Strontium isotopes in pore waters of east equatorial Pacific sediments

Pore-water samples from the equatorial sedimentary bulge area show reversals in depth profiles of 87Sr/86Sr ratios at the sediment/basement interface. Results of this work support inferences made from previous pore-water data (from DSDP drilling in the area) that large-scale horizontal advection of seawater has occurred through the basement underlying the thick sedimentary sequence in this region. The area of apparent advection includes the eastern part of the equatorial high-productivity zone and part of the Guatemala Basin. We attempted to find links between the observed near-basement reversals in pore-water chemistry and sedimentary thickness, age, and topography of the area. Most of the sites that show horizontal advection have disturbed basement topography or outcrops within 10 to 20 km, suggesting that the cooling effects of outcrops may extend for at least 20 km horizontally. Heat-flow data from the area were compared to determine whether sites showing near-bottom chemistry reversals were consistent with areas of low conductive heat flow. This was generally true for the area of the sedimentary bulge and Guatemala Basin. Not enough pore-water data from the Nazca Plate were available to establish any reliable systematics. Because the high-productivity area is well-sealed from hydrothermal circulation, the missing heat must be lost by horizontal advective heat transport. From profiles of strontium isotopes and other elements that show departure from seawater values with increasing depth in the sediments, but return to seawater values near the basement, it appears that water flows relatively freely through much of the oceanic crust, even when sealed by considerable sedimentary cover.

Nd isotopes of ODP Sites 146-893 and 167-1017 samples

Changes in the source of intermediate waters to the southern California margin may have caused variations in seafloor oxygen levels on stadial-interstadial time scales. We test this hypothesis using the Nd isotopic composition of benthic foraminifera and fossil fish debris from ODP Sites 893 and 1017 to track the composition of intermediate waters across interstadials 8-14 (~37-52 ka) during Marine Isotope Stage 3. The epsilon-Nd values of waters bathing the seafloor at Site 893 were typically ~-9 and those bathing Site 1017 were ~-7, both of which are significantly less radiogenic than waters that had originated in either the North Pacific or Southern Ocean (by the time such waters reached the southern California margin). Detrital silicate epsilon-Nd values of nearly -12 suggest that this offset toward lower epsilon-Nd values was likely caused by boundary scavenging that partially overprinted the water mass composition with local/regional fluvial Nd inputs. In spite of the evidence for boundary scavenging, the lack of systematic seawater Nd isotope changes on a stadial-interstadial basis suggests that the provenance of the intermediate waters did not change, and that the waters were derived from the Southern Ocean. Instead, changes in local/regional sea surface productivity may have caused the recorded changes in seafloor oxygenation.

Major nannofossils, carbon and oxygen isotopes and carbon composition of ODP leg 194 site survey gravity cores

Biostratigraphic, sedimentologic, and geochemical analyses of hemipelagic periplatform sediments from shallow gravity cores taken during the Ocean Drilling Program Leg 194 site survey reveal that, despite the strong currents and almost infilled intraplatform bathymetric depressions, recent sedimentation at the location of the Leg 194 drill sites recorded glacial-interglacial cycles. Sediment analyses included determination of sediment type, carbonate content, bulk stable oxygen isotope composition, and calcareous nannofossil zones. Glacial periods, identified by elevated bulk d18O, are characterized by darker sediment color, coarser grain size, and lower carbonate content, whereas interglacial periods yield lighter-colored, finer, and carbonate-rich sediments. These data from the shallowmost few meters of Marion Plateau sediments complement the subsurface information of Leg 194 holes, in which the top few meters have not been analyzed in such a high-resolution fashion. In addition, these gravity cores are more likely to have recovered the sediments closest to the sediment/water interface as compared to the hydraulic piston cores collected during Leg 194.

Stable carbon and oxygen isotopes of foraminifera fand carbon content of ODP Leg 107 holes

High-resolution bio- and chemostratigraphy of an earliest Pliocene section from ODP Site 652 indicates that postflood paleoceanographic conditions in the Tyrrhenian Sea can be sub-divided into two discrete intervals. The first is manifested by an acme of Sphaeroidinellopsis spp., increasing carbonate contents, and a progressive decrease upsection in both the d13C and dl8O values of the planktonic foraminifera. The lower part of the acme interval contains unusual surface-to-bottom water isotope gradients suggesting a stratification of two water masses. Normal gradients in the upper part of the acme interval suggest a well-mixed water body. Between the end of the acme interval and the MP11/MP12 boundary, denoted by the first occurrence (F.O.) of Globorotalia margaritae, a migrational first appearance, there was a catastrophic collapse of the gradient marking an onset of the second post-flood interval. The disintegration of habitable conditions is suggested by a sharp decrease in carbonate content and the disappearance of the benthonic assemblage, which is subsequently replaced predominantly by Uvigerinapygmea, indicative of cold, low-oxygenated bottom waters. The introduction of benthonic species denoting well-oxygenated bottom conditions occurs within the lower MP12 zone. Superimposed on these overall trends are shorter term, warm-cold cycles, which are interpreted as orbitally induced, climatic fluctuations. Correlative studies of the less complete earliest Pliocene sections from ODP Holes 653B and 654A confirm these interpretations. A scenario derived from an integration of all the stratigraphic data indicates that normal paleoceanographic conditions were operating in the Tyrrhenian Sea only approximately 250,000 yr after the cessation of Messinian evaporative conditions at the Miocene/Pliocene boundary. The post-flood interval is marked by an initial period of gradual infilling, the Sphaeroidinellopsis spp. acme interval, followed by a disintegration of oceanographic conditions and a second recovery period. A sudden influx of cold, deep Atlantic waters into the Tyrrhenian Sea, resulting from a major tectonic break in the Gibraltar sill, may have caused this catastrophic reversal in the orderly recovery of normal paleoceanographic conditions in the post-flood period.

