Isotopic composition and Strontium/Calcium ratios of foraminifera of ODP Holes 113-689B and 113-690C

Oxygen and carbon isotopic ratios were measured from Maestrichtian benthic and planktonic foraminifer species and bulk carbonate samples from ODP Sites 689 and 690, drilled on the Maud Rise during Leg 113. Careful scanning electron microscope observations reveal that test calcite in some intervals was diagenetically altered, although Sr/Ca and isotopic ratios of these tests do not appear to have been modified significantly. Foraminifer d18O values at both sites document a cooling trend during early Maestrichtian time, a rapid drop in water temperatures at the time of the first appearance of Abathomphalus mayaroensis in the high southern latitude regions (about 69.9 Ma), and lower water temperatures during late Maestrichtian time. d13C values record a depletion in 13C in the latest early Maestrichtian time beginning at about 72.2 Ma, just prior to the sharp late Maestrichtian increase in d18O values. These trends are similar to those previously reported for well-preserved benthic foraminifer species from Seymour Island, in the Antarctic Peninsula. Paleotemperature estimates are also comparable to those at Seymour Island and suggest temperate climatic conditions in Antarctica and that bottom waters in the southern South Atlantic region were of Antarctic origin. Benthic and planktonic foraminifer 613C values fluctuate sympathetically and are higher in upper Maestrichtian sediments than in the lower Maestrichtian sequence.

Isotope ratios, trace elements and ultrastructure results of Mytilus galloprovincialis shells and experimental site data off Ischia (Italy)

Bivalve shells can provide excellent archives of past environmental change but have not been used to interpret ocean acidification events. We investigated carbon, oxygen and trace element records from different shell layers in the mussels Mytilus galloprovincialis combined with detailed investigations of the shell ultrastructure. Mussels from the harbour of Ischia (Mediterranean, Italy) were transplanted and grown in water with mean pHT 7.3 and mean pHT 8.1 near CO2 vents on the east coast of the island. Most prominently, the shells recorded the shock of transplantation, both in their shell ultrastructure, textural and geochemical record. Shell calcite, precipitated subsequently under acidified seawater responded to the pH gradient by an in part disturbed ultrastructure. Geochemical data from all test sites show a strong metabolic effect that exceeds the influence of the low-pH environment. These field experiments showed that care is needed when interpreting potential ocean acidification signals because various parameters affect shell chemistry and ultrastructure. Besides metabolic processes, seawater pH, factors such as salinity, water temperature, food availability and population density all affect the biogenic carbonate shell archive.

Geochemistry and isotopes at DSDP Leg 80 Holes

Thirty-eight samples from DSDP Sites 549 to 551 were analyzed for major and minor components and trace element abundances. Multivariate statistical analysis of geochemical data groups the samples into two major classes: an organic-carbon- rich group (> 1% TOC) containing high levels of marine organic matter and certain trace elements (Cu, Zn, V, Ni, Co, Ba, and Cr) and an organic-carbon-lean group depleted in these components. The greatest organic and trace metal enrichments occur in the uppermost Albian to Turanian sections of Sites 549 to 551. Carbon-isotopic values of bulk carbonate for the middle Cenomanian section of Site 550 (2.35 to 2.70 per mil) and the upper Cenomanian-Turonian sections of Sites 549 (3.35 to 4.47 per mil) and 551 (3.13 to 3.72 per mil) are similar to coeval values reported elsewhere in the region. The relatively heavy d13C values from Sites 549 and 551 indicate that this interval was deposited during the global "oceanic anoxic event" that occurred at the Cenomanian/Turonian boundary. Variation in the d18O of bulk carbonate for Section 550B-18-1 of middle Cenomanian age suggests that paleosalinity and/or paleotemperature variations may have occurred concurrently with periodic anoxia at this site. Climatically controlled increases in surface-water runoff may have caused surface waters to periodically freshen, resulting in stable salinity stratification

Organic matter, isotopic composition of calcite veins in basement basalt and pore water at DSDP Leg 78A Holes

