Stable isotope ratios and geochemical composition of authigenic carbonates from ODP Sites 186-1150 and 186-1151

Several carbonaceous layers or fragments were recovered from sediments of Sites 1150 and 1151 on the deep-sea terrace of the Japan Trench during Leg 186. The X-ray diffraction analysis (XRD) data indicate that these are predominantly dolomitic. In this study, carbon and oxygen isotopes of these carbonates recovered at Sites 1150 and 1151 are presented. The oxygen isotope ratios of the dolomites analyzed range from +0.4 per mil to +4.1 per mil vs. Peedee formation belemnite (PDB) and those of calcites from +0.6 per mil to +2.8 per mil PDB. The isotopic composition of carbon varies from -7.0 per mil to +12.3 per mil PDB in dolomite and from -13.4 per mil to -24.1 per mil PDB in calcite. The wide range of carbon isotopic compositions indicates that the carbonate samples were formed by the decomposition of organic matter through reactions such as oxidation, sulfate reduction, and methane formation during diagenesis.

Calcareous microfossil isotopes and Miocene datum events of ODP Holes 189-1170A and 189-1172A

Downcore oxygen and carbon stable isotope records of planktonic and benthic foraminifers and fine-fraction carbonate from the southern high latitudes provide critical paleohydrographic constraints on the evolution of the Southern Ocean climate. In particular, the potential effects of an intensified Antarctic Circumpolar Current on the thermal isolation and cooling of the southern high latitudes, production of cold deep waters, and, ultimately, accumulation of continental ice on Antarctica in the middle Miocene are matters of interest. Using sediment materials from Ocean Drilling Program Leg 189 Sites 1170 and 1172 off Tasmania, Ennyu and Arthur (2004, doi:10.1029/151GM13) established the surface- and deepwater stable isotope records in the Southern Ocean across the middle Miocene event of the east Antarctic ice sheet expansion and discussed the paleoclimate proxy records in terms of the thermal evolution of the southern high latitudes and its effect on deepwater circulation. This report provides data tables and other supporting information relevant to discussions presented in Ennyu and Arthur (2004, doi:10.1029/151GM13). Items included in this report are (1) the oxygen and carbon stable isotope data measured on the Miocene bulk fine-fraction (i.e., <63 µm, primarily polyspecific nannofossil assemblage) carbonate and planktonic and benthic foraminifers from Holes 1170A and 1172A and (2) the Miocene depth-age models for the two sites.

Middle Miocene stable carbon and oxygen isotope record of ODP Holes 130-805B and 130-806B

Bulk carbon isotope records are an effective chemostratigraphic tool for the middle Miocene because of the large and systematic variation in first-order d13C signals. Bulk d13C measurements support the presence of a hiatus at 305 mbsf in Hole 805B (latest middle Miocene), provisionally located while on board ship using biostratigraphic and magnetostratigraphic events. Records at Holes 805B and 806B show the middle Miocene Monterey carbon isotope excursion although the record at Hole 806B is apparently more stratigraphically continuous. Detailed analysis of multispecies foraminiferal carbon isotope records during the middle Miocene ("Monterey excursion") segment at Hole 806B support the assertion that this carbon isotope excursion comprises mainly between-reservoir effects. The benthic d18O data increase after 15.3 Ma, which we suggest corresponds to the mid-Miocene cooling step/ice volume increase of other authors. Planktonic foraminiferal d18O evidence exists for steepening of the thermocline at 17.4 Ma. A second-order d13C excursion superimposed at 13.8 Ma on the first-order Monterey excursion is associated with a second-order negative d18O excursion.

Whole-rock oxygen and carbon isorope record across the Cretaceous/Tertiary boundary in ODP Hole 130-807C

Whole-rock d18O analyses of the Paleogene and Upper Cretaceous succession at Ocean Drilling Program Hole 807C suggest the presence of hiatuses between 876.95 and 894.47 mbsf and between 1138.82 and 1140.94 mbsf. The d13C data show a pronounced positive excursion between 1130 and 1180 mbsf that corresponds to the positive d13C values characteristic of the Paleocene. Despite the stratigraphic breaks in the section, the d18O data show a systematic increase between 1360 mbsf and the hiatus between 876.95 and 894.47 mbsf, which is consistent with previous suggestions of long-term climatic cooling through the Paleogene. The Cretaceous/Tertiary transition is apparently complete in this section and is of remarkable thickness. The expanded nature of this portion of the succession is probably the result of secondary depositional processes. High-resolution sampling across this boundary may reveal detailed structure of the d13C decline associated with the extinctions that mark the termination of the Cretaceous.

