Stable isotope records and biogenic barium fluxes of sediment core SO202-07-06

Reduced nitrate supply to the subarctic North Pacific (SNP) surface during the last ice age has been inferred from coupled changes in diatom-bound d15N (DB-d15N), bulk sedimentary d15N, and biogenic fluxes. However, the reliability of bulk sedimentary and DB-d15N has been questioned, and a previously reported d15N minimum during Heinrich Stadial 1 (HS1) has proven difficult to explain. In a core from the western SNP, we report the foraminifera-bound d15N (FB-d15N) in Neogloboquadrina pachyderma and Globigerina bulloides, comparing them with DB-d15N in the same core over the past 25 kyr. The d15N of all recorders is higher during the Last Glacial Maximum (LGM) than in the Holocene, indicating more complete nitrate consumption. N. pachyderma FB-d15N is similar to DB-d15N in the Holocene but 2.2 per mil higher during the LGM. This difference suggests a greater sensitivity of FB-d15N to changes in summertime nitrate drawdown and d15N rise, consistent with a lag of the foraminifera relative to diatoms in reaching their summertime production peak in this highly seasonal environment. Unlike DB-d15N, FB-d15N does not decrease from the LGM into HS1, which supports a previous suggestion that the HS1 DB-d15N minimum is due to contamination by sponge spicules. FB-d15N drops in the latter half of the Bølling/Allerød warm period and rises briefly in the Younger Dryas cold period, followed by a decline into the mid-Holocene. The FB-d15N records suggest that the coupling among cold climate, reduced nitrate supply, and more complete nitrate consumption that characterized the LGM also applied to the deglacial cold events.

(Table 1) Biostratigraphic datums of ODP Leg 133 sites

We use benthic foraminifers to reconstruct the Neogene paleobathymetric history of the Marion Plateau, Queensland Plateau, Townsville Trough, and Queensland Trough on the northeastern Australian margin (Ocean Drilling Program Leg 133). Western Queensland Plateau Site 811/825 (present depth, ~938 m) deepened from the neritic zone (0-200 m) to the upper bathyal zone (200-600 m) during the middle Miocene (~13-14 Ma), with further deepening into the middle bathyal zone (600-1000 m) occurring during the late Miocene (~7 Ma). A depth transect across the southern Queensland Plateau shows that deepening from the outer neritic zone (100-200 m) to the upper bathyal zone began during the latest Miocene (~6 Ma) at the deepest location (Site 813, present depth, 539.1 m), whereas the shallower Sites 812 and 814 (present depths, 461.6 and 520.4 m, respectively) deepened during the late Pliocene (~2.7 and ~2.9 Ma). At Marion Plateau Site 815 (present depth, 465.5 m), water depth increased during the late Miocene (~6.7 Ma) from the outer neritic to the upper bathyal zone. Nearby Site 816 (present water depth, 437.3 m) contains Pliocene upper bathyal assemblages that directly overlie middle Miocene shallow neritic deposits; the timing of the deepening is uncertain because of a late Miocene hiatus. On the northern slope of the Townsville Trough (Site 817, present depth, 1015.8 m), benthic foraminifers and sponge spicules indicate deepening from the lower upper bathyal (400-600 m) to the middle bathyal zone in the late Miocene (by ~6.8 Ma). Benthic foraminiferal faunas at nearby Site 818 (present water depth, 752.1 m) do not show evidence of paleobathymetric change; however, a late Pliocene (~2-3 Ma) increase in downslope transport may have been related to the drowning of the Queensland Plateau. Site 822 (present depth, 955.2 m), at the base of the Great Barrier Reef slope, deepened from the upper bathyal to the middle bathyal zone during the late Pliocene (by ~2.3 Ma). Queensland Trough Site 823 (present depth, 1638.4 m) deepened from the middle bathyal to the lower bathyal (1000-2000 m) zone during the late Miocene (~6.5 Ma). Benthic foraminiferal faunal changes at these Leg 133 sites indicate that rapid deepening occurred during the middle Miocene (~13-14 Ma), late Miocene (6-7 Ma), and late Pliocene (2-3 Ma) along the northeastern Australian margin.

Silicon isotope ratios of ODP Site 177-1089 and sediment core E33-22

Reconstruction of nutrient concentrations in the deep Southern Ocean has produced conflicting results. The cadmium/calcium (Cd/Ca) data set suggests little change in nutrient concentrations during the last glacial period, whereas the carbon isotope data set suggests that nutrient concentrations were higher. We determined the silicon isotope composition of sponge spicules from the Atlantic and Pacific sectors of the Southern Ocean and found higher silicic acid concentrations in the Pacific sector during the last glacial period. We propose that this increase results from changes in the stoichiometric uptake of silicic acid relative to nitrate and phosphate by diatoms, thus facilitating a redistribution of nutrients across the Pacific and Southern Oceans. Our results are consistent with the global Cd/Ca data set and support the silicic acid leakage hypothesis.

