Studies of the microbial diversity on analyzed samples from from Peru Margin, Equatorial Pacific, Hydrate Ridge, and Juan de Fuca Ridge

Marine sediments harbor an enormous quantity of microorganisms, including a multitude of novel species. The habitable zone of the marine sediment column begins at the sediment-water interface and probably extends to depths of several thousands of meters. Studies of the microbial diversity in this ecosystem have mostly relied on molecular biological techniques. We used a complementary method - analysis of intact polar membrane lipids - to characterize the in-situ microbial community in sediments covering a wide range of environmental conditions from Peru Margin, Equatorial Pacific, Hydrate Ridge, and Juan de Fuca Ridge. Bacterial and eukaryotic phospholipids were only detected in surface sediments from the Peru Margin. In contrast, deeply buried sediments, independent of their geographic location, were dominated by archaeal diether and tetraether lipids with various polar head groups and core lipids. We compared ring distributions of archaeal tetraether lipids derived from polar glycosidic precursors with those that are present as core lipids. The distributions of these related compound pools were distinct, suggestive of different archaeal sources, i.e., the polar compounds derive from sedimentary communities and the core lipids are fossil remnants from planktonic communities with possible admixtures of decayed sedimentary archaea. This in-situ production of distinct archaeal lipid populations potentially affects applications of the TEX86 paleotemperature proxy as demonstrated by offsets in reconstructed temperatures between both pools. We evaluated how varying cell and lipid stabilities will influence the sedimentary pool by using a box-model. The results are consistent with (i) a requirement of continuous inputs of freshly synthesized lipids in subsurface sediments for explaining the observed distribution of intact polar lipids, and (ii) decreasing lipid inputs with increasing burial depth.

Stable oxygen isotope record of epibenthic foraminifera and water samples of the Arctic Ocean

We determined d18OCib values of live (Rose Bengal stained) and dead epibenthic foraminifera Cibicidoides wuellerstorfi, Cibicides lobatulus, and Cibicides refulgens in surface sediment samples from the Arctic Ocean and the Greenland, Iceland, and Norwegian seas (Nordic Sea). This is the first time that a comprehensive d18OCib data set is generated and compiled from the Arctic Ocean. For comparison, we defined Atlantic Water (AW), upper Arctic Bottom Water (uABW), and Arctic Bottom Water (ABW) by their temperature/salinity characteristics and calculated mean equilibrium calcite d18Oequ from summer sea-water d18Ow and in situ temperatures. As a result, in the Arctic environment we compensate for Cibicidoides- and Cibicides-specific offsets from equilibrium calcite of -0.35 and -0.55 per mil, respectively. After this taxon-specific adjustment, mean d18OCib values plausibly reflect the density stratification of principle water masses in the Nordic Sea and Arctic Ocean. In addition, mean d18OCib from AW not only significantly differs from mean d18OCib from ABW, but also d18OCib from within AW differentiates in function of provenience and water mass age. Furthermore, in shallow waters brine-derived low d18Ow can significantly lower the d18OCib of Cibicides spp. and thus d18OCib may serve as a paleobrine indicator. There is no statistically significant difference, however, between deeper water masses mean d18OCib of the Nordic Sea, and of the Eurasian and Amerasian basins, and no influence of low-d18Ow brines is recorded in Recent uABW and ABW d18OCib of C. wuellerstorfi. This may be due to dilution of a low-d18Ow brine signal in the deep sea, and/or to preferential incorporation of relatively high-d18Ow brines from high-salinity shelves. Although our data encompass environments with seasonal sea-ice and brine formation supposed to ultimately ventilate the deep Arctic Ocean, d18OCib from uABW and ABW do not indicate negative excursions. This may challenge hypotheses that call for enhanced Arctic brine release to explain negative benthic d18O spikes in deep-sea sediments from the late Pleistocene North Atlantic Ocean.

INTCAL98

The focus of this paper is the conversion of radiocarbon ages to calibrated (cal) ages for the interval 24,00-0 cal BP (Before Present, 0 cal BP = AD 1950), based upon a sample set of dendrochronologically dated tree rings, uranium-thorium dated corals, and varve-counted marine sediment. The 14C age-cal age information, produced by many laboratories, is converted to 14C profiles and calibration curves, for the atmosphere as well as the oceans. We discuss offsets in measured 14C ages and the errors therein, regional 14C age diferences, tree-coral 14C age comparisons and the time dependence of marine reservoir ages, and evaluate decadal vs. single-year 14C results. Changes in oceanic deepwater circulation, especialy for the 16,00-1,00 cal BP interval, are reflected in the Delta14C values of INTCAL98.

