Calcium carbonate content and concentration of phosphorus components in sediments of ODP Leg 171B sites

Quantifying phosphorus (P) concentrations in marine sediments is necessary for constraining the oceanic record of phosphorus burial and helps to constrain P sedimentary geochemistry. To understand P geochemistry in the sediments, we must determine the geochemical forms of P as well as the transformations occurring between these P components with depth and age. Although several records now exist of P geochemistry in the western and eastern equatorial Pacific (Filippelli and Delaney, 1995, doi:10.2973/odp.proc.sr.138.144.1995; 1996, doi:10.1016/0016-7037(96)00042-7), the western equatorial Atlantic (Delaney and Anderson, 1997, doi:10.2973/odp.proc.sr.154.124.1997), the California Current (Delaney and Anderson, in press), and the Benguela Current (Anderson et al., 2001, doi:10.1029/2000GB001270), most of these are Neogene records. Relatively little data exist from sediments of the Paleogene or Cretaceous, time periods when carbon isotope records indicate major carbon shifts and when the nature of P geochemistry has not been well constrained. Samples from several sites at various water depths, oceanographic regions, and ages are needed to understand how P geochemistry and burial in sediments reflect ocean history. We determined P geochemistry and reactive P concentrations in Atlantic sediments of Eocene to Cretaceous age. These are the first records of P geochemistry with good age control from this period. Blake Nose sites are ideal for investigating P geochemistry, as the sediments are shallowly buried at a range of water depths and sedimentation rates. We determined P concentrations and geochemistry, along with calcium carbonate contents, in mid-Cretaceous to upper Eocene sediments drilled on Blake Nose (Ocean Drilling Program Leg 171B) in a depth transect of four sites (Sites 1052, 1051, 1050, and 1049; water depths: 1345, 1983, 2300, and 2656 m, respectively).

Temporal evolution of organic carbon and lipid content and derived SST of sediment core GIK23258-2, Norwegian Sea

Lipids are used for the evaluation of the different organic matter contributions in the north eastern Norwegian sea (M23258 site; 75ºN, 14ºE) over the last 15,000 years. Development of a mass balance model based on the down core quantification of the C37 alkenones, the odd carbon numbered n-alkanes (Aodd) and the unresolved complex mixture of hydrocarbons (UCM) has allowed three main organic matter inputs involving marine, continental and ancient reworked organic matter to be recognized. The model shows a good agreement between measured and reconstructed TOC values. Similarly, a strong parallelism is observed between predicted components such as marine TOC and carbonate content (CaCO3), which was determined independently. Representation of the model results within a time-scale based on 15 AMS-14C measurements shows that the main changes in organic matter constituents are coincident with the major climatic events of the last 15,000 a. Thus, the predominance of reworked organic matter is characteristic of Termination Ia (up to 70%), continental organic matter was dominant during the Bølling-Allerød (B-A) and Younger Dryas (YD) periods (about 85%) and a strong increase of marine organic matter occurred in the Holocene (between 50 and 75%). This agreement reflects the main hydrographic changes that determined the deposition of sedimentary materials during the period studied: ice-rafted detritus from the Barents continental platform, ice-melting waters from the Arctic fluvial system discharging into the Barents sea and dominance of north Atlantic currents, respectively. In this respect, the high-resolution down core record resulting from the mass balance and lipid measurements allows the identification of millennial-scale events such as the increase of reworked organic matter at the final retreat of the Barents ice sheet at the end of the deglaciation period (Termination Ib).

Measurements of trace metal abundances and isotopes in carbonate sediments, Exuma, Bahamas

In order to validate the use of 238U/235U as a paleoredox proxy in carbonates, we examined the incorporation and early diagenetic evolution of U isotopes in shallow Bahamian carbonate sediments. Our sample set consists of a variety of primary precipitates that represent a range of carbonate producing organisms and components that were important in the past (scleractinian corals, calcareous green and red algae, ooids, and mollusks). In addition, four short push cores were taken in different depositional environments to assess the impact of early diagenesis and pore water chemistry on the U isotopic composition of bulk carbonates. We find that U concentrations are much higher in bulk carbonate sediments (avg. 4.1 ppm) than in primary precipitates (avg. 1.5 ppm). In almost all cases, the lowest bulk sediment U concentrations were as high as or higher than the highest concentrations found in primary precipitates. This is consistent with authigenic accumulation of reduced U(IV) during early diagenesis. The extent of this process appears sensitive to pore water H2S, and thus indirectly to organic matter content. d238/235U values were very close to seawater values in all of the primary precipitates, suggesting that these carbonate components could be used to reconstruct changes in seawater U geochemistry. However, d238/235U of bulk sediments from the push cores was 0.2-0.4 per mil heavier than seawater (and primary precipitates). These results indicate that authigenic accumulation of U under open-system sulfidic pore water conditions commonly found in carbonate sediments strongly affects the bulk U concentrations and 238U/235U ratios. We also report the occurrence of dolomite in a tidal pond core which contains low 234U/238U and 238U/235U ratios and discuss the possibility that the dolomitization process may result in sediments depleted in 238U. From this initial exploration, it is clear that 238U/235U variations in ancient carbonate sediments could be driven by changes in global average seawater, by spatial and temporal variations in the local deposition environment, or subsequent diagenesis. To cope with such effects, proxies for syndepositional pore water redox conditions (e.g., organic matter content, iron speciation, and trace metal distributions) and careful consideration of possible post-deposition alteration will be required to avoid spurious interpretation of 238U/235U data from ancient carbonate sediments.

