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.

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.

Miocene benthic foraminifer oxygen and carbon isotope record of ODP Site 115-709

The benthic isotopic record of Miocene Cibicidoides from Site 709 provides a record of conditions in the Indian Ocean at a depth of about 3200 mbsf. As expected, the record qualitatively resembles those of other Deep Sea Drilling Project and Ocean Drilling Program sites. The data are consistent with the scenario for the evolution of thermohaline circulation in the Miocene Indian Ocean proposed by Woodruff and Savin (1989, doi:10.1029/PA004i001p00087). Further testing of that scenario, however, requires isotopic data for Cibicidoides from other Indian Ocean sites. There is a correlation between d13C values of Cibicidoides and planktonic:benthic (P:B)ratios of Site 709 sediments, implying a causal relationship between the corrosiveness of deep waters and concentration of CO2 derived from oxidation of organic matter.

Age determination and stable isotope record of sediment cores at 9°S in the Indian Ocean

A continuous 10-m-long section consisting of roughly two thirds Ethmodiscus rex (a diatom) and one third mixed planktonic foraminifera was identified in a core from 3800 m depth at 9°S on the Indian Ocean's 90°E Ridge. Radiocarbon dates place the onset of deposition of this layer at >30,000 years B.P. and its termination at close to 11,000 years B.P. However, precise dating of the foraminifera from the Ethmodiscus layer itself proved to be impossible owing to the presence of secondary calcite presumably precipitated from the pore waters. During the Holocene, high calcium carbonate content ooze free of diatoms was deposited at this locale. As the site currently lies beneath the pathway taken by upper ocean waters entering the Indian Ocean from the Pacific (via the Indonesian Straits), it appears that during glacial time, thermocline waters moving along this same path provided the silica and other nutrients required by these diatoms.

Planktonic foraminifer assemblages and stable oxygen and carbon isotope record of sediment core MD07-3076Q

We report high-resolution planktonic foraminifer census counts and stable oxygen and carbon isotope measurements of the planktonic foraminifera G. bulloides and N. pachyderma s. from sediment core MD07-3076Q for the last deglaciation, the last glacial maximum and Marine Isotope Stage 3. These data provide insights into the marine cycling of carbon and frontal dynamics in the sub-Antarctic Atlantic during the last 68 ka.

Age model and stable isotope record of eastern equatorial Pacific sediment cores

Six deep sea cores from the eastern equatorial Pacific (EEP) were analyzed for planktonic foraminifera and stable isotopes in order to reconstruct sea surface temperatures (SST) for the last 40 ka. South of the Equatorial Front the abundance of Globorotalia inflata increased, and SST decreased by >5°C (core ODP846B), creating a stronger SST meridional gradient and advection of the Peru Current than present for the ~16-35 ka interval. A sharper SST meridional gradient forced stronger Choco jet events and a moisture increase in western Colombia, which supplied, through the San Juan River and the south-flowing equatorial and the Peru-Chile countercurrents, abundant hemipelagic quartz over the northern Peru basin (core TR163-31B). The Choco jet, and its associated mesoscale convective cells, provoked an increase in snow precipitation over the Central Cordillera of Colombia and the advance of the Murillo glacier. In synchrony with the intensified Choco jet events, the "dry island" effect over the Eastern Cordillera of Colombia intensified, and the level of Fuquene Lake dropped.

Stable foraminifer isotope composition and age of ODP Sites 184-1147 and 184-1148, South China Sea

Sites 1147 (18°50.11'N, 116°33.28'E; water depth = 3246 m) and 1148 (18°50.17'N, 116°33.94'E; water depth = 3294 m) are located on the lowermost continental slope off southern China near the continent/ocean crust boundary of the South China Sea Basin. Site 1147 is located upslope ~0.45 nmi west of Site 1148. Three advanced piston corer holes at Site 1147 and two extended core barrel holes at Site 1148 were cored and combined into a composite (spliced) stratigraphic section, which provided a relatively continuous profile for the lower Oligocene to Holocene (Wang, Prell, Blum, et al., 2000, doi:10.2973/odp.proc.ir.184.2000; Jian, et al., 2001, doi:10.1007/BF02907088) for studying stratigraphy and paleoceanography. A total of 1047 planktonic foraminifers stable isotope measurements were performed on 975 samples covering the upper 409.58 meters composite depth (mcd) at ~42-cm intervals (Tables T1, T2), and a total of 1864 benthic foraminifers measurements were performed on 1650 samples in the upper 837.11 mcd at ~51-cm intervals (Tables T3, T4). We significantly improved the time resolution of the benthic stable isotope record in the upper 476.68 mcd by reducing the average sample spacing to ~29 cm. This translates into an average sampling resolution of ~16 k.y. for the Miocene sequence and ~8 k.y. for the Pliocene-Holocene interval, assuming a change in sedimentation rates from ~1.8 to ~3.5 cm/k.y., as suggested by shipboard stratigraphy. These data sets provide the basis for upcoming studies to establish an oxygen isotope stratigraphy and examine the Neogene evolution of deep and surface water signatures (temperature, salinity, and nutrients) in the South China Sea.

