Stable carbon and oxygen isotope record of foraminifera of IODP Site 303-1307

A major tipping point of Earth's history occurred during the mid-Pliocene: the onset of major Northern-Hemisphere Glaciation (NHG) and of pronounced, Quaternary-style cycles of glacial-to-interglacial climates, that contrast with more uniform climates over most of the preceding Cenozoic and continue until today (Zachos et al., 2001, doi:10.1126/science.1059412). The severe deterioration of climate occurred in three steps between 3.2 Ma (warm MIS K3) and 2.7 Ma (glacial MIS G6/4) (Lisiecki and Raymo, 2005, doi:10.1029/2004PA001071). Various models (sensu Driscoll and Haug, 1998, doi:10.1126/science.282.5388.436) and paleoceanographic records (intercalibrated using orbital age control) suggest clear linkages between the onset of NHG and the three steps in the final closure of the Central American Seaways (CAS), deduced from rising salinity differences between Caribbean and the East Pacific. Each closing event led to an enhanced North Atlantic meridional overturning circulation and this strengthened the poleward transport of salt and heat (warmings of +2-3°C) (Bartoli et al., 2005, doi:10.1016/j.epsl.2005.06.020). Also, the closing resulted in a slight rise in the poleward atmospheric moisture transport to northwestern Eurasia (Lunt et al., 2007, doi:10.1007/s00382-007-0265-6), which probably led to an enhanced precipitation and fluvial run-off, lower sea surface salinity (SSS), and an increased sea-ice cover in the Arctic Ocean, hence promoting albedo and the build-up of continental ice sheets. Most important, new evidence shows that the closing of the CAS led to greater steric height of the North Pacific and thus doubled the low-saline Arctic Throughflow from the Bering Strait to the East Greenland Current (EGC). Accordingly, Labrador Sea IODP Site 1307 displays an abrupt but irreversible EGC cooling of 6°C and freshening by ~2 psu from 3.25/3.16-3.00 Ma, right after the first but still reversible attempt of closing the CAS.

Carbonate record of ODP Leg 167 sites

One of the expected scientific results of Ocean Drilling Program Leg 167 was to reconstruct the Neogene history of biogenic calcium carbonate accumulation in the northeastern Pacific along the California margin (Lyle, Koizumi, Richter, et al., 1997). This aims to constrain inorganic carbon burial rates, deep-water hydrography in the North Pacific, and linkages between deep Atlantic and Pacific circulation and carbonate accumulation or dissolution patterns. Data are presented for four sites. Two of them are located in the California bight-East Cortez Basin (Site 1012: 32°16.970?N 118°23.024?W, 1773 m) and San Nicholas Basin (Site 1013: 32°48.040??, 118°53.992?W, 1564 m). The others are the dedicated Hole 1017E at Site 1017 (34°32.099?N, 121°6.430?W, 955 m) and Site 1019 in the Eel River Basin (41¢X40.972?N, 124°55.975?W, 977 m). Reconstruction of paleo-sea-surface temperatures (SST) by determining the alkenone unsaturation index of the extractable organic matter is an independent technique and helps to verify oxygen-isotope-based estimates. Results from the uppermost 600 cm of the dedicated Hole 1017E are expected to reveal the local temperature history of the last 30 k.y.

