Sedimentation rate calculations and isotopic analysis on sediment cores along the IODP Expedition 311 transect

The oceanographic and tectonic conditions of accretionary margins are well-suited for several potential processes governing methane generation, storage and release. To identify the relevant methane evolution pathways in the northern Cascadia accretionary margin, a four-site transect was drilled during Integrated Ocean Drilling Program Expedition 311. The d13C values of methane range from a minimum value of -82.2 per mil on an uplifted ridge of accreted sediment near the deformation front (Site U1326, 1829 mbsl, meters below sea level) to a maximum value of -39.5 per mil at the most landward location within an area of steep canyons near the shelf edge (Site U1329, 946 mbsl). An interpretation based solely on methane isotope values might conclude the 13C-enrichment of methane indicates a transition from microbially- to thermogenically-sourced methane. However, the co-existing CO2 exhibits a similar trend of 13C-enrichment along the transect with values ranging from -22.5 per mil to +25.7 per mil. The magnitude of the carbon isotope separation between methane and CO2 (Ec = 63.8 ± 5.8) is consistent with isotope fractionation during microbially mediated carbonate reduction. These results, in conjunction with a transect-wide gaseous hydrocarbon content composed of > 99.8% (by volume) methane and uniform dDCH4 values (-172 per mil ± 8) that are distinct from thermogenic methane at a seep located 60 km from the Expedition 311 transect, suggest microbial CO2 reduction is the predominant methane source at all investigated sites. The magnitude of the intra-site downhole 13C-enrichment of CO2 within the accreted ridge (Site U1326) and a slope basin nearest the deformation front (Site U1325, 2195 mbsl) is ~ 5 per mil. At the mid-slope site (Site U1327, 1304 mbsl) the downhole 13C-enrichment of the CO2 is ~ 25 per mil and increases to ~ 40 per mil at the near-shelf edge Site U1329. This isotope fractionation pattern is indicative of more extensive diagenetic alteration at sites with greater 13C-enrichment. The magnitude of the 13C-enrichment of CO2 correlates with decreasing sedimentation rates and a diminishing occurrence of stratigraphic gas hydrate. We suggest the decreasing sedimentation rates increase the exposure time of sedimentary organic matter to aerobic and anaerobic degradation, during burial, thereby reducing the availability of metabolizable organic matter available for methane production. This process is reflected in the occurrence and distribution of gas hydrate within the northern Cascadia margin accretionary prism. Our observations are relevant for evaluating methane production and the occurrence of stratigraphic gas hydrate within other convergent margins.

Stable oxygen isotope record and Mg/Ca ratios at the Mid-Pleistocene Climate Transition, ODP Site 181-1123

Earth's climate underwent a fundamental change between 1250 and 700 thousand years ago, the Mid-Pleistocene Transition (MPT), when the dominant periodicity of climate cycles changed from 41,000 to 100,000 years in the absence of significant change in orbital forcing. Over this time, an increase occurred in the amplitude of change of deep ocean foraminiferal oxygen isotopic ratios, traditionally interpreted as defining the main rhythm of ice ages although containing large effects of changes in deep-ocean temperature. We have separated the effects of decreasing temperature and increasing global ice volume on oxygen isotope ratios. Our results suggest that the MPT was initiated by an abrupt increase in Antarctic ice volume at 900 ka. We see no evidence of a pattern of gradual cooling but near-freezing temperatures occur at every glacial maximum.

(Table 1) Oxygen isotope temperatures from hydrothermally altered breccias at DSDP Hole 60-453

Gabbro-metabasalt polymict breccias cored in Deep Sea Drilling Project Hole 453 are cemented in part by hydrothermal alteration to lower greenschist facies (chlorite-epidote-actinolite) mineral assemblages. Temperature estimates for this alteration, based on oxygen isotope determinations of secondary minerals, are nearly 100°C at the top of the breccias and over 200°C in a zone of intense alteration near the base.