Element concentrations and Osmium, Platinum and Rhenium isotope ratios of ODP Site 153-920 abyssal peridotites

Abyssal peridotites are normally thought to be residues of melting of the mid-ocean ridge basalt (MORB) source and are presumably a record of processes affecting the upper mantle. Samples from a single section of abyssal peridotite from the Kane Transform area in the Atlantic Ocean were examined for 190Pt-186Os and 187Re-187Os systematics. They have uniform 186Os/188Os ratios with a mean of 0.1198353 +/- 7, identical to the mean of 0.1198340 +/-12 for Os-Ir alloys and chromitites believed to be representative of the upper mantle. While the Pt/Os ratios of the upper mantle may be affected locally by magmatic processes, these data show that the Pt/Os ratio for the bulk upper mantle has not deviated by more than about +/- 30% from a chondritic Pt/Os ratio over 4.5 billion years. These observations are consistent with the addition of a chondritic late veneer after core separation as the primary control on the highly siderophile element budget of the terrestrial upper mantle. The 187Os/188Os of the samples range from 0.12267 to 0.12760 and correlate well with Pt and Pt/Os, but not Re/Os. These relationships may be explained by variable amounts of partial melting with changing D(Re), reflecting in part garnet in the residue, with a model-dependent melting age between about 600 and 1700 Ma. A model where the correlation between Pt/Os and 187Os/188Os results from multiple ancient melting events, in mantle peridotites that were later juxtaposed by convection, is also consistent with these data. This melting event or events are evidently unrelated to recent melting under mid-ocean ridges, because recent melting would have disturbed the relationship between Pt/Os and 187Os/188Os. Instead, this section of abyssal peridotite may be a block of refractory mantle that remained isolated from the convecting portions of the upper mantle for 600 Ma to >1 Ga. Alternatively, Pt and Os may have been sequestered during more recent melting and possibly melt/rock reaction processes, thereby preserving an ancient melting history. If representative of other abyssal peridotites, then the rocks from this suite with subchondritic 187Os/188Os are not simple residues of recent MORB source melting at ridges, but instead have a more complex history. This suite of variably depleted samples projects to an undepleted present-day Pt/Os of about 2.2 and 187Os/188Os of about 0.128-0.129, consistent with estimates for the primitive upper mantle.

Coral oxygen isotope and Sr/Ca data from the Northern Gulf of Aqaba (Red Sea)

The last interglacial period (about 125,000 years ago) is thought to have been at least as warm as the present climate (Kukla et al., 2002, doi:10.1006/qres.2001.2316). Owing to changes in the Earth's orbit around the Sun, it is thought that insolation in the Northern Hemisphere varied more strongly than today on seasonal timescales (Berger, 1987, doi:10.1175/1520-0469(1978)035<2362:LTVODI>2.0.CO;2), which would have led to corresponding changes in the seasonal temperature cycle (Montoya et al., 2000, doi:10.1175/1520-0442(2000)013<1057:CSFKBW>2.0.CO;2). Here we present seasonally resolved proxy records using corals from the northernmost Red Sea, which record climate during the last interglacial period, the late Holocene epoch and the present. We find an increased seasonality in the temperature recorded in the last interglacial coral. Today, climate in the northern Red Sea is sensitive to the North Atlantic Oscillation (Felis et al., 2000 doi:10.1029/1999PA000477; Rimbu et al., 2001, doi:10.1029/2001GL013083), a climate oscillation that strongly influences winter temperatures and precipitation in the North Atlantic region. From our coral records and simulations with a coupled atmosphere-ocean circulation model, we conclude that a tendency towards the high-index state of the North Atlantic Oscillation during the last interglacial period, which is consistent with European proxy records (Zagwijn, 1996, doi:10.1016/0277-3791(96)00011-X; Aalbersberg and Litt, 1998, doi:10.1002/(SICI)1099-1417(1998090)13:5<367::AID-JQS400>3.0.CO;2-I; Klotz et al., 2003, doi:10.1016/S0921-8181(02)00222-9), contributed to the larger amplitude of the seasonal cycle in the Middle East.

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.

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.

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.