Age determination of North Atlantic sediment cores

Records of planktonic foraminiferal shell weights for Globigerina bulloides, covering Termination I from four proximal sites at waters depths from 1150 to 4045 m in the northeast Atlantic, demonstrate the influence of dissolution superimposed upon initial shell weight variability. Records of shell weight, unaffected by dissolution, may be used as a reference for interpreting deeper records in terms of preservation history. Combining records of planktonic shell weight (and benthic d13C) from shallow and deep sites suggests that maximum oceanic stratification and incursion of southern sourced deep waters in the North Atlantic occurred at about 18-20 ka, defining the glacial mode of Atlantic circulation. Reduced stratification and enhanced preservation in deeper waters reflect conditions during Heinrich event 1. A state similar to the modern mode of Atlantic circulation was attained by about 10 ka.

Geochemistry of foraminifera from sediment cores of the central California margin

Under present climate conditions, convection at high latitudes of the North Pacific is restricted to shallower depths than in the North Atlantic. To what extent this asymmetry between the two ocean basins was maintained over the past 20 kyr is poorly known because there are few unambiguous proxy records of ventilation from the North Pacific. We present new data for two sediment cores from the California margin at 800 and 1600 m depth to argue that the depth of ventilation shifted repeatedly in the northeast Pacific over the course of deglaciation. The evidence includes benthic foraminiferal Cd/Ca, 18O/16O, and 13C/12C data as well as radiocarbon age differences between benthic and planktonic foraminifera. A number of features in the shallower of the two cores, including an interval of laminated sediments, are consistent with changes in ventilation over the past 20 kyr suggested by alternations between laminated and bioturbated sediments in the Santa Barbara Basin and the Gulf of California [Keigwin and Jones, 1990 doi:10.1029/PA005i006p01009; Kennett and Ingram, 1995 doi:10.1038/377510a0; Behl and Kennett, 1996 doi:10.1038/379243a0]. Data from the deeper of the two California margin cores suggest that during times of reduced ventilation at 800 m, ventilation was enhanced at 1600 m depth, and vice versa. This pronounced depth dependence of ventilation needs to be taken into account when exploring potential teleconnections between the North Pacific and the North Atlantic.

Stable isotope and trace element geochemistry of carbonate sediments at DSDP Holes 87-577 and 6-47.2

Detailed analyses of well-preserved carbonate samples from across the Cretaceous/Tertiary boundary in Hole 577 have revealed a significant decline in the d13C values of calcareous nannoplankton from the Maestrichtian to the Danian Age accompanied by a substantial reduction in carbonate accumulation rates. Benthic foraminifers, however, do not exhibit a shift in carbon composition similar to that recorded by the calcareous nannoplankton, but actually increase slightly over the same time interval. These results are similar to the earlier findings at two North Pacific Deep Sea Drilling Project locations, Sites 47.2 and 465, and are considered to represent a dramatic decrease in oceanic phytoplankton production associated with the catastrophic Cretaceous/Tertiary boundary extinctions. In addition, the change in carbon composition of calcareous nannoplankton across the Cretaceous/Tertiary boundary at Hole 577 is accompanied by only minor changes in the oxygen isotope trends of both calcareous nannoplankton and benthic foraminifers, suggesting that temperature variations in the North Pacific from the late Maestrichtian to the early Danian Age were insignificant.

Composition of sediment pore water and isotopes in carbonate and benthic foraminifera at DSDP Holes 68-501, 69-505 and Site 69-504

