly (MCA) and during recent decades. Here, we show that sequestration of both Fe and Mn in Baltic Sea sediments generally increases with water depth, and we attribute this to shelf-to-basin transfer ("shuttling") of Fe and Mn. Burial of Mn in slope and basin sediments was enhanced following the lake-brackish/marine transition at the beginning of the hypoxic interval during the HTM. During hypoxic intervals, shelf-to-basin transfer of Fe was generally enhanced but that of Mn was reduced. However, intensification of hypoxia within hypoxic intervals led to decreased burial of both Mn and Fe in deep basin sediments. This implies a non-linearity in shelf Fe release upon expanding hypoxia with initial enhanced Fe release relative to oxic conditions followed by increased retention in shelf sediments, likely in the form of iron sulfide minerals. For Mn, extended hypoxia leads to more limited sequestration as Mn carbonate in deep basin sediments, presumably because of more rapid reduction of Mn oxides formed after inflows and subsequent escape of dissolved Mn to the overlying water. Our Fe records suggest that modern Baltic Sea hypoxia is more widespread than in the past. Furthermore, hypoxia-driven variations in shelf-to-basin transfer of Fe may have impacted the dynamics of P and sulfide in the Baltic Sea thus providing potential feedbacks on the further development of hypoxia.

Late Quaternary benthic foraminiferal record of the Bounty Trough, east of New Zealand

The Bounty Trough, east of New Zealand, lies along the southeastern edge of the present-day Subtropical Front (STF), and is a major conduit via the Bounty Channel, for terrigenous sediment supply from the uplifted Southern Alps to the abyssal Bounty Fan. Census data on 65 benthic foraminiferal faunas (>63 µm) from upper bathyal (ODP 1119), lower bathyal (DSDP 594) and abyssal (ODP 1122) sequences, test and refine existing models for the paleoceanographic and sedimentary history of the trough through the last 150 ka (marine isotope stages, MIS 6-1). Cluster analysis allows recognition of six species groups, whose distribution patterns coincide with bathymetry, the climate cycles and displaced turbidite beds. Detrended canonical correspondence analysis and comparisons with modern faunal patterns suggest that the groups are most strongly influenced by food supply (organic carbon flux), and to a lesser extent by bottom water oxygen and factors relating to sediment type. Major faunal changes at upper bathyal depths (1119) probably resulted from cycles of counter-intuitive seaward-landward migrations of the Southland Front (SF) (north-south sector of the STF). Benthic foraminiferal changes suggest that lower nutrient, cool Subantarctic Surface Water (SAW) was overhead in warm intervals, and higher nutrient-bearing, warm neritic Subtropical Surface Water (STW) was overhead in cold intervals. At lower bathyal depths (594), foraminiferal changes indicate increased glacial productivity and lowered bottom oxygen, attributed to increased upwelling and inflow of cold, nutrient-rich, Antarctic Intermediate Water (AAIW) and shallowing of the oxygen-minimum zone (upper Circum Polar Deep Water, CPDW). The observed cyclical benthic foraminiferal changes are not a result of associations migrating up and down the slope, as glacial faunas (dominated by Globocassidulina canalisuturata and Eilohedra levicula at upper and lower bathyal depths, respectively) are markedly different from those currently living in the Bounty Trough. On the abyssal Bounty Fan (1122), faunal changes correlate most strongly with grain size, and are attributed to varying amounts of mixing of displaced and in-situ faunas. Most of the displaced foraminifera in turbiditic sand beds are sourced from mid-outer shelf depths at the head of the Bounty Channel. Turbidity currents were more prevalent during, but not restricted to, glacial intervals.

Siliceous components of Pliocene-Holocene sediments of the South Atlantic

The Pliocene-Holocene sediments recovered on ODP Leg 114 from Holes 699A, 701C, and 704B are the subject of a detailed investigation to interpret changes in the Oceanographic environment of the South Atlantic in the vicinity of the Polar Front Zone (PFZ). The cores sample sediments at shallow (Hole 704B, 2532 m), intermediate (Hole 699A, 3716 m), and basinal (Hole 701C, 4647 m) depths. Sites 699 and 704 come under the influence of the Antarctic Circumpolar Current (ACC) and Circumpolar Deep Water. It is possible that the upper reaches of Antarctic Bottom Water (AABW) may also affect Hole 699A. Site 701 is influenced by AABW. Closely spaced samples were analyzed for grain-size distribution, sand fraction components, biosiliceous microfossils, organic carbon, and water content. PFZ migrations are traced using changes in bulk sedimentaccumulation rates and the abundance of the diatoms Actiniscus ssp. and Genus et species indet. 1 Fenner (1991), as well as changes in sediment grain size and composition. Diatomaceous sediments of Gilbert age in Hole 699A indicate that the PFZ was positioned over this site, but during the Gauss it migrated north, bringing in less productive Antarctic Surface Water. All cores document a very gradual southerly movement of the PFZ throughout the Matuyama (with some sharp fluctuations of the northen PFZ border over Site 704 between 1.45 and 1.83 m.y.). This regressive shift culminated in the late Matuyama. The latest Matuyama to earliest Brunhes record in Hole 699A has been removed by a hiatus lasting from 1.0 to 0.6 m.y., which was probably caused by intensification of the deep-reaching ACC. The corresponding interval in Hole 704B, the shallowest core, contains evidence of winnowing. Sharp fluctuations of large amplitude and high frequency in the lithology of the sediments from Hole 704B in the eastern South Atlantic, starting at about 0.75 m.y. and characterizing the whole Brunhes Epoch, record the rapid movement of the northern border of the PFZ over the site. These reflect strong glacial/interglacial alternations in climate. To a lesser extent, lithologic fluctuations in Hole 701C reflect the same phenomenon, whereas in Hole 699A the lithology does not vary as dramatically.