Age determination of ODP Hole 145-887

Atmospheric carbon dioxide concentrations were significantly lower during glacial periods than during intervening interglacial periods, but the mechanisms responsible for this difference remain uncertain. Many recent explanations call on greater carbon storage in a poorly ventilated deep ocean during glacial periods (Trancois et al., 1997, doi:10.1038/40073; Toggweiler, 1999, doi:10.1029/1999PA900033; Stephens and Keeling, 2000, doi:10.1038/35004556; Marchitto et al., 2007, doi:10.1126/science.1138679; Sigman and Boyle, 2000, doi:10.1038/35038000), but direct evidence regarding the ventilation and respired carbon content of the glacial deep ocean is sparse and often equivocal (Broecker et al., 2004, doi:10.1126/science.1102293). Here we present sedimentary geochemical records from sites spanning the deep subarctic Pacific that -together with previously published results (Keigwin, 1998, doi:10.1029/98PA00874)- show that a poorly ventilated water mass containing a high concentration of respired carbon dioxide occupied the North Pacific abyss during the Last Glacial Maximum. Despite an inferred increase in deep Southern Ocean ventilation during the first step of the deglaciation (18,000-15,000 years ago) (Marchitto et al., 2007, doi:10.1126/science.1138679; Monnin et al., 2001, doi:10.1126/science.291.5501.112), we find no evidence for improved ventilation in the abyssal subarctic Pacific until a rapid transition ~14,600 years ago: this change was accompanied by an acceleration of export production from the surface waters above but only a small increase in atmospheric carbon dioxide concentration (Monnin et al., 2001, doi:10.1126/science.291.5501.112). We speculate that these changes were mechanistically linked to a roughly coeval increase in deep water formation in the North Atlantic (Robinson et al., 2005, doi:10.1126/science.1114832; Skinner nd Shackleton, 2004, doi:10.1029/2003PA000983; McManus et al., 2004, doi:10.1038/nature02494), which flushed respired carbon dioxide from northern abyssal waters, but also increased the supply of nutrients to the upper ocean, leading to greater carbon dioxide sequestration at mid-depths and stalling the rise of atmospheric carbon dioxide concentrations. Our findings are qualitatively consistent with hypotheses invoking a deglacial flushing of respired carbon dioxide from an isolated, deep ocean reservoir periods (Trancois et al., 1997, doi:10.1038/40073; Toggweiler, 1999, doi:10.1029/1999PA900033; Stephens and Keeling, 2000, doi:10.1038/35004556; Marchitto et al., 2007, doi:10.1126/science.1138679; Sigman and Boyle, 2000, doi:10.1038/35038000; Boyle, 1988, doi:10.1038/331055a0), but suggest that the reservoir may have been released in stages, as vigorous deep water ventilation switched between North Atlantic and Southern Ocean source regions.

Geochemistry of planktonic foraminifera from DSDP sites in the Atlantic and Pacific Ocean

The lithium content of planktonic foraminiferal calcite has been determined to evaluate temporal variability of seawater Li concentrations over the past 116 m.y. Mean foraminiferal calcite lithium/calcium in each time interval is no more than 16% greater nor 25% less than the mean Li/Ca of all samples. Li/Ca minima are observed for samples from 50-60 m.y. and 80-90 m.y., with Li/Ca about 25% lower than in adjacent time intervals. At no time during the past 40 m.y does mean Li/Ca appear to be higher than that at present. Subject to the limitations imposed by sample coverage and diagenesis, a similar conclusion holds for the past 116 m.y. Coupled with an oceanic mass balance model for Li, these data suggest that: (1) oceanic Li concentrations and, therefore, high-temperature hydrothermal circulation fluxes during the past 40 m.y. (and perhaps the past 100 m.y.) have not been more than perhaps 30-40% greater than at present for intervals any longer than a million years at most, and (2) these fluxes were not a factor of two higher 100 m.y. ago. By inference, variations in oceanic crustal generation rates over these time periods are similarly limited. Decreases in hydrothermal circulation fluxes and crustal generation rates or fluctuations up to 20% in these rates of a few million years duration are not necessarily ruled out by the Li/Ca data. The lack of variability in Li/Ca over time is not unequivocal evidence that hydrothermal fluxes have not varied because the rates of removal processes may be linked to changes in input fluxes.