Stable oxygen isotope ratios of pore waters from ODP Leg 166 sites

This study investigates the d18O of pore waters from Sites 1003 through 1007, drilled along the western margin of the Great Bahama Bank during Leg 166 of the Ocean Drilling Program. These pore waters generally show a positive correlation between d18O and the concentration of chloride. The exception to this trend is Site 1006, where the pore waters exhibit nonlinear behavior with respect to chloride. The correlation between the concentration of Cl- and d18O at most of the sites appears to be a coincidence because although the increase in Cl- is a result of diffusion from an underlying source, the increases in d18O result from the recrystallization of metastable carbonates in the presence of a geothermal gradient. The difference in behavior in the d18O of the pore water at Site 1006 is probably a result of the relative reduced rate of carbonate recrystallization at this site. The d18O of the pore waters in the upper portion of the cores shows a pattern similar to the concentration of chloride in that there is an interval of 30-50 m in which neither the d18O nor the concentration of Cl- changes. This interval is consistent with either an interval of very rapid deposition of sediment or the advection of fluid through the platform. Both the d18O and the concentration of Cl- increase toward the platform, suggesting an input of saline and isotopically heavy water from the platform surface.

Carbonate, organic carbon, pyrolysis and composition of the extracts at DSDP Holes 76-534A and 44-391

The geochemical studies of Sites 534 and 391 and their comparison allow us to improve the chemical characterization of different geological formations dating from the early Callovian to the Maestrichtian along the continental margin of eastern North America. Three of the formations are favorable for the preservation of organic matter: (1) the unnamed formation (middle Callovian to Oxfordian), (2) the Blake-Bahama Formation (Berriasian to Barremian), and (3) the Hatteras Formation (Aptian to Cenomanian). The organic matter is mainly detrital, except for a few organic-rich layers where a contribution of aquatic material occurs. In these organic-rich layers, the petroleum potential is medium to good. Maturation has not quite reached the beginning of the oil window even for the deepest organic material.

Calcium carbonate, isotopes and Rock-Eval pyrolysis at DSDP Holes 77-535 and 77-540

At DSDP Sites 534 (Central Atlantic) and 535 and 540 (Gulf of Mexico), and in the Vocontian Basin (France), Lower Cretaceous deposits show a very pronounced alternation of limestone and marl. This rhythm characterizes the pelagic background sedimentation and is independent of detritic intercalations related to contour and turbidity currents. Bed-scale cycles, estimated to be 6000-26,000 yr. long, comprise major and minor units. Their biological and mineralogic components, burrowing, heavy isotopes C and O, and some geochemical indicators, vary in close correlation with CaCO3 content. Vertical changes of frequency and asymmetry of the cycles are connected with fluctuations of the sedimentation rate. Plots of cycle thickness ("cyclograms") permit detailed correlations of the three areas and improve the stratigraphic subdivision of Neocomian deposits at the DSDP sites. Small-scale alternations, only observed in DSDP cores, comprise centimetric to millimetric banding and millimetric to micrometric lamination, here interpreted as varvelike alternations between laminae that are rich in calcareous plankton and others rich in clay. The laminations are estimated to correspond to cycles approximately 1,3, and 13 yr. in duration. The cyclic patterns appear to be governed by an interplay of continental and oceanic processes. Oceanic controls express themselves in variations of the biogenic carbonate flux, which depends on variations of such elements as temperature, oxygenation, salinity, and nutrient content. Continental controls modulate the influxes of terrigenous material, organic matter, and nutrients derived from cyclic erosion on land. Among the possible causes of cyclic sedimentation, episodic carbonate dissolution has been ruled out in favor of climatic fluctuations with a large range of periods. Such fluctuations are consistent with the great geographic extension shown by alternation controls and with the continuous spectrum of scales that characterizes limestone-marl cycles. The climatic variations induced by the Earth's orbital parameters (Milankovitch cycles) could be connected to bed-interbed alternations.

