Magnesium/Calcium ratios and sea surface temperature estimation for sediments of the Timor Sea

We use a multiproxy approach to monitor changes in the vertical profile of the Indonesian Throughflow as well as monsoonal wind and precipitation patterns in the Timor Sea on glacial-interglacial, precessional, and suborbital timescales. We focus on an interval of extreme climate change and sea level variation: marine isotope (MIS) 6 to MIS 5e. Paleoproductivity fluctuations in the Timor Sea follow a precessional beat related to the intensity of the Australian (NW) monsoon. Paired Mg/Ca and d18O measurements of surface- and thermocline-dwelling planktonic foraminifers (G. ruber and P. obliquiloculata) indicate an increase of >4°C in both surface and thermocline water temperatures during Termination II. Tropical sea surface temperature changed synchronously with ice volume (benthic d18O) during deglaciation, implying a direct coupling of high- and low-latitude climate via atmospheric and/or upper ocean circulation. Substantial cooling and freshening of thermocline waters occurred toward the end of Termination II and during MIS 5e, indicating a change in the vertical profile of the Indonesian Throughflow from surface- to thermocline-dominated flow.

Feldspar Pb-isotope ratios for earliest Pleistocene sediments of the sub-polar North Atlantic Ocean

Relatively little is known in detail about the locations of the early Pleistocene ice-sheets responsible for ice-rafted debris (IRD) inputs to the sub-polar North Atlantic Ocean during intensification of northern hemisphere glaciation (iNHG). To shed new light on this problem, we present the first combined in-depth analysis of IRD flux and geochemical provenance of individual sand-sized IRD deposited in the sub-polar North Atlantic Ocean during the earliest large amplitude Pleistocene glacial, marine isotope stage (MIS) 100 (~2.52 Ma), arguably the key glacial during iNHG. IRD provenance is assessed using laser ablation lead (Pb) isotope analyses of single feldspar grains. We find that the Pb-isotope composition (206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb) of individual ice-rafted (>150 µm) feldspars deposited at DSDP Site 611A, ODP Site 981 and IODP Site U1308 during MIS 100 records a shift from predominantly Archaean-aged circum-North Atlantic Ocean continental sources during early glacial ice-rafting events to dominantly Palaeozoic and Proterozoic-aged sources during full glacial conditions. The distribution of feldspars in Pb-Pb space for full glacial MIS 100 more closely resembles that documented for feldspars deposited at the centre of the last glacial IRD belt (at IODP/DSDP Site U1308/609) during ambient (non-Heinrich-event) ice-rafting episodes of MIS 2 (~23.8 ka) than that documented for MIS 5d (~106 ka). Comparison of our early Pleistocene and last glacial cycle datasets suggests that MIS 100 was characterised by abundant iceberg calving from large ice-sheets on multiple continents in the high northern latitudes (not just on Greenland).

Isotope composition of dolomite, calcite and pore-waters of ODP Leg 210 samples

Early diagenetic dolomite beds were sampled during the Ocean Drilling Programme (ODP) Leg 201 at four reoccupied ODP Leg 112 sites on the Peru continental margin (Sites 1227/684, 1228/680, 1229/681 and 1230/685) and analysed for petrography, mineralogy, d13C, d18O and 87Sr/86Sr values. The results are compared with the chemistry, and d13C and 87Sr/86Sr values of the associated porewater. Petrographic relationships indicate that dolomite forms as a primary precipitate in porous diatom ooze and siliciclastic sediment and is not replacing the small amounts of precursor carbonate. Dolomite precipitation often pre-dates the formation of framboidal pyrite. Most dolomite layers show 87Sr/86Sr-ratios similar to the composition of Quaternary seawater and do not indicate a contribution from the hypersaline brine, which is present at a greater burial depth. Also, the d13C values of the dolomite are not in equilibrium with the d13C values of the dissolved inorganic carbon in the associated modern porewater. Both petrography and 87Sr/86Sr ratios suggest a shallow depth of dolomite formation in the uppermost sediment (<30 m below the seafloor). A significant depletion in the dissolved Mg and Ca in the porewater constrains the present site of dolomite precipitation, which co-occurs with a sharp increase in alkalinity and microbial cell concentration at the sulphate-methane interface. It has been hypothesized that microbial 'hot-spots', such as the sulphate-methane interface, may act as focused sites of dolomite precipitation. Varying d13C values from -15 per mil to +15 per mil for the dolomite are consistent with precipitation at a dynamic sulphate-methane interface, where d13C of the dissolved inorganic carbon would likewise be variable. A dynamic deep biosphere with upward and downward migration of the sulphate-methane interface can be simulated using a simple numerical diffusion model for sulphate concentration in a sedimentary sequence with variable input of organic matter. Thus, the study of dolomite layers in ancient organic carbon-rich sedimentary sequences can provide a useful window into the palaeo-dynamics of the deep biosphere.