Grain entrainment and transport rates of magnetic minerals of coastal sediment samples from the Bay of Plenty, New Zealand

Heavy (magnetic & non-magnetic) minerals are found concentrated by natural processes in many fluvial, estuarine, coastal and shelf environments with a potential to form economic placer deposits. Understanding the processes of heavy mineral transport and enrichment is prerequisite to interpret sediment magnetic properties in terms of hydro- and sediment dynamics. In this study, we combine rock magnetic and sedimentological laboratory measurements with numerical 3D discrete element models to investigate differential grain entrainment and transport rates of magnetic minerals in a range of coastal environments (riverbed, mouth, estuary, beach and near-shore). We analyzed grain-size distributions of representative bulk samples and their magnetic mineral fractions to relate grain-size modes to respective transport modes (traction, saltation, suspension). Rock magnetic measurements showed that distribution shapes, population sizes and grain-size offsets of bulk and magnetic mineral fractions hold information on the transport conditions and enrichment process in each depositional environment. A downstream decrease in magnetite grain size and an increase in magnetite concentration was observed from riverine source to marine sink environments. Lower flow velocities permit differential settling of light and heavy mineral grains creating heavy mineral enriched zones in estuary settings, while lighter minerals are washed out further into the sea. Numerical model results showed that higher heavy mineral concentrations in the bed increased the erosion rate and enhancing heavy mineral enrichment. In beach environments where sediments contained light and heavy mineral grains of equivalent grain sizes, the bed was found to be more stable with negligible amount of erosion compared to other bed compositions. Heavy mineral transport rates calculated for four different bed compositions showed that increasing heavy mineral content in the bed decreased the transport rate. There is always a lag in transport between light and heavy minerals which increases with higher heavy mineral concentration in all tested bed compositions. The results of laboratory experiments were validated by numerical models and showed good agreement. We demonstrate that the presented approach bears the potential to investigate heavy mineral enrichment processes in a wide range of sedimentary settings.

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.

Magnesium/Calcium ratios measured on planktonic foraminifera of the LGM

As part of the Multi-proxy Approach for the Reconstruction of the Glacial Ocean (MARGO) incentive, published and unpublished temperature reconstructions for the Last Glacial Maximum (LGM) based on planktonic foraminiferal Mg/Ca ratios have been synthesised and made available in an online database. Development and applications of Mg/Ca thermometry are described in order to illustrate the current state of the method. Various attempts to calibrate foraminiferal Mg/Ca ratios with temperature, including culture, trap and core-top approaches have given very consistent results although differences in methodological techniques can produce offsets between laboratories which need to be assessed and accounted for where possible. Dissolution of foraminiferal calcite at the sea-floor generally causes a lowering of Mg/Ca ratios. This effect requires further study in order to account and potentially correct for it if dissolution has occurred. Mg/Ca thermometry has advantages over other paleotemperature proxies including its use to investigate changes in the oxygen isotopic composition of seawater and the ability to reconstruct changes in the thermal structure of the water column by use of multiple species from different depth and or seasonal habitats. Presently available data are somewhat limited to low latitudes where they give fairly consistent values for the temperature difference between Late Holocene and the LGM (2-3.5 °C). Data from higher latitudes are more sparse, and suggest there may be complicating factors when comparing between multi-proxy reconstructions.

Calibration and application of B/Ca, Cd/Ca, and d11B in Neogloboquadrina pachyderma (sinistral)