Stable isotopes and calcium carbonate at DSDP Holes 85-574 and 85-574A

Detailed stable isotopic and calcium carbonate records (with a sampling resolution of 3000 yr.) from the middle Miocene section of hydraulic piston corer (HPC) Hole 574A provide a sequence that records the major shift in the oxygen isotopic composition of the world's oceans that occurred at about 14 Ma. The data suggest that this transition was rapid and spans about 30,000 yr. of sediment deposition. In intervals before and after the shift, the mean d18O values are characterized by a constant mean with a high degree of variability. The degree of variability in both the d18O and d13C records is comparable to that observed for the Pliocene and earliest Pleistocene and does not show a significant change before or after the major shift in the d18O record. Whereas the oxygen isotopic record is characterized by relatively stable mean values before and after the middle Miocene event, the d13C record shows a number of significant offsets in the mean value separated by intervals of high-frequency variations. Time and frequency domain analysis of all records from Hole 574A indicate that the frequency components shown to be related to orbital changes in the Pleistocene record are also present in the middle Miocene. The high variability observed in the Site 574 isotopic records places important constraints on models describing the role of formation of the Antarctic ice sheet during the middle Miocene climatic transitions. Thus, HPC Hole 574A provides a valuable sequence for detailed study of climatic variability during an important time in the Earth's history, although we cannot provide a definitive explanation of the major oxygen isotopic event of the middle Miocene.

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.

Grain-size distribution, carbon and calcium carbonate at DSDP Leg 63 Holes

Sand-silt-clay distribution was determined at Scripps on samples collected at the time the cores were split and described. The sediment classification used here is that of Shepard (1954); sand, silt, and clay boundaries are determined on the basis of the Wentworth (1922) scale. Thus the sand, silt, and clay fractions are composed of particles whose diameters range from 2000 to 62.5 µm, 62.5 to 3.91 µm, and less than 3.91 µm, respectively. This classification is applied regardless of sediment type and origin.

Elemental contents, non-carbonate, fatty acids and alcohols analysis from different Holes of IODP Expedition 310

During IODP Expedition 310 (Tahiti Sea Level), drowned Pleistocene-Holocene barrier-reef terraces were drilled on the slope of the volcanic island. The deglacial reef succession typically consists of a coral framework encrusted by coralline algae and later by microbialites; the latter make up < 80% of the rock volume. Lipid biomarkers were analyzed in order to identify organisms involved in reef-microbialite formation at Tahiti, as the genesis of deglacial microbialites and the conditions favoring their formation are not fully understood. Sterols plus saturated and monounsaturated short-chain fatty acids predominantly derived from both marine primary producers (algae) and bacteria comprise 44 wt% of all lipids on average, whereas long-chain fatty acids and long-chain alcohols derived from higher land plants represent an average of only 24 wt%. Bacterially derived mono-O-alkyl glycerol ethers (MAGEs) and branched fatty acids (10-Me-C16:0; iso- and anteiso-C15:0 and -C17:0) are exceptionally abundant in the microbial carbonates (average, 19 wt%) and represent biomarkers of intermediate-to-high specificity for sulfate-reducing bacteria. Both are relatively enriched in 13C compared to eukaryotic lipids. No lipid biomarkers indicative of cyanobacteria were preserved in the microbialites. The abundances of Al, Si, Fe, Mn, Ba, pyroxene, plagioclase, and magnetite reflect strong terrigenous influx with Tahitian basalt as the major source. Chemical weathering of the basalt most likely elevated nutrient levels in the reefs and this fertilization led to an increase in primary production and organic matter formation, boosting heterotrophic sulfate reduction. Based on the observed biomarker patterns, sulfate-reducing bacteria were apparently involved in the formation of microbialites in the coral reefs off Tahiti during the last deglaciation.

Changes in bottom water corrosiveness and carbonate ion concentrations in the sub-Antarctic Atlantic during the last glacial period

The glacial climate system transitioned rapidly between cold (stadial) and warm (interstadial) conditions in the Northern Hemisphere. This variability, referred to as Dansgaard-Oeschger variability, is widely believed to arise from perturbations of the Atlantic Meridional Overturning Circulation. Evidence for such changes during the longer Heinrich stadials has been identified, but direct evidence for overturning circulation changes during Dansgaard-Oeschger events has proven elusive. Here we reconstruct bottom water [CO3]2- variability from B/Ca ratios of benthic foraminifera and indicators of sedimentary dissolution, and use these reconstructions to infer the flow of northern-sourced deep water to the deep central sub-Antarctic Atlantic Ocean. We find that nearly every Dansgaard-Oeschger interstadial is accompanied by a rapid incursion of North Atlantic Deep Water into the deep South Atlantic. Based on these results and transient climate model simulations, we conclude that North Atlantic stadial-interstadial climate variability was associated with significant Atlantic overturning circulation changes that were rapidly transmitted across the Atlantic. However, by demonstrating the persistent role of Atlantic overturning circulation changes in past abrupt climate variability, our reconstructions of carbonate chemistry further indicate that the carbon cycle response to abrupt climate change was not a simple function of North Atlantic overturning.