Characterization of late Campanian and Maastrichtian planktonic foraminiferal depth habitats and vital activities based on stable isotopes

Depth habitats of 56 late Cretaceous planktonic foraminiferal species from cool and warm climate modes were determined based on stable isotope analyses of deep-sea samples from the equatorial Pacific DSDP Sites 577A and 463, and South Atlantic DSDP Site 525A. The following conclusions can be reached: Planoglobulina multicamerata (De Klasz) and Heterohelix rajagopalani (Govindan) occupied the deepest plankton habitats, followed by Abathomphalus mayaroensis (Bolli), Globotruncanella havanensis (Voorwijk), Gublerina cuvillieri Kikoine, and Laeviheterohelix glabrans (Cushman) also at subthermocline depth. Most keeled globotruncanids, and possibly Globigerinelliodes and Racemiguembelina species, lived at or within the thermocline layer. Heterohelix globulosa (Ehrenberg) and Rugoglobigerina, Pseudotextularia and Planoglobulina occupied the subsurface depth of the mixed layer, and Pseudoguembelina species inhabited the surface mixed layer. However, depth ranking of some species varied depending on warm or cool climate modes, and late Campanian or Maastrichtian age. For example, most keeled globotruncanids occupied similar shallow subsurface habitats as Rugoglobigerina during the warm late Campanian, but occupied the deeper thermocline layer during cool climatic intervals. Two distinct types of "vital effect" mechanisms reflecting photosymbiosis and respiration effects can be recognized by the exceptional delta13C signals of some species. (1) Photosymbiosis is implied by the repetitive pattern of relatively enriched delta13C values of Racemiguembelina (strongest), Planoglobulina, Rosita and Rugoglobigerina species, Pseudoguembelina excolata (weakest). (2) Enriched respiration 12C products are recognized in A. mayaroensis, Gublerina acuta De Klasz, and Heterohelix planata (Cushman). Isotopic trends between samples suggest that photosymbiotic activities varied between localities or during different climate modes, and may have ceased under certain environmental conditions. The appearance of most photosymbiotic species in the late Maastrichtian suggests oligotrophic conditions associated with increased water-mass stratification.

Stable oxygen isotope record and relative abundances of planktonic foraminifera of ODP Hole 117-728A

High resolution stratigraphy based on oxygen isotope ratios of the planktonic foraminifers Neogloboquadrina dutertrei (d'Orbigny), Globigeriniodes ruber (d'Orbigny), and Globigerina bulloides (d'Orbigny), magnetic susceptibility, and calcium carbonate content covers the sedimentary record of ODP Hole 728A drilled on the Oman Margin from approximately 10 k.y. to 525 k.y., comprising isotopic stages 1-13. Below stage 13 isotopic stage boundaries cannot be defined with certainty in our data. Sediment accumulation rates were calculated from the isotopic record of N. dutertrei by matching it with the age model SPECMAP curve. During the glacial periods sediment accumulation rates were higher than during the interglacial periods, reflecting increased input from the shelf during low-stands of sea level and increased eolian input. Periodograms for the past 524 k.y. on oxygen isotope records of N. dutertrei, G. ruber, and G. bulloides, on calcium carbonate content, magnetic susceptibility, and on a foraminiferal fragmentation record show powers matching the Milankovitch periodicities. High powers are concentrated around 103 k.y. In the spectra of oxygen isotope ratios of N. dutertrei, magnetic susceptibility, and foraminiferal fragmentation these are significant at the 80% confidence level with respect to a first order autoregressive model. Power concentrations near 43 k.y., matching obliquity, are present but subdued in all spectra. Power concentrations near 23 k.y., matching precession, are significant in the spectra of the oxygen isotope record of N. dutertrei, magnetic susceptibility, and calcium carbonate content record. Fragmentation of planktonic foraminifers increased during the interglacial periods. This is attributed to dissolution of the tests in an expanded oxygen minimum zone (OMZ), where undersaturation of calcium carbonate is caused by enhanced production in the euphotic zone, which would suggest stronger monsoonal induced upwelling during interglacial periods. Extension of the OMZ could also be increased by outflow of low oxygen marginal basin bottom water.