Geochemical and stable isotope composition of Middle Campanian marl-limestone rhythmites of the Lehrte West Syncline near Hannover (Lower Saxony, northern Germany)

A cyclic marl-limestone succession of Middle-Late Campanian age has been investigated with respect to a Milankovitch-controlled origin of geochemical data. In general, the major element geochemistry of the marl-limestone rhythmites can be explained by a simple two-component mixing model with the end-members calcium carbonate and 'average shale'-like material. Carbonate content varies from 55 to 90%. Non-carbonate components are clay minerals (illite, smectite) and biogenic silica from sponge spicules, as well as authigenically formed zeolites (strontian heulandite) and quartz. The redox potential suggests oxidizing conditions throughout the section. Trace element and stable isotopic data as well as SEM investigations show that the carbonate mud is mostly composed of low-magnesium calcitic tests of planktic coccolithophorids and calcareous dinoflagellate cysts (calcispheres). Diagenetic overprint results in a decrease of 2% d18O and an increase in Mn of up to 250 ppm. However, the sediment seems to preserve most of its high Sr content compared to the primary low-magnesium calcite of co-occurring belemnite rostra. The periodicity of geochemical cycles is dominated by 413 ka and weak signals between 51 and 22.5 ka, attributable to orbital forcing. Accumulation rates within these cycles vary between 40 and 50 m/Ma. The resulting cyclic sedimentary sequence is the product of (a) changes in primary production of low-magnesium calcitic biogenic material in surface waters within the long eccentricity and the precession, demonstrated by the CaCO3 content and the Mg/Al, Mn/Al and Sr/Al ratios, and (b) fluctuations in climate and continental weathering, which changed the quality of supplied clay minerals (the illite/smectite ratio), demonstrated by the K/Al ratio. High carbonate productivity correlates with smectite-favouring weathering (semi-arid conditions, conspicuously dry and moist seasonal changes in warmer climates). Ti as the proxy indicator for the detrital terrigenous influx, as well as Rb, Si, Zr and Na, shows only low frequency signals, indicating nearly constant rates of supply throughout the more or less pure pelagic carbonate deposition of the long-lasting third-order Middle-Upper Campanian sedimentary cycle.

Experiment: Acidified seawater impacts sea urchin larvae pH regulatory systems relevant for calcification

Calcifying echinoid larvae respond to changes in seawater carbonate chemistry with reduced growth and developmental delay. To date, no information exists on how ocean acidification acts on pH homeostasis in echinoderm larvae. Understanding acid-base regulatory capacities is important because intracellular formation and maintenance of the calcium carbonate skeleton is dependent on pH homeostasis. Using H(+)-selective microelectrodes and the pH-sensitive fluorescent dye BCECF, we conducted in vivo measurements of extracellular and intracellular pH (pH(e) and pH(i)) in echinoderm larvae. We exposed pluteus larvae to a range of seawater CO(2) conditions and demonstrated that the extracellular compartment surrounding the calcifying primary mesenchyme cells (PMCs) conforms to the surrounding seawater with respect to pH during exposure to elevated seawater pCO(2). Using FITC dextran conjugates, we demonstrate that sea urchin larvae have a leaky integument. PMCs and spicules are therefore directly exposed to strong changes in pH(e) whenever seawater pH changes. However, measurements of pH(i) demonstrated that PMCs are able to fully compensate an induced intracellular acidosis. This was highly dependent on Na(+) and HCO(3)(-), suggesting a bicarbonate buffer mechanism involving secondary active Na(+)-dependent membrane transport proteins. We suggest that, under ocean acidification, maintained pH(i) enables calcification to proceed despite decreased pH(e). However, this probably causes enhanced costs. Increased costs for calcification or cellular homeostasis can be one of the main factors leading to modifications in energy partitioning, which then impacts growth and, ultimately, results in increased mortality of echinoid larvae during the pelagic life stage.

Planktic foraminifera of sediment core GeoB1710-3

In this study, we test various parameters in deep-sea sediments (bulk sediment parameters and changes in microfossil abundances and preservation character) which are generally accepted as indicators of calcium carbonate dissolution. We investigate sediment material from station GeoB 1710-3 in the northern Cape Basin (eastern South Atlantic), 280 km away from the Namibian coast, well outside today's coastal upwelling. As northern Benguela upwelling cells were displaced westward and periodically preceded the core location during the past 245 kyr (Volbers et al., submitted), GeoB 1710-3 sediments reflect these changes in upwelling productivity. Results of the most commonly used calcium carbonate dissolution proxies do not only monitor dissolution within these calcareous sediments but also reflect changes in upwelling intensity. Accordingly, these conventional proxy parameters misrepresent, to some extent, the extent of calcium carbonate dissolution. These results were verified by an independent dissolution proxy, the Globigerina bulloides dissolution index (BDX') (Volbers and Henrich, 2002, doi:10.1016/S0025-3227(02)00333-X). The BDX' is based on scanning electronic microscope ultrastructural investigation of planktonic foraminiferal tests and indicates persistent good carbonate preservation throughout the past 245 kyr, with the exception of one pronounced dissolution event at early oxygen isotopic stage (OIS) 6. The early OIS 6 is characterized by calcium carbonate contents, sand contents, and planktonic foraminiferal concentrations all at their lowest levels for the last 245 kyr. At the same time, the ratio of radiolarian to planktonic foraminiferal abundances and the ratio of benthic to planktonic foraminiferal tests are strongly increased, as are the rain ratio, the fragmentation index, and the BDX'. The sedimentary calcite lysocline rose above the core position and GeoB 1710-3 sediments were heavily altered, as attested to by the unusual accumulation of pellets, aggregates, sponge spicules, radiolaria, benthic foraminifera, and planktonic foraminiferal assemblages. Solely the early OIS 6 dissolution event altered the coarse fraction intensely, and is therefore reflected by all conventional calcium carbonate preservation proxies and the BDX'. We attribute the more than 1000 m rise of the sedimentary calcite lysocline to the combination of two processes: (a) a prominent change in the deep-water mass distribution within the South Atlantic and (b) intense degradation of organic material within the sediment (preserved as maximum total organic carbon content) creating microenvironments favorable for calcium carbonate dissolution.