The North Atlantic and Norwegian Sea are prominent sinks of atmospheric CO2 today, but their roles in the past remain poorly constrained. In this study, we attempt to use B/Ca and d11B ratios in the planktonic foraminifera Neogloboquadrina pachyderma (sinistral variety) to reconstruct subsurface water pH and pCO2 changes in the polar North Atlantic during the last deglaciation. Comparison of core-top results with nearby hydrographic data shows that B/Ca in N. pachyderma (s) is mainly controlled by seawater [B(OH)4]?/[HCO3]? with a roughly constant partition coefficient (KD =([B/Ca]of CaCO3)/([B(OH)4]-/[HCO3]-)of seawater) of 1.48 ± 0.15 * 10**-3 (2sigma), and d11B in this species is offset below d11B of the borate in seawater by 3.38 ± 0.71 per mil (2sigma). These values represent our best estimates with the sparse available hydrographic data close to our core-tops. More culturing and sediment trap work is needed to improve our understanding of boron incorporation into N. pachyderma (s). Application of a constant KD of 1.48 * 10**-3 to high resolution N. pachyderma (s) B/Ca records from two adjacent cores off Iceland shows that subsurface pCO2 at the habitat depth of N. pachyderma (s) (~50 m) generally followed the atmospheric CO2 trend but with negative offsets of ~10-50 ppmv during 19-10 ka. These B/Ca-based reconstructions are supported by independent estimates from low-resolution d11B measurements in the same cores. We also calibrate and apply Cd/Ca in N. pachyderma (s) to reconstruct nutrient levels for the same down cores. Like today's North Atlantic, past subsurface pCO2 variability off Iceland was significantly correlated with nutrient changes that might be linked to surface nutrient utilization and mixing within the upper water column. Because surface pCO2 (at 0 m water depth) is always lower than at deeper depths and if the application of a constant KD is valid, our results suggest that the polar North Atlantic has remained a CO2 sink during the calcification seasons of N. pachyderma (s) over the last deglaciation.

Neptunian dikes and their fillings in carbonates of the Warstein area (northeastern Rhenish massif)

Neptunian dikes and cavities as weil as their fillings are described from Middle to Upper Devonian carbonates of the Warstein area. The genesis of the pre-Upper Carboniferous dikes is due to pre-orogenic synsedimentary tensional movements. Lifting, subsidence and tilting caused joints and cracks, which are enlarged to dikes and cavities on submarine conditions. The post-Upper Carboniferous dikes are based on the orogenesis during Upper Carboniferous time, causing numerous tectonical divisional planes in the sediments. Along these planes a far-reaching karstification took place since mesozoic time. According to their size the cavities are subdivided into macro-, mega- and microdikes. With the exception of one macrodike all the others are limited to the massive limestone. Megadikes especially occur in Upper Devonian cephalopod limestone and in the Erdbach limestone, microdikes can be found in all carbonatic rocks. The dikes follow pre-orogenic, tectonical and sedimentary divisional planes and are orientated to ac-, bc- as well as bedding planes and diagonal directions. The fillings happened down from above either in a solitary event or repeatedly in long-lived dikes during a span of several ten millions of years. More seldom the fillings took place laterally or upside from beneath. The dikes contain - without regard to autochthonous conodont faunas - older and/or younger mixed faunas, too. Occasionally they were used as life district by a trilobite fauna adapted to the dikes. The dikes represent sedimentary pitfalls and conserve sediments eroded in other places. Therefore, by aid of the fillings, it can be demonstrated, that stratigraphic gaps are not absolutely due to primary interruptions of sedimentation, but were caused by reworking. Some dikes contain the distal offsets of slides and suspension streams. Relations between condensation and development of dikes could not be derived in the Warstein area. However, an increase of the frequency of dikes towards east to the eastern margin of the Warstein carbonate platform could be pointed out. This margin is a slope, persisting more than 10 millions of years, between a block and a basin. Evidently cracks and dikes, which were caused by settlements, slides and earth quakes, occured there frequently. The Warstein dikes and cavities, caused by karstification, are filled with terrestrial Lower Cretaceous, marine Upper Cretaceous and terrestrial Pleistocene to Holocene sediments. Tertiary sediments could not be detected.

Age determination of sediment cores from the northern Mid-Atlantic Ridge

We construct age models for a suite of cores from the northeast Atlantic Ocean by means of accelerator mass spectrometer dating of a key core, BOFS 5K, and correlation with the rest of the suite. The effects of bioturbation and foraminiferal species abundance gradients upon the age record are modeled using a simple equation. The degree of bioturbation is estimated by comparing modeled profiles with dispersal of the Vedde Ash layer in core 5K, and we find a mixing depth of roughly 8 cm for sand-sized material. Using this value, we estimate that age offsets between unbioturbated sediment and some foraminifera species after mixing may be up to 2500 years, with lesser effect on fine carbonate (< 10 µm) ages. The bioturbation model illustrates problems associated with the dating of 'instantaneous' events such as ash layers and the 'Heinrich' peaks of ice-rafted detritus. Correlations between core 5K and the other cores from the BOFS suite are made on the basis of similarities in the downcore profiles of oxygen and carbon isotopes, magnetic susceptibility, water and carbonate content, and via marker horizons in X radiographs and ash beds.

