Nd bulk isotopes and 40Ar/39Ar ages of individual minerals from Aurora and Wilkes sub-glacial basin sediments

The Wilkes and Aurora basins are large, low-lying sub-glacial basins that may cause areas of weakness in the overlying East Antarctic ice sheet. Previous work based on ice-rafted debris (IRD) provenance analyses found evidence for massive iceberg discharges from these areas during the late Miocene and Pliocene. Here we characterize the sediments shed from the inferred areas of weakness along this margin (94°E to 165°E) by measuring40Ar/39Ar ages of 292 individual detrital hornblende grains from eight marine sediment core locations off East Antarctica and Nd isotopic compositions of the bulk fine fraction from the same sediments. We further expand the toolbox for Antarctic IRD provenance analyses by exploring the application of 40Ar/39Ar ages of detrital biotites; biotite as an IRD tracer eliminates lithological biases imposed by only analyzing hornblendes and allows for characterization of samples with low IRD concentrations. Our data quadruples the number of detrital 40Ar/39Ar ages from this margin of East Antarctica and leads to the following conclusions: (1) Four main sectors between the Ross Sea and Prydz Bay, separated by ice drainage divides, are distinguishable based upon the combination of 40Ar/39Ar ages of detrital hornblende and biotite grains and the e-Nd of the bulk fine fraction; (2) 40Ar/39Ar biotite ages can be used as a robust provenance tracer for this part of East Antarctica; and (3) sediments shed from the coastal areas of the Aurora and Wilkes sub-glacial basins can be clearly distinguished from one another based upon their isotopic fingerprints.

Stable oxygen isotopes of Antarctic snow pits

Stable oxygen analyses and snow accumulation rates from snow pits sampled in the McMurdo Dry Valleys have been used to reconstruct variations in summer temperature and moisture availability over the last four decades. The temperature data show a common interannual variability, with strong regional warmings occurring especially in 1984/85, 1995/96 and 1990/91 and profound coolings during 1977/78, 1983/84, 1988/89, 1993/94, and 1996/97. Annual snow accumulation shows a larger variance between sites, but the early 1970s, 1984, 1997, and to a lesser degree 1990/91 are characterized overall by wetter conditions, while the early and late 1980s show low snow accumulation values. Comparison of the reconstructed and measured summer temperatures with the Southern Oscillation Index (SOI) and the Antarctic Oscillation (AAO) yield statistically significant correlations, which improve when phase-relationships are considered. A distinct change in the phase relationship of the correlation is observed, with the SOI-AAO leading over the temperature records by one year before, and lagging by one year after 1988. These results suggest that over the last two decades summer temperatures are influenced by opposing El Niño Southern Oscillation and AAO forcings and support previous studies that identified a change in the Tropical-Antarctic teleconnection between the 1980s and 1990s.

Dissolved inorganic carbon isotopes in pore waters of ODP Leg 204 sediments

Isotopic characterization of carbon in the dissolved inorganic carbon (DIC) pool is fundamental for a wide array of scientific studies directly related to gas hydrate research. In order to generate integrated and internally consistent data of d13C of DIC in pore waters from Hydrate Ridge, we used the modern continuous flow technology of a GasBench II automated sampler interfaced to a gas source stable isotope mass spectrometer for the rapid determination (~80 samples/day) of d13C DIC in small-volume water samples. The overall precision of this technique is conservatively estimated to be better than ±0.15 per mil (1 sigma), which is similar to the precision of methods in current use. Here we present the data generated from Ocean Drilling Program Leg 204 pore water samples.

Modeling the sensitivity of precipitation oxygen isotopes to the Last Glacial Maximum boundary conditions: A study using Community Atmosphere Model (CAM3.0)

To understand the validity of d18O proxy records as indicators of past temperature change, a series of experiments was conducted using an atmospheric general circulation model fitted with water isotope tracers (Community Atmosphere Model version 3.0, IsoCAM). A pre-industrial simulation was performed as the control experiment, as well as a simulation with all the boundary conditions set to Last Glacial Maximum (LGM) values. Results from the pre-industrial and LGM simulations were compared to experiments in which the influence of individual boundary conditions (greenhouse gases, ice sheet albedo and topography, sea surface temperature (SST), and orbital parameters) were changed each at a time to assess their individual impact. The experiments were designed in order to analyze the spatial variations of the oxygen isotopic composition of precipitation (d18Oprecip) in response to individual climate factors. The change in topography (due to the change in land ice cover) played a significant role in reducing the surface temperature and d18Oprecip over North America. Exposed shelf areas and the ice sheet albedo reduced the Northern Hemisphere surface temperature and d18Oprecip further. A global mean cooling of 4.1 °C was simulated with combined LGM boundary conditions compared to the control simulation, which was in agreement with previous experiments using the fully coupled Community Climate System Model (CCSM3). Large reductions in d18Oprecip over the LGM ice sheets were strongly linked to the temperature decrease over them. The SST and ice sheet topography changes were responsible for most of the changes in the climate and hence the d18Oprecip distribution among the simulations.