Geochemistry of sediment cores of the Southern Ocean

We examine the possibility that glacial increase in the areal extent of reducing sediments might have changed the oceanic Cd inventory, thereby decoupling Cd from PO4. We suggest that the precipitation of Cd-sulfide in suboxic sediments is the single largest sink in the oceanic Cd budget and that the accumulation of authigenic Cd and U is tightly coupled to the organic carbon flux into the seafloor. Sediments from the Subantarctic Ocean and the Cape Basin (South Atlantic), where oxic conditions currently prevail, show high accumulation rates of authigenic Cd and U during glacial intervals associated with increased accumulation of organic carbon. These elemental enrichments attest to more reducing conditions in glacial sediments in response to an increased flux of organic carbon. A third core, overlain by Circumpolar Deep Water (CPDW) as are the other two cores but located south of the Antarctic Polar Front, shows an approximately inverse pattern to the Subantarctic record. The contrasting patterns to the north and south of the Antarctic Polar Front suggest that higher accumulation rates of Cd and U in Subantarctic sediments were driven primarily by increased productivity. This proposal is consistent with the hypothesis of glacial stage northward migration of the Antarctic Polar Front and its associated belt of high siliceous productivity. However, the increase in authigenic Cd and U glacial accumulation rates is higher than expected simply from a northward shift of the polar fronts, suggesting greater partitioning of organic carbon into the sediments during glacial intervals. Lower oxygen content of CPDW and higher organic carbon to biogenic silica rain rate ratio during glacial stages are possible causes. Higher glacial productivity in the Cape Basin record very likely reflects enhanced coastal up-welling in response to increased wind speeds. We suggest that higher productivity might have doubled the areal extent of suboxic sediments during the last glacial maximum. However, our calculations suggest low sensitivity of seawater Cd concentrations to glacial doubling of the extent of reducing sediments. The model suggests that during the last 250 kyr seawater Cd concentrations fluctuated only slightly, between high levels (about 0.66 nmol/kg) on glacial initiations and reaching lowest values (about 0.57 nmol/kg) during glacial maxima. The estimated 5% lower Cd content at the last glacial maximum relative to modern levels (0.60 nmol/kg) cannot explain the discordance between Cd and delta13C, such as observed in the Southern Ocean. This low sensitivity is consistent with foraminiferal data, suggesting minimal change in the glacial Cd mean oceanic content.

Stable carbon and oxygen isotope ratios of Planulina wuellerstorfi from sediments of the Sierra Leone Rise

Causes of change in deep water delta13C can be either global or local in extent. Global causes include (1) climatically-induced changes in the amount of terrestrial biomass which alter the average carbon isotopic composition of the oceanic reservoir (Shackleton, 1977), and (2) erosion and deposition of organic-rich, continental shelf sediments during sea level fluctuations which change the mean oceanic carbon: phosphorus ratio (Broecker, 1982 doi:10.1016/0079-6611(82)90007-6). Regional gradients of delta13C are created by remineralization of organic detritus within the deep ocean itself thus reflecting the distribution of water masses and modern thermohaline flow. Changes in a single geological record of benthic foraminiferal delta13C can result from any combination of these global and abyssal circulation effects. By sampling a large number of cores collected over a wide bathymetric range yet confined to a small geographical region we have minimized the ambiguity. We can assume that each delta13C record was equally affected by global causes of delta13C variation. The differences seen between the delta13C records must, therefore, reflect changes in the distribution of delta13C in the deep ocean. We interpret these differences in distribution in terms of changes in the ocean's abyssal circulation. Benthic foraminiferal carbon isotopic evidence from a suite of Sierra Leone Rise cores indicates that the deeper parts of the eastern Atlantic basins underwent a reduction in [O2] during the maximum of the last glaciation. Reduced advection of O2-rich deep water through low-latitude fracture zones, associated with increased delivery of organic matter to the deep ocean, lowered the delta13C of deep water SumCO2 at all depths below the sill separating the eastern and western Atlantic basins (Metcalf et al., 1964 doi:10.1016/0011-7471(64)91078-2). This decreased advection into the eastern Atlantic Ocean coincides with the overall decrease in deep water production in the North Atlantic during the last glacial maximum (Curry and Lohmann, 1982 doi:10.1016/0033-5894(82)90071-0; Boyle and Keigwin, 1982 doi:10.1126/science.218.4574.784; Schnitker, 1979 doi:10.1016/0377-8398(79)90020-3; Streeter and Shackleton, 1979 doi:10.1126/science.203.4376.168).