Automated composite depth scale reconstruction of ODP Leg 138 and 154 sites

A composite section, which reconstructs a continuous stratigraphic record from cores of multiple nearby holes, and its associated composite depth scale are important tools for analyzing sediment recovered from a drilling site. However, the standard technique for creating composite depth scales on drilling cruises does not correct for depth distortion within each core. Additionally, the splicing technique used to create composite sections often results in a 10-15% offset between composite depths and measured drill depths. We present a new automated compositing technique that better aligns stratigraphy across holes, corrects depth offsets, and could be performed aboard ship. By analyzing 618 cores from seven Ocean Drilling Program (ODP) sites, we estimate that ?80% of the depth offset in traditional composite depth scales results from core extension during drilling and extraction. Average rates of extension are 12.4 ± 1.5% for calcareous and siliceous cores from ODP Leg 138 and 8.1 ± 1.1% for calcareous and clay-rich cores from ODP Leg 154. Also, average extension decreases as a function of depth in the sediment column, suggesting that elastic rebound is not the dominant extension mechanism.

Deep water formation in the North Pacific and deglacial CO2 rise

Deep water formation in the North Atlantic and Southern Ocean is widely thought to influence deglacial CO2 rise and climate change; here we suggest that deep water formation in the North Pacific may also play an important role. We present paired radiocarbon and boron isotope data from foraminifera from sediment core MD02-2489 at 3640 m in the North East Pacific. These show a pronounced excursion during Heinrich Stadial 1, with benthic-planktic radiocarbon offsets dropping to ~350 years, accompanied by a decrease in benthic d11B. We suggest this is driven by the onset of deep convection in the North Pacific, which mixes young shallow waters to depth, old deep waters to the surface, and low-pH water from intermediate depths into the deep ocean. This deep water formation event was likely driven by an increase in surface salinity, due to subdued atmospheric/monsoonal freshwater flux during Heinrich Stadial 1. The ability of North Pacific Deep Water (NPDW) formation to explain the excursions seen in our data is demonstrated in a series of experiments with an intermediate complexity Earth system model. These experiments also show that breakdown of stratification in the North Pacific leads to a rapid ~30 ppm increase in atmospheric CO2, along with decreases in atmospheric d13C and D14C, consistent with observations of the early deglaciation. Our inference of deep water formation is based mainly on results from a single sediment core, and our boron isotope data are unavoidably sparse in the key HS1 interval, so this hypothesis merits further testing. However we note that there is independent support for breakdown of stratification in shallower waters during this period, including a minimum in d15N, younging in intermediate water 14C, and regional warming. We also re-evaluate deglacial changes in North Pacific productivity and carbonate preservation in light of our new data, and suggest that the regional pulse of export production observed during the Bølling-Allerød is promoted by relatively stratified conditions, with increased light availability and a shallow, potent nutricline. Overall, our work highlights the potential of NPDW formation to play a significant and hitherto unrealized role in deglacial climate change and CO2 rise.

Geochemistry of planktonic foraminifera of sediment core MD97-2121

In situ measurements of Mg/Ca, Zn/Ca, Mn/Ca, and Ba/Ca in Globigerinoides bulloides and Globigerina ruber from southwest Pacific core top sites and plankton tow are reported and their potential as paleoproxies is explored. The modern samples cover 20° of latitude from 34°S to 54°S, 7-19°C water temperature, and variable influence of subantarctic (SAW) and subtropical (STW) surface waters. Trace element signatures recorded in core top and plankton tow planktic foraminifera are examined in the context of the chemistry and nutrient profiles of their modern water masses. Our observations suggest that Zn/Ca and Mn/Ca may have the potential to trace SAW and STW. Intraspecies and interspecies offsets identified by in situ measurements of Mg/Ca and Zn/Ca indicate that these ratios may also record changes in thermal and nutrient stratification in the upper ocean. We apply these potential proxies to fossilized foraminifera from the high-resolution core MD97 2121. At the Last Glacial Maximum, surface water Mg/Ca temperature estimates indicate that temperatures were approximately 6-7°C lower than those of the present, accompanied by low levels of Mn/Ca and Zn/Ca and minimal thermal and nutrient stratification. This is consistent with regional dominance of SAW and reduced STW inflow associated with a reduced South Pacific Gyre (SPG). Upper ocean thermal and nutrient stratification collapsed during the Antarctic Cold Reversal, before poleward migration of the zonal winds and ocean fronts invigorated the SPG and increased STW inflow in the early Holocene. Together with reduced winds, this favored a stratified upper ocean from circa 10 ka to the present.