Sable isotope record and sediment composition of Cretaceous samples of Deremara Rise

We estimate tropical Atlantic upper ocean temperatures using oxygen isotope and Mg/Ca ratios in well-preserved planktonic foraminifera extracted from Albian through Santonian black shales recovered during Ocean Drilling Program Leg 207 (North Atlantic Demerara Rise). On the basis of a range of plausible assumptions regarding seawater composition at the time the data support temperatures between 33° and 42°C. In our low-resolution data set spanning ~84-100 Ma a local temperature maximum occurs in the late Turonian, and a possible minimum occurs in the mid to early late Cenomanian. The relation between single species foraminiferal d18O and Mg/Ca suggests that the ratio of magnesium to calcium in the Turonian-Coniacian ocean may have been lower than in the Albian-Cenomanian ocean, perhaps coincident with an ocean 87Sr/86Sr minimum. The carbon isotopic compositions of distinct marine algal biomarkers were measured in the same sediment samples. The d13C values of phytane, combined with foraminiferal d13C and inferred temperatures, were used to estimate atmospheric carbon dioxide concentrations through this interval. Estimates of atmospheric CO2 concentrations range between 600 and 2400 ppmv. Within the uncertainty in the various proxies, there is only a weak overall correspondence between higher (lower) tropical temperatures and more (less) atmospheric CO2. The GENESIS climate model underpredicts tropical Atlantic temperatures inferred from ODP Leg 207 foraminiferal d18O and Mg/Ca when we specify approximate CO2 concentrations estimated from the biomarker isotopes in the same samples. Possible errors in the temperature and CO2 estimates and possible deficiencies in the model are discussed. The potential for and effects of substantially higher atmospheric methane during Cretaceous anoxic events, perhaps derived from high fluxes from the oxygen minimum zone, are considered in light of recent work that shows a quadratic relation between increased methane flux and atmospheric CH4 concentrations. With 50 ppm CH4, GENESIS sea surface temperatures approximate the minimum upper ocean temperatures inferred from proxy data when CO2 concentrations specified to the model are near those inferred using the phytane d13C proxy. However, atmospheric CO2 concentrations of 3500 ppm or more are still required in the model in order to reproduce inferred maximum temperatures.

Strontium and oxygen isotope data for DSDP Hole 44-390A and ODP Leg 171 holes

Differences in regional responses to climate fluctuations are well documented on short time scales (e.g., El Niño-Southern Oscillation), but with the exception of latitudinal temperature gradients, regional patterns are seldom considered in discussions of ancient greenhouse climates. Contrary to the expectation of global warming or global cooling implicit in most treatments of climate evolution over millions of years, this paper shows that the North Atlantic warmed by as much as 6°C (1.5% decrease in d18O values of planktic foraminifera) during the Maastrichtian global cooling interval. We suggest that warming was the result of the importation of heat from the South Atlantic. Decreasing North Atlantic d18O values are also associated with increasing gradients in planktic d13C values, suggesting increasing surface-water stratification and a correlated strengthening of the North Atlantic Polar Front. If correct, this conclusion predicts arctic cooling during the late Maastrichtian. Beyond implications for the Maastrichtian, these data demonstrate that climate does not behave as if there is a simple global thermostat, even on geologic time scales.

AMS 14C ages and isotopic compositions of samples from the Derugin Basin, Sea of Okhotsk