IRD, benthic foraminifera and stable isotopic record of northern Sargasso Sea sediments

New geochemical proxy data from Bermuda Rise piston cores reveal ocean and climate conditions in the northern Sargasso Sea during marine isotope stage 3. Using ?18O on the planktonic foraminifer Globigerinoides ruber, we can correlate explicitly with every stadial/interstadial change in Greenland ice between ~32 and 58 ka. These data suggest repetitive changes of ~4°C in the annual average sea surface temperature (SST), with maximum cooling comparable to or greater than SST during glacial maximum conditions. The extent of SST depression is about the same for typical stadial events and for Heinrich events 4 and 5, which we have identified on the Bermuda Rise by traces of ice rafting. Benthic foraminiferal d13C decreases during every stadial event, consistent with reduced production of the deepest component of North Atlantic Deep Water and shoaling of its interface with Antarctic Bottom Water. This interpretation is supported by benthic Cd/Ca data from the climate cycle associated with interstadial 8.

Age determination and stable isotope record of ODP Hole 162-980B

The conversion of surface water to deep water in the North Atlantic results in the release of heat from the ocean to the atmosphere, which may have amplified millennial-scale climate variability during glacial times (Broecker et al., 1990, doi:10.1029/PA005i004p00469) and could even have contributed to the past 11,700 years of relatively mild climate (known as the Holocene epoch) (Bond et al., 2001, doi:10.1126/science.1065680; Alley et al., 1997, doi:10.1130/0091-7613(1997)025<0483:HCIAPW>2.3.CO;2; Keigwin and Boyle, 2000, doi:10.1073/pnas.97.4.1343). Here we investigate changes in the carbon-isotope composition of benthic foraminifera throughout the Holocene and find that deep-water production varied on a centennial-millennial timescale. These variations may be linked to surface and atmospheric events that hint at a contribution to climate change over this period.

DNA alignment and Bayesian trees of partial sequences of COI, COIII and the haemocyanin functional unit f-g of 28 octopod species

Background: Octopods have successfully colonised the world's oceans from the tropics to the poles. Yet, successful persistence in these habitats has required adaptations of their advanced physiological apparatus to compensate impaired oxygen supply. Their oxygen transporter haemocyanin plays a major role in cold tolerance and accordingly has undergone functional modifications to sustain oxygen release at sub-zero temperatures. However, it remains unknown how molecular properties evolved to explain the observed functional adaptations. We thus aimed to assess whether natural selection affected molecular and structural properties of haemocyanin that explains temperature adaptation in octopods. Results: Analysis of 239 partial sequences of the haemocyanin functional units (FU) f and g of 28 octopod species of polar, temperate, subtropical and tropical origin revealed natural selection was acting primarily on charge properties of surface residues. Polar octopods contained haemocyanins with higher net surface charge due to decreased glutamic acid content and higher numbers of basic amino acids. Within the analysed partial sequences, positive selection was present at site 2545, positioned between the active copper binding centre and the FU g surface. At this site, methionine was the dominant amino acid in polar octopods and leucine was dominant in tropical octopods. Sites directly involved in oxygen binding or quaternary interactions were highly conserved within the analysed sequence. Conclusions: This study has provided the first insight into molecular and structural mechanisms that have enabled octopods to sustain oxygen supply from polar to tropical conditions. Our findings imply modulation of oxygen binding via charge-charge interaction at the protein surface, which stabilize quaternary interactions among functional units to reduce detrimental effects of high pH on venous oxygen release. Of the observed partial haemocyanin sequence, residue 2545 formed a close link between the FU g surface and the active centre, suggesting a role as allosteric binding site. The prevalence of methionine at this site in polar octopods, implies regulation of oxygen affinity via increased sensitivity to allosteric metal binding. High sequence conservation of sites directly involved in oxygen binding indicates that functional modifications of octopod haemocyanin rather occur via more subtle mechanisms, as observed in this study.