Composition of soil samples from injection location

CO2 leakage from subsurface storage sites is one of the main concerns connected with the CCS technology. As CO2 leakages into near surface formations appear to be very unlikely within pilot CCS projects, the aim of this work is to emulate a leakage by injecting CO2 into a near surface aquifer. The two main questions pursued by the injection test are (1) to investigate the impact of CO2 on the hydrogeochemistry of the groundwater as a base for groundwater risk assessment and (2) to develop and apply monitoring methods and monitoring concepts for detecting CO2 leakages in shallow aquifers. The presented injection test is planned within the second half of 2010, as a joint project of the University of Kiel (Germany), the Helmholtz-Centre for Environmental Research (Leipzig, Germany) and the Engineering Company GICON (Dresden, Germany). The test site has been investigated in detail using geophysical methods as well as direct-push soundings, groundwater well installation and soil and groundwater analyses. The present paper presents briefly the geological and hydrogeological conditions at the test site as well as the planned injection test design and monitoring concept.

Chemical composition of DSDP cherts and associated host sediments

Chert and associated host sediments from Monterey Formation and Deep Sea Drilling Project (DSDP) sequences were analyzed in order to assess chemical behavior during diagenesis of biogenic sediments. The primary compositional contrast between chert and host sediment is a greater absolute SiO2 concentration in chert, often with final SiO2 >=98 wt%. This contrast in SiO2 (and Si/Al) potentially reflects precursor sediment heterogeneity, diagenetic chemical fractionation, or both. SiO2 concentrations and Si/Al ratios in chert are far greater than in modern siliceous oozes, however and often exceed values in acid-cleaned diatom tests. Compositional contrasts between chert and host sediment are also orders-of-magnitude greater than between multiple samples of the host sediment. Calculations based on the initial composition of adjacent host, observed porosity reductions from host to chert and a postulated influx of pure SiO2, construct a chert composition which is essentially identical to observed SiO2 values in chert. Thus, precursor heterogeneity does not seem to be the dominant factor influencing the current chert composition for the key elements of interest. In order to assess the extent of chemical fractionation during diagenesis, we approximate the precursor composition by analyzing host sediments adjacent to the chert. The SiO2 concentration contrast seems caused by biogenic SiO2 dissolution and transport from the local adjacent host sediment and subsequent SiO2 reprecipitation in the chert. Along with SiO2, other elements are often added (with respect to Al) to Monterey and DSDP chert during silicification, although absolute concentrations decrease. The two Monterey quartz chert nodules investigated, in contrast to the opal-CT and quartz chert lenses, formed primarily by extreme removal of carbonate and phosphate, thereby increasing relative SiO2 concentrations. DSDP chert formed by both carbonate/phosphate dissolution and SiO2 addition from the host. Manganese is fractionated during chert formation, resulting in MnO/Al2O3 ratios that no longer record the depositional signal of the precursor sediment. REE data indicate only subtle diagenetic fractionation across the rare earth series. Ce/Ce* values do not change significantly during diagenesis of either Monterey or DSDP chert. Eu/Eu* decreases slightly during formation of DSDP chert. Normative La/Yb is affected only minimally as well. During formation of one Monterey opal-CT chert lens, REE/Al ratios show subtle distribution changes at Gd and to a lesser extent near Nd and Ho. REE compositional contrasts between diagenetic states of siliceous sediment and chert are of a vastly smaller scale than has been noted between different depositional environments of marine sediment, indicating that the paleoenvironmental REE signature is not obscured by diagenetic overprinting.

Trace element concentrations and Li isotope composition in DSDP and ODP sediments from island arcs

We have studied the sedimentary and basaltic inputs of lithium to subduction zones. Various sediments from DSDP and ODP drill cores in front of the Mariana, South Sandwich, Banda, East Sunda and Lesser Antilles island arcs have been analysed and show highly variable Li contents and d7Li values. The sediment piles in front of the Mariana and South Sandwich arcs largely consist of pelagic sediments (clays and oozes). The pelagic clays have high Li contents (up to 57.3 ppm) and Li isotope compositions ranging from +1.3? to +4.1?. The oozes have lower Li contents (7.3-16 ppm) with d7Li values of the diatom oozes from the South Sandwich lower (+2.8? to +3.2?) than those of the radiolarian oozes from the Mariana arc (+8.1? to +14.5?). Mariana sediment also contains a significant portion of volcanogenic material, which is characterised by a moderate Li content (14 ppm) and a relatively heavy isotope composition (+6.4?). Sediments from the Banda and Lesser Antilles contain considerable amounts of continental detritus, and have high Li contents (up to 74.3 ppm) and low d7Li values (around 0?), caused by weathering of continental bedrock. East Sunda sediments largely consist of calcareous oozes. These carbonate sediments display intermediate to high Li contents (2.4-41.9 ppm) and highly variable d7Li values (-1.6? to +12.8?). Basaltic oceanic crust samples from worldwide DSDP and ODP drill cores are characterised by enrichment of Li compared to fresh MORB (6.6-33.1 vs. 3.6-7.5 ppm, respectively), and show a large range in Li isotope compositions (+1.7? to +11.8?). The elemental and isotopic enrichment of Li in altered basalts is due to the uptake of isotopically heavy seawater Li during weathering. However, old oceanic crust samples from Sites 417/418 exhibit lighter Li isotope compositions compared to young basaltic crust samples from Sites 332B and 504B. This lighter Li isotope signature in old crust is unexpected and further research is needed to explore this issue.