An area of massive barite precipitations was studied at a tectonic horst in 1500 m water depth in the Derugin Basin, Sea of Okhotsk. Seafloor observations and dredge samples showed irregular, block- to column-shaped barite build-ups up to 10 m high which were scattered over the seafloor along an observation track 3.5 km long. High methane concentrations in the water column show that methane expulsion and probably carbonate precipitation is a recently active process. Small fields of chemoautotrophic clams (Calyptogena sp., Acharax sp.) at the seafloor provide additional evidence for active fluid venting. The white to yellow barites show a very porous and often layered internal fabric, and are typically covered by dark-brown Mn-rich sediment; electron microprobe spectroscopy measurements of barite sub-samples show a Ba substitution of up to 10.5 mol% of Sr. Rare idiomorphic pyrite crystals (~1%) in the barite fabric imply the presence of H2S. This was confirmed by clusters of living chemoautotrophic tube worms (1 mm in diameter) found in pores and channels within the barite. Microscopic examination showed that micritic aragonite and Mg-calcite aggregates or crusts are common authigenic precipitations within the barite fabric. Equivalent micritic carbonates and barite carbonate cemented worm tubes were recovered from sediment cores taken in the vicinity of the barite build-up area. Negative d13C values of these carbonates (>-43.5 per mill PDB) indicate methane as major carbon source; d18O values between 4.04 and 5.88 per mill PDB correspond to formation temperatures, which are certainly below 5°C. One core also contained shells of Calyptogena sp. at different core depths with 14C-ages ranging from 20 680 to >49 080 yr. Pore water analyses revealed that fluids also contain high amounts of Ba; they also show decreasing SO4**2- concentrations and a parallel increase of H2S with depth. Additionally, S and O isotope data of barite sulfate (d34S: 21.0-38.6 per mill CDT; d18O: 9.0-17.6 per mill SMOW) strongly point to biological sulfate reduction processes. The isotope ranges of both S and O can be exclusively explained as the result of a mixture of residual sulfate after a biological sulfate reduction and isotopic fractionation with 'normal' seawater sulfate. While massive barite deposits are commonly assumed to be of hydrothermal origin, the assemblage of cheomautotrophic clams, methane-derived carbonates, and non-thermally equilibrated barite sulfate strongly implies that these barites have formed at ambient bottom water temperatures and form the features of a Giant Cold Seep setting that has been active for at least 49 000 yr.

Stable isotopes and element concentrations of samples from the Wadi Bih, United Arab Emirates

Ocean acidification triggered by Siberian Trap volcanism was a possible kill mechanism for the Permo-Triassic Boundary mass extinction, but direct evidence for an acidification event is lacking. We present a high-resolution seawater pH record across this interval, using boron isotope data combined with a quantitative modeling approach. In the latest Permian, increased ocean alkalinity primed the Earth system with a low level of atmospheric CO2 and a high ocean buffering capacity. The first phase of extinction was coincident with a slow injection of carbon into the atmosphere, and ocean pH remained stable. During the second extinction pulse, however, a rapid and large injection of carbon caused an abrupt acidification event that drove the preferential loss of heavily calcified marine biota.

Geochemistry of middle Eocene-lower Oligocene pelagic sediments of ODP Hole 105-647A

Geochemical analyses of the middle Eocene through lower Oligocene lithologic Unit IIIC (260-518 meters below seafloor [mbsf]) indicate a relatively constant geochemical composition of the detrital fraction throughout this depositional interval at Ocean Drilling Program (ODP) Site 647 in the southern Labrador Sea. The main variability occurs in redox-sensitive elements (e.g., iron, manganese, and phosphorus), which may be related to early diagenetic mobility in anaerobic pore waters during bacterial decomposition of organic matter. Initial preservation of organic matter was mediated by high sedimentation rates (36 m/m.y.). High iron (Fe) and manganese (Mn) contents are associated with carbonate concretions of siderite, manganosiderite, and rhodochrosite. These concretions probably formed in response to elevated pore-water alkalinity and total dissolved carbon dioxide (CO2) concentrations resulting from bacterial sulfate reduction, as indicated by nodule stable-isotope compositions and pore-water geochemistry. These nodules differ from those found in upper Cenozoic hemipelagic sequences in that they are not associated with methanogenesis. Phosphate minerals (carbonate-fluorapatite) precipitated in some intervals, probably as the result of desorption of phosphorus from iron and manganese during reduction. The bulk chemical composition of the sediments differs little from that of North Atlantic Quaternary abyssal red clays, but may contain a minor hydrothermal component. The silicon/ aluminum (Si/Al) ratio, however, is high and variable and probably reflects original variations in biogenic opal, much of which is now altered to smectite and/or opal CT. An increase in the sodium/potassium (Na/K) ratio in the upper Eocene corresponds to the beginning of coarsergrained feldspar flux to the site, possibly marking the onset of more vigorous deep currents. Although the Site 647 cores provide a nearly complete high-resolution, high-latitude Eocene-Oligocene record, the high sedimentation rate and somewhat unusual diagenetic conditions have led to variable alteration of benthic foraminifers and fine-fraction carbonate and have overprinted the original stable-isotope records. Planktonic foraminifers are less altered, but on the whole, there is little chance of sorting out the nature and timing of environmental change on the basis of our stable-isotope analyses.