Sediments of the Barbados Ridge complex, cored on DSDP Leg 78A, contain low concentrations of acid-insoluble carbon (0.05-0.25%) and nitrogen (C/N 1.5-5) and dispersed C1-C6 hydrocarbons (100-800 ppb). The concentrations of organic carbon and 13C in organic carbon decrease with depth, whereas the concentration of dispersed hydrocarbons increases slightly with depth. These trends may reflect the slow oxidation of organic matter, with selective removal of 13C and slow conversion of the residual organic matter to hydrocarbons. Very minor indications of nitrogen gas were observed at about 250 meters sub-bottom at two of the drilling sites. Basement basalts have calcite veins with d13C values in the range of 2.0 to 3.2 per mil and d18O-SMOW values ranging from 28.5 to +30.6 per mil. Interstitial waters have d18O-SMOW of 0.2 to -3.5 per mil and dD-SMOW of -2 to -15 per mil. The oxygen isotopic composition of the calcite veins in the basement basalts gives estimated equilibrium fractionation temperatures in the range of 11 to 24°C, assuming precipitation from water with d18O-SMOW in the range of +0.1 to -1.0 per mil. This suggests that basalt alteration and precipitation of vein calcite occurred in contact either with warmer Campanian seawater or, later, with pore water, after burial to depths of 200- 300 meters. Pore waters from all three sites are depleted in deuterium and 18O, and dissolved sulfate is enriched in 34S at Sites 541 and 542, but not at Site 543.

Sedimentology and origin of lower Cretaceous pelagic carbonates and redeposited clastics at DSDP Hole 76-534A

Drilling at Site 534 in the Blake-Bahama Basin recovered 268 m of Lower Cretaceous, Berriasian to Hauterivian, pelagic carbonates, together with volumetrically minor intercalations of claystone, black shales, and terrigenous and calcareous elastics. Radiolarian nannofossil pelagic carbonates accumulated in water depths of about 3300 to 3650 m, below the ACD (aragonite compensation depth) but close to the CCD (calcite compensation depth). Radiolarian abundance points to a relatively fertile ocean. In the Hauterivian and Barremian, during times of warm, humid climate and rising sea level, turbiditic influxes of both terrigenous and calcareous sediments, and minor debris flows were derived from the adjacent Blake Plateau. The claystones and black shales accumulated on the continental rise, then were redeposited onto the abyssal plain by turbidity currents. Dark organic-rich and pale organic-poor couplets are attributed to climatic variations on land, which controlled the input of terrigenous organic matter. Highly persistent, fine, parallel lamination in the pelagic chalks is explained by repeated algal "blooms." During early diagenesis, organic-poor carbonates remained oxygenated and were cemented early, whereas organic-rich intervals, devoid of burrowing organisms, continued to compact later in diagenesis. Interstitial dissolved-oxygen levels fluctuated repeatedly, but bottom waters were never static nor anoxic. The central western Atlantic in the Lower Cretaceous was thus a relatively fertile and wellmixed ocean basin.

Stable isotopes and calcium carbonate at DSDP Holes 85-574 and 85-574A

Detailed stable isotopic and calcium carbonate records (with a sampling resolution of 3000 yr.) from the middle Miocene section of hydraulic piston corer (HPC) Hole 574A provide a sequence that records the major shift in the oxygen isotopic composition of the world's oceans that occurred at about 14 Ma. The data suggest that this transition was rapid and spans about 30,000 yr. of sediment deposition. In intervals before and after the shift, the mean d18O values are characterized by a constant mean with a high degree of variability. The degree of variability in both the d18O and d13C records is comparable to that observed for the Pliocene and earliest Pleistocene and does not show a significant change before or after the major shift in the d18O record. Whereas the oxygen isotopic record is characterized by relatively stable mean values before and after the middle Miocene event, the d13C record shows a number of significant offsets in the mean value separated by intervals of high-frequency variations. Time and frequency domain analysis of all records from Hole 574A indicate that the frequency components shown to be related to orbital changes in the Pleistocene record are also present in the middle Miocene. The high variability observed in the Site 574 isotopic records places important constraints on models describing the role of formation of the Antarctic ice sheet during the middle Miocene climatic transitions. Thus, HPC Hole 574A provides a valuable sequence for detailed study of climatic variability during an important time in the Earth's history, although we cannot provide a definitive explanation of the major oxygen isotopic event of the middle Miocene.