Geochemistry and isotopes at DSDP Site 76-533

Concentrations and d34S and d13C values were determined on SO4, HCO3, CO2, and CH4 in interstitial water and gas samples from the uppermost 400 m of sediment on the Blake Outer Ridge. These measurements provide the basis for detailed interpretation of diagenetic processes associated with anaerobic respiration of electrons generated by organic- matter decomposition. The sediments are anaerobic at very shallow depths (<1 m) below the seafloor. Sulfate reduction is confined to the uppermost 15 m of sediment and results in a significant outflux of oxidized carbon from the sediments. At the base of the sulfate reduction zone, upward-diffusing CH4 is being oxidized, apparently in conjunction with SO4 reduction. CH4 generation by CO2 reduction is the most important metabolic process below the 15-m depth. CO2 removal is more rapid than CO2 input over the depth interval from 15 to 100 m, and results in a slight decrease in HCO3 concentration accompanied by a 40 per mil positive shift in d13C. The differences among coexisting CH4, CO2, and HCO3 are consistent with kinetic fractionation between CH4 and dissolved CO2, and equilibrium fractionation between CO2 and HCO3. At depths greater than 100 m, the rate of input of CO2 (d13C = -25 per mil) exceeds by 2 times the rate of removal of CO2 by conversion to CH4 (d13C of -60 to -65 per mil). This results in an increase of dissolved HCO3 concentration while maintaining d13C of HCO3 relatively constant at +10 per mil. Non-steady-state deposition has resulted in significantly higher organic carbon contents and unusually high (70 meq/l) pore-water alkalinities below 150 m. These high alkalinities are believed to be related more to spontaneous decarboxylation reactions than to biological processes. The general decrease in HCO3 concentration with constant d13C over the depth interval of 200 to 400 m probably reflects increased precipitation of authigenic carbonate. Input-output carbon isotope-mass balance calculations, and carbonate system equilibria in conjunction with observed CO2-CH4 ratios in the gas phase, independently suggest that CH4 concentrations on the order of 100 mmol/kg are present in the pore waters of Blake Outer Ridge sediments. This quantity of CH4 is believed to be insufficient to saturate pore waters and stabilize the CH4*6H2O gas hydrate. Results of these calculations are in conflict with the physical recovery of gas hydrate from 238 m, and with the indirect evidence (seismic reflectors, sediment frothing, slightly decreasing salinity and chlorinity with depth, and pressure core barrel observations) of gas-hydrate occurrence in these sediments. Resolution of this apparent conflict would be possible if CH4 generation were restricted to relatively thin (1-10 m) depth intervals, and did not occur uniformly at all depths throughout the sediment column, or if another methanogenic process (e.g., acetate fermentation) were a major contributor of gas.

Oxygen isotopes and Sr/Ca ratios of fossil corals from Bonaire

Explanations for the demise of the Classic Maya civilization on the Yucatán Peninsula during the Terminal Classic Period (TCP; CE 750-1050) are controversial. Multiyear droughts are one likely cause, but the role of the Caribbean Sea, the dominant moisture source for Mesoamerica, remains largely unknown. Here we present bimonthly resolved snapshots of reconstructed sea surface temperature (SST) and salinity (SSS) variability in the southern Caribbean from precisely dated fossil corals. Our fossil coral results from Bonaire indicate strong interannual to decadal SST and SSS variability in the southern Caribbean Sea during the TCP with multiyear extremes of high SSS and high SST that coincide with droughts on the Yucatán Peninsula. The results are best explained by changed Caribbean SST gradients affecting the Caribbean low-level atmospheric jet with consequences for Mesoamerican precipitation, possibly linked to changes in Atlantic Meridional Overturning Circulation strength. Our findings provide a new perspective on the anomalous hydrological changes on the Yucatán Peninsula during the TCP that complement the often-suggested southward displacement of the Intertropical Convergence Zone. We advocate for a strong role of ocean-atmosphere interactions in the Caribbean Sea related to the multiyear variations in Caribbean Sea surface conditions as an important driver of the spatially complex pattern of hydrological anomalies during the TCP.

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.

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.