Two sites on the southern flank of the Costa Rica Rift were drilled on DSDP Legs 68 and 69, one on crust 3.9 m.y. old and the other on crust 5.9 m.y. old. The basement of the younger site is effectively cooled by the circulation of seawater. The basement of the older site has been sealed by sediment, and an interval in the uppermost 560 meters of basement recently reheated to temperatures of 60 to 120°C. Although the thickness of the sediments at the two sites is similar (150-240 m versus 270 m), the much rougher basement topography at the younger Site 505 produces occasional basement outcrops, through which 80 to 90% of the total heat loss apparently occurs by advection of warm seawater. This seawater has been heated only slightly, however; the temperature at the base of the sediments is only 9°C. Changes in its composition due to reaction with the basement basalts are negligible, as indicated by profiles of sediment pore water chemistry. Bacterial sulfate reduction in the sediments produces a decrease in SO4 (and Ca) and an increase in alkalinity (and Sr and NH3) as depth increases to an intermediate level, but at deeper levels these trends reverse, and all of these species plus Mg, K, Na, and chlorinity approach seawater values near basement. Si, however, is higher, and Li may be lower. At the older site, Site 501/504, where heat loss is entirely by conduction, the temperature at the sediment/basement contact is 59°C. Sediment pore water chemistry is heavily affected by reaction with the basaltic basement, as indicated by large decreases in d18O, Mg, alkalinity, Na, and K and an increase in Ca with increasing depth. The size of the changes in d18O, Mg, alkalinity, Ca, Sr, and SO4 varies laterally over 500 meters, indicating lateral gradients in pore water chemistry that are nearly as large as the vertical gradients. The lateral gradients are believed to result from similar lateral gradients in the composition of the basement formation water, which propagate upward through the sediments by diffusion. A model of the d18O profile suggests that the basement at Site 501/504 was sealed off from advection about 1 m.y. ago, so that reaction rates began to dominate the basement pore water chemistry. A limestone-chert diagenetic front began to move upward through the lower sediments less than 200,000 yr. ago.

Organic matter in sediments of ODP Site 131-808

Microscopic studies reveal a predominance of terrestrial organic matter in sediments of Site 808. Terrestrial vitrinite and inertinite are more abundant (73% to 100%) than marine organic matter (alginite, 0% to 27%), which increases from open oceanic deposits of the Shikoku Basin sediments to sediments of the outer trench wedge. The abundance of terrestrial organic matter is also reflected through carbon isotope values of -23 per mil to -25.9 per mil. Mass accumulation rates of organic carbon are low in hemipelagic sediments of the Shikoku Basin (<0.2 g/cm**2/k.y.) but increase significantly in sediments of the Nankai Trench (0.2 to 1.7 g/cm**2/k.y.). Although the organic mass accumulation is high in sediments of the Nankai Trench, a comparison of sedimentation rates and total organic carbon suggests relative dilution of organic carbon through turbidite flows. Calculated marine paleoproductivity of organic carbon is low in sediments of the open ocean (Shikoku Basin) and increases closer to the shore (Nankai Trench). Thermal evolution of organic matter is obtained from vitrinite reflectance measurements. Two populations of vitrinites have been observed between 600 and 1234 mbsf. Reflectance values change with increasing depth and temperature in both groups of vitrinite (0.3% to 0.68% in group 1; 0.6% to 1% in group 2).

Analysis of organic matter from DSDP Leg 81 Holes

Organic geochemical and visual kerogen analyses were carried out on approximately 50 samples from Leg 81 (Rockall Plateau, North Atlantic). The sediments are from four sites (Sites 552-555), Pleistocene to Paleocene in age, and represent significantly different depositional environments and sources of organic matter. The Pleistocene glacial-interglacial cycles show differences in sedimentary organic matter based on Rock-Eval pyrolysis, organic phosphorus, and pyrolysis/mass-spectrometry analyses. Glacial samples contain more organic carbon, with a larger proportion of reworked organic matter. This probably reflects increased erosion of continental and shelf areas as a result of low sea level stands. Inter glacial samples contain a larger proportion of marine organic matter as determined by organic phosphorus and pyrolysis analyses. This immature, highly oxidized marine organic matter may be associated with the skeletal organic matrix of calcareous organisms. In addition, Rock-Eval data indicate no significant inorganic-carbonate contribution to the S3 pyrolysis peak. The Pliocene-Miocene sediments consist of pelagic, biogenic carbonates. The organic matter is similar to that of the Pleistocene interglacial periods; a mixture of oxidized marine organic matter and reworked, terrestrial detritus. The Paleocene-Oligocene organic matter reflects variations in source and depositional factors associated with the isolation of Rockall from Greenland. Paleocene sediments contain primarily terrestrial organic matter with evidence of in situ thermal stress resulting from interbedded lava flows. Late Paleocene and early Eocene organic matter suggests a highly oxidized marine environment, with major periods of deposition of terrestrially derived organic matter. These fluctuations in organic-matter type are probably the result of episodic shallowing and deepening of Rockall Basins. The final stage of Eocene/Oligocene sedimentation records the accelerating subsidence of Rockall and its isolation from terrestrial sources (Rockall and Greenland). This is shown by the increasingly marine character of the organic matter. The petroleum potential of sediments containing more than 0.5% organic carbon is poor because of their thermal immaturity and their highly oxidized and terrestrial organic-matter composition.