Geochemistry of sediment cores from METEOR cruise M76/1b

Marine sediments are the main sink in the oceanic phosphorus (P) cycle. The activity of benthic microorganisms is decisive for regeneration, reflux, or burial of inorganic phosphate (Pi), which has a strong impact on marine productivity. Recent formation of phosphorites on the continental shelf and a succession of different sedimentary environments make the Benguela upwelling system a prime region for studying the role of microbes in P biogeochemistry. The oxygen isotope signature of pore water phosphate (d18OP) carries characteristic information of microbial P cycling: Intracellular turnover of phosphorylated biomolecules results in isotopic equilibrium with ambient water, while enzymatic regeneration of Pi from organic matter produces distinct offsets from equilibrium. The balance of these two processes is the major control for d18OP. Our study assesses the importance of microbial P cycling relative to regeneration of Pi from organic matter from a transect across the Namibian continental shelf and slope by combining pore water chemistry (sulfate, sulfide, ferrous iron, Pi), steady-state turnover rate modeling, and oxygen isotope geochemistry of Pi. We found d18OP values in a range from 12.8 per mill to 26.6 per mill, both in equilibrium as well as pronounced disequilibrium with water. Our data show a trend towards regeneration signatures (disequilibrium) under low mineralization activity and low Pi concentrations, and microbial turnover signatures (equilibrium) under high mineralization activity and high Pi concentrations. These findings are opposite to observations from water column studies where regeneration signatures were found to coincide with high mineralization activity and high Pi concentrations. It appears that preferential Pi regeneration in marine sediments does not necessarily coincide with a disequilibrium d18OP signature. We propose that microbial Pi uptake strategies, which are controlled by Pi availability, are decisive for the alteration of the isotope signature. This hypothesis is supported by the observation of efficient microbial Pi turnover (equilibrium signatures) in the phosphogenic sediments of the Benguela upwelling system.

Core alignment and composite depth scale of DSDP Site 86-577

Deep Sea Drilling Project Site 577 on Shatsky Rise (North Pacific Ocean) recovered a series of cores at three holes that contain calcareous nannofossil ooze of latest Cretaceous (late Maastrichtian) through early Eocene age. Several important records have been generated using samples from these cores, but the stratigraphy has remained outdated and confusing. Here we revise the stratigraphy at Site 577. This includes refining several age datums, realigning cores in the depth domain, and placing all stratigraphic markers on a current time scale. The work provides a template for appropriately bringing latest Cretaceous and Paleogene data sets at old drill sites into current paleoceanographic literature for this time interval. While the Paleocene Eocene Thermal Maximum (PETM) lies within core gaps at Holes 577* and 577A, the sedimentary record at the site holds other important events and remains crucially relevant to understanding changes in oceanographic conditions from the latest Cretaceous through early Paleogene.

Sr/Ca ratios of Cenozoic benthic foraminifera

A Cenozoic multi-species record of benthic foraminiferal calcite Sr/Ca has been produced and is corrected for interspecific offsets (typically less than 0.3 mmol/mol) and for the linear relationship between decreasing benthic foraminiferal Sr/Ca and increasing water depth. The water depth correction, determined from Holocene, Late Glacial Maximum and Eocene paleowater-depth transects, is ~0.1 mmol/mol/km. The corrected Cenozoic benthic foraminiferal Sr/Ca record ranges from 1.2 to 2.0 mmol/mol, and has been interpreted in terms of long-term changes in seawater Sr/Ca, enabling issues related to higher-resolution variability in Sr/Ca to be ignored. We estimate that seawater Sr/Ca was ~1.5 times modern values in the late Cretaceous, but declined rapidly into the Paleogene. Following a minimum in the Eocene, seawater Sr/Ca increased gradually through to the present day with a minimum superimposed on this trend centered in the late Miocene. By assuming scenarios for changing seawater calcium concentration, and using published carbonate accumulation rate data combined with suitable values for Sr partition coefficients into carbonates, the seawater Sr/Ca record is used to estimate global average river Sr fluxes. These fluxes are used in conjunction with the seawater strontium isotope curve and estimates of hydrothermal activity/tectonic outgassing to calculate changes in global average river 87Sr/86Sr through the Cenozoic. The absolute magnitude of Sr fluxes and isotopic compositions calculated in this way are subject to relatively large uncertainties. Nevertheless, our results suggest that river Sr flux increased from 35 Ma to the present day (roughly two-fold) accompanied by an overall increase in 87Sr/86Sr (by ~0 to 0.001). Between 75 and 35 Ma, river 87Sr/86Sr also increased (by ~0.001 to 0.002) but was accompanied by a decrease (two- to three-fold) in river Sr flux.