Geochemistry and petrology of ODP Site 136-843 basalts

About 13 m of Cretaceous, tholeiitic basalt, ranging from normal (N-MORB) to transitional (T-MORB) mid-ocean-ridge basalts, was recovered at Ocean Drilling Program Site 843 west of the island of Hawaii. These moderately fractionated, aphyric lavas are probably representative of the oceanic basement on which the Hawaiian Islands were built. Whole-rock samples from parts of the cores exhibiting only slight, low-temperature, seawater alteration were analyzed for major element, trace element, and isotopic composition. The basalts are characterized by enrichment in the high field strength elements relative to N-MORB, by a distinct positive Eu anomaly, and by Ba/Nb and La/Nb ratios that are much lower than those of other crustal or mantle-derived rocks, but their isotope ratios are similar to those of present-day N-MORB from the East Pacific Rise. Hole 843A lavas are isotopically indistinguishable from Hole 843B lavas and are probably derived from the same source at a lower degree of partial melting, as indicated by lower Y/Nb and Zr/Nb ratios and by higher concentrations of light and middle rare earth elements and other incompatible elements relative to Hole 843B lavas. Petrographic and trace-element evidence indicates that the Eu anomaly was the result of neither plagioclase assimilation nor seawater alteration. The Eu anomaly and the enrichments in Ta, Nb, and possibly U and K relative to N-MORB apparently are characteristic of the mantle source. Age-corrected Nd and Sr isotopic ratios indicate that the source for the lavas recovered at ODP Site 843 was similar to the source for Southeast Pacific MORB. An enriched component within the Cretaceous mantle source of these basalts is suggested by their initial 208Pb/204Pb-206Pb/204Pb and epsilon-Nd-206Pb/204Pb ratios. The Sr-Pb isotopic trend of Hawaiian post-shield and post-erosional lavas cannot be explained by assimilation of oceanic crust with the isotopic composition of the Site 843 basalts.

Stable isotope record, Mg/Ca ratios and age model of St. Stephens Quarry, Alabama

In the largest global cooling event of the Cenozoic Era, between 33.8 and 33.5 Myr ago, warm, high-CO2 conditions gave way to the variable 'icehouse' climates that prevail today. Despite intense study, the history of cooling versus ice-sheet growth and sea-level fall reconstructed from oxygen isotope values in marine sediments at the transition has not been resolved. Here, we analyse oxygen isotopes and Mg/Ca ratios of benthic foraminifera, and integrate the results with the stratigraphic record of sea-level change across the Eocene-Oligocene transition from a continental-shelf site at Saint Stephens Quarry, Alabama. Comparisons with deep-sea (Sites 522 (South Atlantic) and 1218 (Pacific)) d18O and Mg/Ca records enable us to reconstruct temperature, ice-volume and sea-level changes across the climate transition. Our records show that the transition occurred in at least three distinct steps, with an increasing influence of ice volume on the oxygen isotope record as the transition progressed. By the early Oligocene, ice sheets were ~25% larger than present. This growth was associated with a relative sea-level decrease of approximately 105 m, which equates to a 67 m eustatic fall.

Chemical and isotope compositions of interstitial water in sediments from Mediterranean basin at DSDP Sites 42-372 and 42-374

The Br/Cl, Li/Cl and B/Cl ratios and boron isotope compositions of hypersaline pore fluids from DSDP Sites 372 and 374 were measured in an attempt to evaluate the origin of the brines. In Site 374 the relationships between the Cl concentrations (up to 5000 mM) and Br/Cl (~0.012), Na/Cl (as low as 0.1), B/Cl (0.0025), and d11B values (43-55?) of the deep pore water between 380 and 405 mbsf, located within the Messinian sediments, reflect remnants of ~65-fold evaporated sea water. The original evaporated sea water was modified by: (1) dilution with overlying or less saline water by about 30%; and (2) slight dissolution of NaCl evaporites. The variations in d11B show a continuous increase in d11B values with depth in Site 374, up to 66.7? at a depth of 300 mbsf (Upper Pliocene marl sediments). The conspicuous 11B enrichment trend is consistent with elemental boron depletion, which was calculated from the expected boron concentrations of evaporated sea water with corresponding Br/Cl and Na/Cl ratios. Li/Cl variations also show a depletion of Li relative to evaporated sea water. The apparent depletions of B and Li, as well as the 11B enrichment, reflect uptake of these elements by clay minerals at low water/sediment ratios.