Chemistry of interstitial waters and sediments at DSDP Leg 64 Holes

Studies of interstitial waters obtained from DSDP Leg 64 drill sites in the Gulf of California have revealed information both on early diagenetic processes in the sediments resulting from the breakdown of organic matter and on hydrothermal interactions between sediments and hot doleritic sill intrusions into the sediments. In all the sites drilled sulfate reduction occurred as a result of rapid sediment accumulation rates and of relatively high organic carbon contents; in most sites methane production occurred after sulfate depletion. Associated with this methane production are high values of alkalinity and high concentrations of dissolved ammonia, which causes ion exchange processes with the solid phases leading to intermediate maxima in Mg++, K+, Rb+, and Sr++(?). Though this phenomenon is common in Leg 64 drill sites, these concentration reversals had been noticed previously only in Site 262 (Timor Trough) and Site 440 (Japan Trench). Penetrating, hot dolerite sills have led to substantial hydrothermal alteration in sediments at sites drilled in the Guaymas Basin. Site 477 is an active hydrothermal system in which the pore-water chemistry typically shows depletions in sulfate and magnesium and large increases in lithium, potassium, rubidium, calcium, strontium, and chloride. Strontium isotope data also indicate large contributions of volcanic matter and basalt to the pore-water strontium concentrations. At Sites 478 and 481 dolerite sill intrusions have cooled to ambient temperatures but interstitial water concentrations of Li+, Rb+, Sr++ , and Cl- show the gradual decay of a hydrothermal signal that must have been similar to the interstitial water chemistry at Site 477 at the time of sill intrusion. Studies of oxygen isotopes of the interstitial waters at Site 481 indicate positive values of d18O (SMOW) as a result of high-temperature alteration reactions occurring in the sills and the surrounding sediments. A minimum in dissolved chloride at about 100-125 meters sub-bottom at Sites 478, 481, and particularly Site 479 records a possible paleosalinity signal, associated with an event that substantially lowered salinities in the inner parts of the Gulf of California during Quaternary time.

Stable oxygen and carbon isotope ratios of foraminifera and test results after different sample cleaning procedures from ODP Leg 207 sediments

We report oxygen and carbon stable isotope analyses of foraminifers, primarily planktonic, sampled at low resolution in the Cretaceous and Paleogene sections from Sites 1257, 1258, and 1260. Data from two samples from Site 1259 are also reported. The very low resolution of the data only allows us to detect climate-driven isotopic events on the timescale of more than 500 k.y. A several million-year-long interval of overall increase in planktonic 18O is seen in the Cenomanian at Site 1260. Before and after this interval, foraminifers from Cenomanian and Turonian black shales have d18O values in the range -4.2 per mil to -5.0 per mil, suggestive of upper ocean temperatures higher than modern tropical values. The d18O values of upper ocean dwelling Paleogene planktonics exhibit a long-term increase from the early Eocene to the middle Eocene. During shipboard and postcruise processing, it proved difficult to extract well-preserved foraminifer tests from black shales by conventional techniques. Here, we report results of a test of procedures for cleaning foraminifers in Cretaceous organic-rich mudstone sediments using various combinations of soaking in bleach, Calgon/hydrogen peroxide, or Cascade, accompanied by drying, repeat soaking, or sonication. A procedure that used 100% bleach, no detergent, and no sonication yielded the largest number of clean, whole individual foraminifers with the shortest preparation time. We found no significant difference in d18O or d13C values among sets of multiple samples of the planktonic foraminifer Whiteinella baltica extracted following each cleaning procedure.