Lithogeochemical and isotope (Rb-Sr, Sm-Nd, Pb-Pb whole rock and Lu-Hf zircon) composition of samples from the Shackleton Range, East Antarctica

Three distinct, spatially separated crustal terranes have been recognised in the Shackleton Range, East Antarctica: the Southern, Eastern and Northern Terranes. Mafic gneisses from the Southern Terrane provide geochemical evidence for a within-plate, probably back-arc origin of their protoliths. A plume-distal ridge origin in an incipient ocean basin is the favoured interpretation for the emplacement site of these rocks at c. 1850 Ma, which, together with a few ocean island basalts, were subsequently incorporated into an accretionary continental arc/supra-subduction zone tectonic setting. Magmatic underplating resulted in partial melting of the lower crust, which caused high-temperature granulite-facies metamorphism in the Southern Terrane at c. 1710-1680 Ma. Mafic and felsic gneisses there are characterised by isotopically depleted, positive Nd and Hf initials and model ages between 2100 and 2000 Ma. They may be explained as juvenile additions to the crust towards the end of the Palaeoproterozoic. These juvenile rocks occur in a narrow, c. 150 km long E-W trending belt, inferred to trace a suture that is associated with a large Palaeoproterozoic accretionary orogenic system. The Southern Terrane contains many features that are similar to the Australo-Antarctic Mawson Continent and may be its furthermost extension into East Antarctica. The Eastern Terrane is characterised by metagranitoids that formed in a continental volcanic arc setting during a late Mesoproterozoic orogeny at c. 1060 Ma. Subsequently, the rocks experienced high-temperature metamorphism during Pan-African collisional tectonics at 600 Ma. Isotopically depleted zircon grains yielded Hf model ages of 1600-1400 Ma, which are identical to Nd model ages obtained from juvenile metagranitoids. Most likely, these rocks trace the suture related to the amalgamation of the Indo-Antarctic and West Gondwana continental blocks at ~600 Ma. The Eastern Terrane is interpreted as the southernmost extension of the Pan-African Mozambique/Maud Belt in East Antarctica and, based on Hf isotope data, may also represent a link to the Ellsworth-Whitmore Mountains block in West Antarctica and the Namaqua-Natal Province of southern Africa. Geochemical evidence indicates that the majority of the protoliths of the mafic gneisses in the Northern Terrane formed as oceanic island basalts in a within-plate setting. Subsequently the rocks were incorporated into a subduction zone environment and, finally, accreted to a continental margin during Pan-African collisional tectonics. Felsic gneisses there provide evidence for a within-plate and volcanic arc/collisional origin. Emplacement of granitoids occurred at c. 530 Ma and high-temperature, high-pressure metamorphism took place at 510-500 Ma. Enriched Hf and Nd initials and Palaeoproterozoic model ages for most samples indicate that no juvenile material was added to the crust of the Northern Terrane during the Pan-African Orogeny but recycling of older crust or mixing of crustal components of different age must have occurred. Isotopically depleted mafic gneisses, which are spatially associated with eclogite-facies pyroxenites, yielded late Mesoproterozoic Nd model ages. These rocks occur in a narrow, at least 100 km long, E-W trending belt that separates alkaline ocean island metabasalts and within-plate metagranitoids from volcanic arc metabasalts and volcanic arc/syn-collisional metagranitoids in the Northern Terrane. This belt is interpreted to trace the late Neoproterozoic/early Cambrian Pan-African collisional suture between the Australo-Antarctic and the combined Indo-Antarctic/West Gondwana continental blocks that formed during the final amalgamation of Gondwana.

Sedimentology, planktonic foraminifera distribution and stable isotope composition during marine isotope stage 3 of ODP Site 172-1060 in the West Atlantic