Chemical and isotopic analysis of bulk organic matter and hydrocarbon biomarkers from IODP Holes 311-U1327C, 311-U1328B and 311-U1328C

The chemical and isotopic compositions of sedimentary organic matter (SOM) from two mid-slope sites of the northern Cascadia margin were investigated during Integrated Ocean Drilling Program (IODP) Expedition 311 to elucidate the organic matter origins and identify potential microbial contributions to SOM. Gas hydrate is present at both locations (IODP Sites U1327 and U1328), with distinct patterns of near-seafloor structural accumulations at the cold seep Site U1328 and deeper stratigraphic accumulations at the slope-basin Site U1327. Source characterization and evidence that some components of the organic matter have been diagenetically altered are determined from the concentrations and isotopic compositions of hydrocarbon biomarkers, total organic carbon (TOC), total nitrogen (TN) and total sulfur (TS). The carbon isotopic compositions of TOC (d13C TOC = -26 to -22 per mil) and long-chain n-alkanes (C27, C29 and C31, d13C = -34 to -29 per mil) suggest the organic matter at both sites is a mixture of 1) terrestrial plants that employ the C3 photosynthetic pathway and 2) marine algae. In contrast, the d15N TN values of the bulk sediment (+4 to +8 per mil) are consistent with a predominantly marine source, but these values most likely have been modified during microbial organic matter degradation. The d13C values of archaeal biomarker pentamethylicosane (PMI) (-46.4 per mil) and bacterial-sourced hopenes, diploptene and hop-21-ene (-40.9 to -34.7 per mil) indicate a partial contribution from methane carbon or a chemoautotrophic pathway. Our multi-isotope and biomarker-based conclusions are consistent with previous studies, based only on the elemental composition of bulk sediments, that suggested a mixed marine-terrestrial organic matter origin for these mid-slope sites of the northern Cascadia margin.

Oxygen and carbon isotope composition of Globoquadrina venezuelana and Oridorsalis umbonatus at DSDP Leg 85 Holes