Geochemistry, isotopes, trace elements and fluid inclusion geothermometry at DSDP Hole 83-504B

Stockwork-like metal sulfide mineralizations were found at 910-928 m below seafloor (BSF) in the pillow/dike transition zone of Hole 504B. This is the same interval where most physical properties of the 5.9-m.y.-old crust of the Costa Rica Rift change from those characteristic of Layer 2B to those of Layer 2C. The pillow lavas, breccias, and veins of the stockwork-like zone were studied by transmitted and reflected light microscopy, X-ray diffraction, and electron microprobe analysis. Bulk rock oxygen isotopic analyses as well as isolated mineral oxygen and sulfur isotopic analyses and fluid inclusion measurements were carried out. A complex alteration history was reconstructed that includes three generations of fissures, each followed by precipitation of characteristic hydrothermal mineral parageneses: (1) Minor and local deposition of quartz occurred on fissure walls; adjacent wall rocks were silicified, followed by formation of chlorite and minor pyrite I in the veins, whereas albite, sphene, chlorite and chlorite-expandable clay mixtures, actinolite, and pyrite replaced igneous phases in the host rocks. The hydrothermal fluids responsible for this first stage were probably partially reacted seawater, and their temperatures were at least 200-250° C. (2) Fissures filled during the first stage were reopened and new cracks formed. They were filled with quartz, minor chlorite and chlorite-expandable clay mixtures, traces of epidote, common pyrite, sphalerite, chalcopyrite, and minor galena. During the second stage, hydrothermal fluids were relatively evolved metal- and Si-rich solutions whose temperatures ranged from 230 to 340° C. The fluctuating chemical composition and temperature of the solutions produced a complex depositional sequence of sulfides in the veins: chalcopyrite I, ± Fe-rich sphalerite, chalcopyrite II ("disease"), Fe-poor sphalerite, chalcopyrite III, galena, and pyrite II. (3) During the last stage, zeolites and Mg-poor calcite filled up the remaining spaces and newly formed cracks and replaced the host rock plagioclase. Analcite and stilbite were first to form in veins, possibly at temperatures below 200°C; analcite and earlier quartz were replaced by laumontite at 250°C, whereas calcite formation temperature ranged from 135 to 220°C. The last stage hydrothermal fluids were depleted in Mg and enriched in Ca and 18O compared to seawater and contained a mantle carbon component. This complex alteration history paralleling a complex mineral paragenesis can be interpreted as the result of a relatively long-term evolution of a hydrothermal system with superimposed shorter term fluctuations in solution temperature and composition. Hydrothermal activity probably began close to the axis of the Costa Rica Rift with the overall cooling of the system and multiple fracturing stages due to movement of the crust away from the axis and/or cooling of a magmatic heat source.

Stable carbon isotopes, Methane Index, and distributions of different GDGTs

Gas hydrates represent one of the largest pools of readily exchangeable carbon on Earth's surface. Releases of the greenhouse gas methane from hydrates are proposed to be responsible for climate change at numerous events in geological history. Many of these inferred events, however, were based on carbonate carbon isotopes which are susceptible to diagenetic alterations. Here we propose a molecular fossil proxy, i.e., the "Methane Index (MI)", to detect and document the destabilization and dissociation of marine gas hydrates. MI consists of the relative distribution of glycerol dibiphytanyl glycerol tetraethers (GDGTs), the core membrane lipids of archaea. The rational behind MI is that in hydrate-impacted environments, the pool of archaeal tetraether lipids is dominated by GDGT-1, -2 and -3 due to the large contribution of signals from the methanotrophic archaeal community. Our study in the Gulf of Mexico cold-seep sediments demonstrates a correlation between MI and the compound-specific carbon isotope of GDGTs, which is strong evidence supporting the MI-methane consumption relationship. Preliminary applications of MI in a number of hydrate-impacted and/or methane-rich environments show diagnostic MI values, corroborating the idea that MI may serve as a robust indicator for hydrate dissociation that is useful for studies of global carbon cycling and paleoclimate change.

Iridium and other element concentrations and magnetostratigraphy across the Cretaceous/Tertiarty boundary in ODP Hole 122-761C

Samples from Ocean Drilling Program Hole 761C, collected on both sides of the Cretaceous/Tertiary boundary have been analyzed for their chemical and mineralogical content. The sediment consists of nannofossil ooze with variable amounts of clay. The boundary is marked by a color change associated with a nearly step-like decrease of the carbonate fraction. Paleomagnetic data and the drop of the carbonate content indicate that a strong reduction of the sedimentation rate occurred at the boundary and persisted for million of years. An iridium anomaly of 80 ng/cm**2, together with overabundances of Cr and Fe, are found in close coincidence with the planktonic crisis. These enrichments can be explained by the infall of =0.16 g/cm2 of Cl-like chondritic material. Co and Ni enrichments and a great quantity of Ni-rich magnetites are also observed in the basal Danian. These elements and minerals excepted, the composition of the insoluble fraction appears to be nearly unchanged across the boundary. Chemical and mineralogical observations support a cosmic origin for the Cretaceous/Tertiary event but do not reveal the presence of any significant impact ejecta.