We have studied Ocean Drilling Program Site 1060 on the Blake Outer Ridge, which lies beneath the Gulf Stream. We focus on marine isotope stage 3, 60-25 thousand years before present (ka). Sea surface temperatures (SSTs) inferred both from foraminiferal fauna and alkenone ratios, as well as counts of iceberg melt-out debris and benthic stable isotope analyses, enable our record to be interpreted in terms of regional hydrographic changes as well as changing thermohaline circulation (THC). The observed SST record is consistent with the air temperature record from the Greenland ice cores. However, Site 1060 exhibits important differences in detail compared with the ice core record, and when compared to other sites within the North Atlantic, significant longitudinal differences emerge. At Site 1060 in the western Atlantic, all Greenland stadials (GS) whether associated with Heinrich events (HEs) or not, show a similar small amplitude of cooling; mean faunal-based SSTaug during GS is only 1.5°C colder than during Greenland interstadials (GIS). In addition, during GS the coldest SSTs are limited to apparently brief events. This is in contrast to several eastern Atlantic sites where HE stadials exhibit coolings that are enhanced by 2°C compared to other GS and where cold conditions are not restricted to cold pulses but cover 2 ka-long intervals. Furthermore, Site 1060 SSTs remained warm right through each interstadial, in contrast to the sustained and uniform cooling trend through interstadials that is consistently observed in Greenland, indicated by measurements of delta18O in ice.

Age and strontium isotope composition for Cretaceous in DSDP Hole 74-525

Firm stratigraphic correlations are needed to evaluate the global significance of unconformity bounded units (sequences). We correlate the well-developed uppermost Campanian and Maestrichtian sequences of the New Jersey Coastal Plain to the geomagnetic polarity time scale (GPTS) by integrating Sr-isotopic stratigraphy and biostratigraphy. To do this, we developed a Maestrichtian (ca. 73-65 Ma) Sr-isotopic reference section at Deep Sea Drilling Project Hole 525A in the southeastern Atlantic Ocean. Maestrichtian strata can then be dated by measuring their 87Sr/86Sr composition, calibrating to the GPTS of S. C. Cande and D. V. Kent (1993, personal commun.), and using the equation Age (Ma) = 37326.894-52639.89 (87Sr/86Sr). Sr-stratigraphic resolution for the Maestrichtian is estimated as +-1.2 to +-2 m.y. At least two unconformity-bounded units comprise the uppermost Campanian to Maestrichtian strata in New Jersey. The lower one, the Marshalltown sequence, is assigned to calcareous nannofossil Zones CC20/21 (~NC19) and CC22b (~NC20). It ranges in age from ~74.1 to 69.9 Ma based on Sr-isotope age estimates. The overlying Navesink sequence is assigned to calcareous nannoplankton Zones CC25-26 (~NC21-23); it ranges in age from 69.3 to 65 Ma based on Sr-isotope age estimates. The upper part of this sequence, the Tinton Formation, has no calcareous planktonic control; Sr-isotopes provide an age estimate of 66 +- 1.2 Ma (latest Maestrichtian). Sequence boundaries at the base and the top of the Marshalltown sequence match boundaries elsewhere in the Atlantic Coastal Plain (Owens and Gohn, 1985) and the inferred global sea-level record of Haq et al. (1987); they support eustatic changes as the mechanism controlling depositional history of this sequence. However, the latest Maestrichtian record in New Jersey does not agree with Haq et al. (1987); we attribute this to correlation and time-scale differences near the Cretaceous/Paleogene boundary. High sedimentation rates in the latest Maestrichtian of New Jersey (Shrewsbury Member of the Red Bank Formation and the Tinton Formation) suggest tectonic uplift and/or rapid progradation during deposition of the highstand systems tract.

Calcium isotope ratios of porewaters of ODP Leg 204 holes

The calcium isotopic composition of porewaters and authigenic carbonates in the anoxic sediments of a convergent continental margin drilled during Ocean Drilling Program (ODP) provides first insight into the different processes that control Ca geochemistry in clastic marine, organic-rich sedimentary environments. In 4 sites drilled during Leg 204 at Hydrate Ridge (Cascadia Margin, offshore Oregon/USA), sulfate is consumed during anaerobic oxidation of methane and of organic matter via sulfate reduction within the upper meters of the sedimentary section. These reactions promote the precipitation of authigenic carbonates through the generation of bicarbonate, which is reflected in a pronounced decrease in calcium concentration. Although Ca isotope fractionation is observed during carbonate precipitation, Ca concentration in the pore fluids from ODP Leg 204 is decoupled from Ca isotopy, which seems to be mainly controlled by the release of light Ca isotopes that completely overprint the carbonate formation effect. Different processes, such as the release of organically bound Ca, ion exchange and ion pair formation may be responsible for the released light Ca. Deeper within the sedimentary section, additional processes such as ash alteration influence the Ca isotopic composition of the porewater. Two sites, drilled into the deeper core of the accretionary prism, reveal the nature of fluids which have reacted with the oceanic basement. These deep fluids are characterized by relatively high Ca concentrations and low d44/40Ca ratios.