Late Neogene time scale for ODP Leg 138 sites

The sediments recovered during Leg 138 provide a remarkable opportunity to improve the geological time scale of the late Neogene. We have developed new time scales in the following steps. First, we constructed age models on the basis of shipboard magnetostratigraphy and biostratigraphy, using the time scale of Berggren, Kent, and Flynn (1985). Second, we refined these age models using shipboard GRAPE density measurements to provide more accurate correlation points. Third, we calibrated a time scale for the past 6 m.y. by matching the high-frequency GRAPE density variations to the orbital insolation record of Berger and Loutre (1991); we also took into account d18O records, where they were available. Fourth, we generated a new seafloor anomaly time scale using our astronomical calibration of C3A.n (t) at 5.875 Ma and an age of 9.639 Ma for C5n.1n (t) that is based on a new radiometric calibration (Baksi, 1992). Fifth, we recalibrated the records older than 6 Ma to this new scale. Finally, we reconsidered the 6- to 10-Ma interval and found that this could also be partially tuned astronomically.

Chemistry of altered basalts from ODP Hole 123-765D

Volcanic basement recovered at Hole 765D is characterized by nonpervasive, oxidative alteration, typical of seafloor weathering. Chilled margins and the mesostasis of the lavas are variably altered to assemblages of celadonite, Fe-oxyhydroxides, zeolites, and calcite with trace saponite. Plagioclase is partially altered to Ca-Na zeolites and/or albite. Well-developed alteration halos parallel fracture surfaces and extend several centimeters into the surrounding rock. These clay-rich halos are enriched in K2O and Fe2O3 relative to the adjacent clay-poor rock. The halos and adjacent rock are characterized by d18O values 2 per mil-3 per mil higher than those of fresh MORB. The "freshness" of the samples and the scarcity of saponite suggest that the duration of seawater circulation was short-lived. Albitization of plagioclase indicates that the volcanic rocks were altered initially at low temperatures and were subsequently reheated off-axis in a closed environment. Reheating did not result in significant modification of the bulk composition of the crust.

Displaced diatom, discoasters and benthic foraminifers at DSDP Hole 72-515A

Late Pliocene to Recent sediments from the southern Brazil Basin (DSDP Hole 515A, hydraulic piston core) were analyzed for evidence of episodic flow of Antarctic Bottom Water (AABW) through the Vema Channel. Carbonate-enriched layers punctuate the post-Pliocene section, otherwise composed predominantly of terrigenous silt and clay. Carbonate enrichment is thought to result from rapid deposition of fine-grained calcareous turbidites, originating in canyons incised on the northern margin of the Rio Grande Rise. The composition of benthic foraminiferal assemblages and the presence of stratigraphically displaced discoasters is consistent with a turbidite origin. Based on the presence of displaced Antarctic diatoms, AABW flow through the Vema Channel apparently has had a major influence on this site for only four periods during the last 2.7 Ma (about 45 to 250; 375 to 430; 700 to 780; 1320 to 1345 thousand yr. ago).

Benthic foraminiferal carbon isotopic records and the development of abyssal circulation at DSDP Sites 9-77, 12-119, 30-289, 82-563 and 94-608

The North Atlantic at present is ventilated by overflow of the Denmark Strait, Iceland-Faeroe Ridge, Faeroe Bank Channel, and Wyville-Thompson Ridge. The evolution of Cenozoic abyssal circulation of this region was related to tectonic opening and subsidence of these sills. We used d13C records of the benthic foraminifer Cibicidoides to decipher the timing of tectonically controlled changes in bottom-water circulation in the eastern basins (Biscay and Iberian) of the northern North Atlantic. Records from Site 608 (Kings Trough, northeastern North Atlantic) show that from about 24 to 15 Ma (early to early middle Miocene), d13C values in the Kings Trough area were depleted relative to western North Atlantic values and were more similar to Pacific d13C values. This reflects less ventilation of the Kings Trough region as compared to the well-oxygenated western North Atlantic. Comparison of Oligocene d13C records from Site 119 (Bay of Biscay) with western North Atlantic records suggests that the eastern basin was also relatively isolated prior to 24 Ma. At about 15 Ma, d13C values at Site 608 attained values similar to the western North Atlantic, indicating increased eastern basin ventilation in the middle Miocene. This increased advection into the eastern basin predated a major d18O increase which occurred at about 14.6 Ma. Subsidence estimates of the Greenland-Scotland Ridge indicate that the deepening of the Iceland-Faeroe Ridge was coincident with the marked change in eastern basin deep-water ventilation.