Oxygen and carbon isotope stratigraphies are given for the planktonic foraminifer Globoquadrina venezuelana (a deep-dwelling species) at three DSDP sites located along a north-south transect at approximately 133°W across the Pacific equatorial high-productivity zone. The records obtained at Sites 573 and 574 encompass the lower Miocene. At Site 575 the record includes the middle Miocene and extends into the lowermost lower Miocene. The time resolution of the planktonic foraminifer isotope record varies from 50,000 to 500,000 yr. The benthic foraminifer Oridorsalis umbonatus was analyzed for isotope composition at a few levels of Site 575. Isotope stratigraphies for all three sites are compared with carbonate, foraminifer preservation, and grain size records. We identified a number of chemostratigraphic signals that appear to be synchronous with previously recognized signals in the western equatorial Pacific and the tropical Indian Ocean, and thus provide useful tools for chronostratigraphic correlations. The sedimentary sequence at Site 573 is incomplete and condensed, whereas the sequences from Sites 574 and 575 together provide a complete lower Miocene record. The expanded nature of this record, which was recovered with minimum disturbance and provides excellent calcareous and siliceous biostratigraphic control, offers a unique opportunity to determine the precise timing of early Miocene events. Paleomagnetic data from the hydraulic piston cores at Site 575 for the first time allow late early Miocene paleoceanographic events to be tied directly to the paleomagnetic time scale. The multiple-signal stratigraphies provide clues for paleoceanographic reconstruction during the period of preconditioning before the major middle Miocene cooling. In the lowermost lower Miocene there is a pronounced shift toward greater d13C values (by -1%) within magnetic Chron 16 (between approximately 17.5 and 16.5 Ma). The "Chron 16 Carbon Shift" coincides with the cessation of an early Miocene warming trend visible in the d18O signals. Values of d13C remain high until approximately 15 Ma, then decrease toward initial (early Miocene) values near 13.5 Ma. The broad lower to middle Miocene d13C maximum appears to correlate with the deposition of organic-carbon-rich sediments around the margin of the northern Pacific in the Monterey Formation of California and its lateral equivalents. The sediments rimming the Pacific were probably deposited under coastal upwelling conditions that may have resulted from the development of a strong permanent thermocline. Deposition in the upwelling areas occurred partly under anaerobic conditions, which led to the excess extraction of organic carbon from the ocean. The timing of the middle Miocene cooling, which began after the Chron 16 Carbon Shift, suggests that the extraction of organic carbon preconditioned the ocean-atmosphere system for subsequent cooling. A major carbonate dissolution event in the late early Miocene, starting at approximately 18.7 Ma, is associated with the enrichment in 13C. The maximum dissolution is coeval with the Chron 16 Carbon Shift. It corresponds to a prominent acoustic horizon that can be traced throughout the equatorial Pacific.

Geochemistry, sediment components, and paleoproductivity reconstruction for the Miocene to early Pliocene sediments

We reconstruct paleoproductivity at three sites in the Atlantic Ocean (Ocean Drilling Program Sites 982, 925, and 1088) to investigate the presence and extent of the late Miocene to early Pliocene 'biogenic bloom' from 9 to 3 Ma. Our approach involves construction of multiple records including benthic foraminiferal and CaCO3 accumulation rates, Uvigerina counts, dissolution proxies, and geochemical tracers for biogenic and detrital fluxes. This time interval also contains the so-called late Miocene carbon isotope shift, a well-known decrease in benthic foraminiferal d13C values. We find that the timing of paleoproductivity maxima differs among the three sites. At Site 982 (North Atlantic), benthic foraminifera and CaCO3 accumulation were both at a maximum at ~5 Ma, with smaller peaks at ~6 Ma. The paleoproductivity maximum was centered earlier (~6.6-6.0 Ma) in the tropical Atlantic (Site 925). In the South Atlantic (Site 1088), paleoproductivity increased even earlier, between 8.2 Ma and 6.2 Ma, and remained relatively high until ~5.4 Ma. We note that there is some overlap between the interval of maximum productivity between Sites 925 and 1088, as well as the minor productivity increase at Site 982. We conclude that the paleoproductivity results support hypotheses aiming to place the biogenic bloom into a global context of enhanced productivity. In addition, we find that at all three sites the d13C shift is accompanied by carbonate dissolution. This observation is consistent with published studies that have sought a relationship between the late Miocene carbon isotope shift and carbonate preservation.

Geochemical and biogeochemical parameters of bottom sediments from the area of the Spitsbergen (Svalbard) Archipelago

Quantitative characteristics for rates of diagenetic processes in the upper (0-30 cm) layer of sedimentary deposits in the area of the Spitsbergen (Svalbard) Archipelago (78°-80°N) were obtained by lithologo-geochemical, radioisotope (35S, 14C), and stable isotope (d34S, d13C) studies. It was proved that rates of diagenetic processes in polar deposits at 123-395 m depth affected by the East Spitsbergen ''warm'' current are mostly determined by bioproductivity and are commensurate with rates of processes in shelf deposits of temperate latitudes. High contents of migratory methane (up to 263 ml/dm**3) and isotopically-light organic carbon (Corg, d13C = -30 per mil PDB) were found in the 1 m layer of shelf deposits (at 123 m sea depth) with low bacterial in situ production of methane. It was shown that methane is not utilized in the deposits by the methanotrophic bacterial community and it may be supplied to the water mass and, probably, to the atmosphere.