Calcium isotope fractionation in cultured, modern and fossil scleractinian coral skeleton

The present study investigates the influence of environmental (temperature, salinity) and biological (growth rate, inter-generic variations) parameters on calcium isotope fractionation (d44/40Ca) in scleractinian coral skeleton to better constrain this record. Previous studies focused on the d44/40Ca record in different marine organisms to reconstruct seawater composition or temperature, but only few studies investigated corals. This study presents measurements performed on modern corals from natural environments (from the Maldives for modern and from Tahiti for fossil corals) as well as from laboratory cultures (Centre Scientifique de Monaco). Measurements on Porites sp., Acropora sp., Montipora verrucosa and Stylophora pistillata allow constraining inter-generic variability. Our results show that the fractionation of d44/40Ca ranges from 0.6 to 0.1 per mil, independent of the genus or the environmental conditions. No significant relationship between the rate of calcification and d44/40Ca was found. The weak temperature dependence reported in earlier studies is most probably not the only parameter that is responsible for the fractionation. Indeed, sub-seasonal temperature variations reconstructed by d18O and Sr/Ca ratio using a multi-proxy approach, are not mirrored in the coral's d44/40Ca variations. The intergeneric variability and intrageneric variability among the studied samples are weak except for S. pistillata, which shows calcium isotopic values increasing with salinity. The variability between samples cultured at a salinity of 40 is higher than those cultured at a salinity of 36 for this species. The present study reveals a strong biological control of the skeletal calcium isotope composition by the polyp and a weak influence of environmental factors, specifically temperature and salinity (except for S. pistillata). Vital effects have to be investigated in situ to better constrain their influence on the calcium isotopic signal. If vital effects could be extracted from the isotopic signal, the calcium isotopic composition of coral skeletons could provide reliable information on the calcium composition and budget in ocean.

Strontium, oxygen and hydrogen isotope ratios of basalts from DSDP Hole 504B

DSDP Hole 504B was drilled into 6 Ma crust, about 200 km south of the Costa Rica Rift, Galapagos Spreading Center, penetrating 1.35 km into a section that can be divided into four zones-Zone I: oxic submarine weathering; Zone II: anoxic alteration; Zones III and IV: hydrothermal alteration to greenschist facies. In Zone III there is intense veining of pillow basalts. Zone IV consists of altered sheeted dikes. Isotopic geochemical signatures in relation to the alteration zones are recorded in Hole 504B, as follows: Zone Depth(m) Average87Sr/86Sr Average delta18O (?) Average deltaD (?) I 275-550 0.7032 7.3 -63 II 550-890 0.7029 6.5 -45 III 890-1050 0.7035 5.6 -31 IV 1050-1350 0.7032 5.5 -36 Alteration temperatures are as low as 10°C in Zones I and II based on oxygen isotope fractionation. Strontium isotopic data indicate that a circulation of seawater is much more restricted in Zone II than in Zone I. Fluid inclusion measurements of vein quartz indicate the alteration temperature was mainly 300 +/- 20°C in Zones III and IV, which is consistent with secondary mineral assemblages. The strontium, oxygen, and hydrogen isotopic compositions of hydrothermal fluids which were responsible for the greenschist facies alteration in Zones III and IV are estimated to be 0.7037, 2?, and 3?, respectively. Strontium and oxygen isotope data indicate that completely altered portions of greenstones and vein minerals were in equilibrium with modified seawater under low water/rock ratios (in weight) of about 1.6. This value is close to that of the end-member hydrothermal fluids issuing at 21°N EPR. Basement rocks are not completely hydrothermally altered. About 32% of the greenstones in Zones III and IV have escaped alteration. Thus 1 g of fresh basalt including the 32% unaltered portion are required in order to make 1 g of end-member solution from fresh seawater in water-rock reactions.