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

Geochemistry and Mg-isotopes of carbonate sediments and porefluids of ODP Site 130-807

Deep-sea pore fluids are potential archives of ancient seawater chemistry. However, the primary signal recorded in pore fluids is often overprinted by diagenetic processes. Recent studies have suggested that depth profiles of Mg concentration in deep-sea carbonate pore fluids are best explained by a rapid rise in seawater Mg over the last 10-20 Myr. To explore this possibility we measured the Mg isotopic composition of pore fluids and carbonate sediments from Ocean Drilling Program (ODP) site 807. Whereas the concentration of Mg in the pore fluid declines with depth, the isotopic composition of Mg in the pore fluid increases from -0.78 per mil near the sediment-water interface to -0.15 per mil at 778 mbsf. The Mg isotopic composition of the sediment, with few important exceptions, does not change with depth and has an average d26Mg value of -4.72 per mil. We reproduce the observed changes in sediment and pore-fluid Mg isotope values using a numerical model that incorporates Mg, Ca and Sr cycling and satisfies existing pore-fluid Ca isotope and Sr data. Our model shows that the observed trends in magnesium concentrations and isotopes are best explained as a combination of two processes: a secular rise in the seawater Mg over the Neogene and the recrystallization of low-Mg biogenic carbonate to a higher-Mg diagenetic calcite. These results indicate that burial recrystallization will add Mg to pelagic carbonate sediments, leading to an overestimation of paleo-temperatures from measured Mg/Ca ratios. The Mg isotopic composition of foraminiferal calcite appears to be only slightly altered by recrystallization making it possible to reconstruct the Mg isotopic composition of seawater through time.

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.

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.

3He/4He and 4He/20Ne ratios in pore water and gas in Pacific deep-sea sediments

We have measured the 3He/3He and 3He/20 Ne ratios of thirty-nine pore water and gas samples in deep-sea sediments collected at twelve sites on the Pacific Ocean bottom during the cruises of Deep Sea Drilling Project Legs 87, 89, 90 and 92. The 3He/4He and 4He/20Ne ratios vary from 0.000000215 to 0.00000165 and from 0.29 to 20, respectively. He in the sample is composed of four components: (1) atmospheric He dissolved in seawater; (2) atmospheric He with mantle-derived He in Pacific bottom water; (3) in situ radiogenic He in the sediment; and (4) crustal He in the basement rock. Assuming that the 20Ne contents are constant with the value of seawater, the depth variations in the 4He/20Ne ratios at five Sites, 583D, 594, 597A, 598A and 504B, may provide useful information on 4He flux at the ocean bottom. The estimated 4He fluxes vary from 2000 to 40000 atoms cm**-2 s**-1 and are one to three orders of magnitude less than those calculated from the excess He in deep ocean water. An overall similarity between the geographical distribution of the 3He/4He ratios and heat flow data is found in the study area, between the East Pacific Rise across the Pacific Ocean and the Japanese Islands. The tendency is well explained by a conventional sea-floor spreading model.

Stable Water Isotopologue data collected during HCCT-2010

Cloud samples for the isotopic analysis were collected in the framework of the Hill Cap Cloud Thuringia 2010 (HCCT-2010) campaign on Schmücke (50° 39'N/ 10° 46'E, 937 m a.s.l.; Germany) in September and October 2010 with a three-stage Caltech Active Strand Cloudwater Collector (CASCC) during 13 different cloud events with a temporal resolution of 1 to 3 hours. In a first step, we ensured that no additional fractionation occurred during sampling with the CASCC. The d values of the three sizes classes of the CASCC (4 µm to 16 µm, 16 µm to 22 µm and >22 µm) did not differ significantly, revealing that the cloud droplets of different sizes quickly equilibrate their delta value with the one of the surrounding vapor. delta values in the cloud droplets varied from -77 per mil to -15 per mil in d2H and from -12.1 per mil to -3.9 per mil in d18O and were fitted by d2H =7.8*d18O +13*10**-3. delta values decreased with temperature as well as towards the end of the campaign, representing a seasonal trend which is known from d values in precipitation. The deuterium excess of the cloud samples was generally higher than the Local Meteoric Water Line of the closest GNIP (Global Network of Isotopes in Precipitation) station. Rain decreases its deuterium excess during falling through an unsaturated air column, while the cloud droplets conserve the deuterium excess of the initial evaporation and thus have been found to be a good indicator for the airmass source region: higher deuterium excess was measured for polar air masses and lower deuterium excess for Mediterranean air masses. Changes in d values during one cloud event were up to 3.6 per mil (d2H) and 0.23 per mil (d18O), except for frontal passages, which were associated with increases of ~6 per mil per hour (d2H) and ~0.6 per mil per hour (d18O). Using a box model, we showed that the influence of condensation only was able to explain the variation in the isotope signal of two cloud passages. Consequently, we deduced that the water vapor "feeding" the cloud advected the measured changes. A trajectory analysis and moisture source diagnostic revealed that it is very likely that the variations were either related to rain out along the trajectories or to meteorological changes in the moisture source region. This was the first study using stable water isotopologues in cloud water manifesting their potential in the context of atmospheric water vapor circulation.