Water chemistry and sediment age of lake Terrasovoje, Amery Oasis, East Antarctica

The late Quaternary palaeoenvironmental history of the southern Windmill Islands, East Antarctica, has been reconstructed using diatom assemblages from two long, well-dated sediment cores taken in two marine bays. The diatom assemblage of the lowest sediment layers suggests a warm climate with mostly open water conditions during the late Pleistocene. During the following glacial, the Windmill Islands were covered by grounded ice preventing any in situ bioproductivity. Following deglaciation, a sapropel with a well-preserved diatom assemblage was deposited from ~10?500 cal yr BP. Between ~10?500 and ~4000 cal yr BP, total organic carbon (Corg) and total diatom valve concentrations as well as the diatom species composition suggest relatively cool summer temperatures. Hydrological conditions in coastal bays were characterised by combined winter sea-ice and open water conditions. This extensive period of glacial retreat was followed by the Holocene optimum (~4000 to ~1000 cal yr BP), which occurred later in the southern Windmill Islands than in most other Antarctic coastal regions. Diatom assemblages in this period suggest ice-free conditions and meltwater-stratified waters in the marine bays during summer, which is also reflected in high proportions of freshwater diatoms in the sediments. The diatom assemblage in the upper sediments of both cores indicates Neoglacial cooling from ~1000 cal yr BP, which again led to seasonally persistent sea-ice on the bays. The Holocene optimum and cooling trends in the Windmill Islands did not occur contemporaneously with other Antarctic coastal regions, showing that the here presented record reflects partly local environmental conditions rather than global climatic trends.

Age models and foraminifer isotopes of four ODP Leg 202 sites

We present benthic isotope stratigraphies for Sites 1236, 1237, 1239, and 1241 that span the late Miocene-Pliocene time interval from 6 to 2.4 Ma. Orbitally tuned timescales were generated for Sites 1237 and 1241 by correlating the high-frequency variations in gamma ray attenuation density, percent sand of the carbonate fraction, and benthic d13C to variations in Earth's orbital parameters. The astronomical timescales for Sites 1237 and 1241 are in agreement with the one from Atlantic Site 925/926 (Ocean Drilling Program Leg 154). The comparison of benthic d18O and d13C records from the east Pacific sites and Atlantic Site 925/926 revealed a surprising clarity of the "41-k.y. signal" in d13C records and a remarkably good correlation between their d13C records. This suggests that the late Miocene-Pliocene amplitudes of obliquity-related d13C cycles reflect a magnitude of global response often larger than that provided by obliquity-related d18O cycles. At Site 1237, the orbitally derived ages of Pliocene magnetic reversal boundaries between the base of Réunion and the top of Thvera confirm astronomical datings of the generally accepted ATNTS2004 timescale, except for the top of Kaena and the base of Sidufjall. Our astronomical age for the top of Kaena is about one obliquity cycle older. The base of Sidufjall appears to be about one precession cycle younger. The age models of Sites 1236 and 1239 were established by correlating their benthic d18O and d13C records directly to the orbitally tuned isotope record of Site 1241.