Oxygen- and carbon-isotopes of Globigerina bulloides and Neogloboquadrina pachyderma at DSDP Holes 80-548 and 80-549A

Oxygen- and carbon-isotope analyses have been performed on the Quaternary planktonic foraminifers of Sites 548 and 549 (DSDP Leg 80) to investigate major water mass changes that occurred in the northeastern Atlantic at different glacial-interglacial cycles and to compare them with the well-defined picture of 18,000 yr. ago. Oxygen-isotope stratigraphy also provides a chronological framework for the more important data on the fauna and flora. Although bioturbation and sedimentary gaps obliterate the climatic and stratigraphic record, general trends in the oceanographic history can be deduced from the isotopic data. Isotopic stratigraphy has tentatively been delineated down to isotopic Stage 16 at Site 548 and in Hole 549A. This stratigraphy fits well with that deduced from benthic foraminiferal d18O changes and with bioclimatic zonations based on foraminiferal associations at Site 549. Variations in the geographic extension and in the flux of the Gulf Stream subtropical waters are inferred from both d18O and d13C changes. Maximal fluxes occurred during the late Pliocene. Northward extension of subtropical waters increased through the various interglacial phases of the early Pleistocene and decreased through the late Pleistocene interglacial phases. Conversely, glacial maxima were more intense after Stage 16. Isotopic Stages 12 and 16 mark times of important change in water mass circulation. Oxygen- and carbon-isotope analyses have been performed on the Quaternary planktonic foraminifers of Sites 548 and 549 (DSDP Leg 80) to investigate major water mass changes that occurred in the northeastern Atlantic at different glacial-interglacial cycles and to compare them with the well-defined picture of 18,000 yr. ago. Oxygen-isotope stratigraphy also provides a chronological framework for the more important data on the fauna and flora. Although bioturbation and sedimentary gaps obliterate the climatic and stratigraphic record, general trends in the oceanographic history can be deduced from the isotopic data. Isotopic stratigraphy has tentatively been delineated down to isotopic Stage 16 at Site 548 and in Hole 549A. This stratigraphy fits well with that deduced from benthic foraminiferal d18O changes and with bioclimatic zonations based on foraminiferal associations at Site 549. Variations in the geographic extension and in the flux of the Gulf Stream subtropical waters are inferred from both d18O and d13C changes. Maximal fluxes occurred during the late Pliocene. Northward extension of subtropical waters increased through the various interglacial phases of the early Pleistocene and decreased through the late Pleistocene interglacial phases. Conversely, glacial maxima were more intense after Stage 16. Isotopic Stages 12 and 16 mark times of important change in water mass circulation.

Geochemistry and isotopes at DSDP Site 68-503

Nodules occur in the siliceous calcareous ooze and siliceous marl at Site 503 in the eastern equatorial Pacific. They are present below a depth of about 11 meters throughout the green-colored reduced part of the section down to 228 meters, although they are most abundant between 30 and 85 meters. They are cylindrical or barrel-shaped, up to 70 mm long, and usually have an axial channel through them or are hollow. They appear to have formed around and/or within burrows. XRD studies and microprobe analyses show that they are homogeneous and consist of calcian rhododrosite and minor calcite; Mn is present to the extent of about 30%. Isotopic analyses of the carbonate give carbon values which range from -1.2 per mil to -3.8 per mil, and oxygen isotope compositions vary from +4.0 per mil to +6.0 per mil. These values are different from those for marine-derived carbonates as exemplified by the soft sediment filling of a burrow: d13C, -0.26 per mil; d18O, +1.05 per mil. The carbon isotope data indicate that carbonate derived (possibly indirectly) from seawater was mixed with some produced by organic diagenesis to form the nodules. The d18O values suggest that although they formed near the sediment surface, some modification or the introduction of additional diagenetic carbonate occurred during burial.