Biomarkers in surface sediments from the Ob and Yenisei estuaries and the southern Kara Sea

Organic-geochemical bulk parameter (Total organic carbon contents, C/N ratios and d13Corg values), biogenic opal and biomarkers (n-alkanes, fatty acids, sterols and amino acids) were determined in surface sediments from the Ob and Yenisei estuaries and the adjacent southern Kara Sea. Maximum TOC contents were determined in both estuaries, reaching up to 3 %. Relatively high C/N ratios around 10, light d13Corg values of -26.5 per mil (Yenisei) and -28 to -28.7 per mil (Ob), and maximum concentrations of long-chain n-alkanes of up to about 10 µg/g Sed clearly show the predominance of terrigenous organic matter in the sediments from the estuaries. Towards the open Kara Sea, all p arameters indicate a decrease in terrigenous organic carbon. Brassicasterol as well as the short-chain n-alkanes parallel this trend, suggesting that these biomarkers are probably also related to a terrigenous (fresh-water phytoplankton) source. Amino acid spectra show characteristic trends from the Yenisei Estuary to the open Kara Sea revealing increasing state of degradation. Sedimentary organic matter in the Yenisei Estuary is relatively less degraded compared to the Ob Estuary and the open Kara Sea.

Chemical, isotope and mineral composition of hydrothermally altered upper oceanic crust drilled at ODP Site 129-801C

ODP Hole 801C penetrates >400 m into 170-Ma oceanic basement formed at a fast-spreading ridge. Most basalts are slightly (10-20%) recrystallized to saponite, calcite, minor celadonite and iron oxyhydroxides, and trace pyrite. Temperatures estimated from oxygen isotope data for secondary minerals are 5-100°C, increasing downward. At the earliest stage, dark celadonitic alteration halos formed along fractures and celadonite, and quartz and chalcedony formed in veins from low-temperature (<100°C) hydrothermal fluids. Iron oxyhydroxides subsequently formed in alteration halos along fractures where seawater circulated, and saponite and pyrite developed in the host rock and in zones of restricted seawater flow under more reducing conditions. Chemical changes include variably elevated K, Rb, Cs, and H2O; local increases in FeT, Ba, Th, and U; and local losses of Mg and Ni. Secondary carbonate veins have 87Sr/86Sr = 0.706337 - 0.707046, and a negative correlation with d18O results from seawater-basalt interaction. Carbonates could have formed at any time since the formation of Site 801 crust. Variable d13C values (-11.2? to 2.9?) reflect the incorporation of oxidized organic carbon from intercalated sediments and changes in the d13C of seawater over time. Compared to other oceanic basements, a major difference at Site 801 is the presence of two hydrothermal silica-iron deposits that formed from low-temperature hydrothermal fluids at the spreading axis. Basalts associated with these horizons are intensely altered (60-100%) to phyllosilicates, calcite, K-feldspar, and titanite; and exhibit large increases in K, Rb, Cs, Ba, H2O, and CO2, and losses of FeT, Mn, Mg, Ca, Na, and Sr. These effects may be common in crust formed at fast-spreading rates, but are not ubiquitous. A second important difference is that the abundance of brown oxidation halos along fractures at Site 801 is an order of magnitude less than at some other sites (2% vs. 20-30%). Relatively smooth basement topography (<100 m) and high sedimentation rate (8 m/Ma) probably restricted the access of oxygenated seawater. Basement lithostratigraphy and early low-temperature hydrothermal alteration and mineral precipitation in fractures at the spreading axis controlled permeability and limited later flow of oxygenated seawater to restricted depth intervals.

Sedimentation rates and isotope data of Pyrgo murrhina from DSDP Hole 14-141

Oxygen and carbon stable isotope data of Pyrgo murrhina and flux rates of calcium carbonate in the bio- and magnetostratigraphically dated sediment sequence at DSDP Site 141 were used for a reconstruction of the deep-water circulation in the Northeast Atlantic during Late Miocene and Pliocene times. A distinct change towards reduced advection of deep water recorded near 5.4 Ma is contemporaneous with the cessation of the outflow of the saline Mediterranean water into the Atlantic. During the Pliocene, between 4.5 and 2.75 Ma and between 2.1 and 1.8 Ma, North Atlantic Deep Water (NADW) circulation was sluggish and Site 141 possibly influenced by Antarctic Bottom Water (AABW). Near 2.75 Ma, the advection of well-oxidized NADW was strongly intensified. This change is related to an onset of major Arctic ice growth and/or a major cooling of NADW.