Paleoclimate reconstructions from sediment core MD01-2378

On the basis of the radiocarbon (14C) plateau-tuning method a new age model for Timor Sea Core MD01-2378 was established. It revealed a precise centennial-scale phasing of climate events in the ocean, cryo-, and atmosphere during the last deglacial and provides important new insights into causal linkages controlling events of global climate change. At Site MD01-2378 reservoir ages of surface waters dropped from 1600 yr prior to 20 cal ka to 250-500 yr after 18.8 cal ka. This evidence was crucial for generating a high-resolution age model for deglacial events in the Indo-Pacific Warm Pool. Sea-surface temperatures (SST) started to change near 18.8 cal ka, that is ~500 yr after the start of, presumably northern hemispheric, deglacial melt and sea level rise as shown by the benthic foraminiferal oxygen isotope ratio (d18O). However, the SST rise occurred 500-1000 yr prior to the onset of deglacial Antarctic warming and the first major rise in atmospheric carbon dioxide at about 18 ka. The increase in SST may partly reflect reduced seasonal upwelling of cold subsurface waters along the eastern margin of the Indian Ocean, which is reflected by a doubling of the thermal gradient between the sea surface and the thermocline, a halving of chlorin productivity from 19 to 18.5 cal ka, and in particular, by the strong decrease in surface water reservoir ages. Two significant increases in deglacial Timor Sea surface salinities from 19-18.5 and 15.5-14.5 cal ka, may partly reflect the deglacial increase in the distance of local river mouths, partly an inter-hemispheric millennial-scale see-saw in tropical monsoon intensity, possibly linked to a deglacial increase in the dominance of Pacific El Niño regimes over Heinrich stadial 1.

Terrigenous proxy record from ODP Site 202-1237 and sediment core RRV9702a-69PC

ODP Site 1237 and sediment core RRV9702a-69PC were investigated for siliciclastic grain-size distributions and changes in geochemical composition to reconstruct southeast trade-wind variability during the past 5 Ma. Because both, working and archive halves of all ODP Site 1237 cores were completely depleted between 3.3 and 8.1 meters composite depths, (mcd), the corresponding sections of pre-site survey core RRV9702A-69PC were sampled and investigated to fill the gap.

Chemistry of biogenic sediments from the equatorial Pacific

To increase our understanding of the mechanisms that control the distribution of Al and Ti within marine sediment, we performed sequential extractions targeting the chemical signatures of the loosely bound, exchangeable, carbonate, oxide, organic, opal, and residual fraction of sediment from a carbonate-dominated regime (equatorial Pacific) and from a mixed opal-terrigenous regime (West Antarctic Peninsula). We observe a systematic partitioning of Al and Ti between sediment phases that is related to bulk Al/Ti. We show that, where we can quantify an Al(excess) component, the dissolved Al is preferentially affiliated with the oxide fraction, resulting in Al/Ti molar ratios of 500-3000. This is interpreted as the result of surface complexation in the water column of dissolved Al onto oxyhydroxides. We also observe a previously undetected Ti(excess) with as much as 80% of the total Ti in the organic fraction, which is most likely a function of metal-organic colloidal removal from the water column. In samples where the excess metals are obscured by the detrital load, the Al and Ti are almost exclusively found in the residual phase. This argues for the paired removal of Al (preferentially by the oxide component) and Ti (preferentially by the organic component) from the water column by settling particulate matter. This research builds upon earlier work that shows changes in the bulk ratio of Al to Ti in carbonate sediment from the central-equatorial Pacific that coincide with changes in the sedimentary bulk accumulation rate (BAR). The ratios that are observed are as much as three times higher than typical shale values, and were interpreted as the result of scavenging of dissolved Al onto particles settling in the water column. Because this non-terrigenous Al(excess) accounts for up to 50% of the total sedimentary Al inventory and correlates best with BAR, the bulk Al/Ti may be a sensitive tracer of particle flux and, therefore, export production. Because we show that the excess metals are the result of scavenging processes, the bulk Al/Ti may be considered a sensitive proxy for this region.

Ice-rafted debris record in the Prydz Bay

Ice-rafted debris mass accumulation rates (IRD MAR) at a drill site on the Antarctic continental margin are investigated to evaluate the linkages between East Antarctic Ice Sheet extent and Southern Ocean temperatures in the early to mid-Pliocene. ODP Site 1165 is within 400 km of the Antarctic coastline and in the direct pathway of icebergs released by the Amery Ice Shelf. The Amery Ice Shelf is the largest ice shelf in East Antarctica and it buttresses the Lambert Glacier drainage system, which accounts for 14% of the outflow from the East Antarctic Ice Sheet. IRD MAR were low during peak Southern Ocean warming in the early Pliocene. After a brief precursor, a tenfold increase in IRD MAR at 3.3 Ma marks the termination of the early Pliocene ice sheet minimum, coincident with the M2 glacial. For the mid-Pliocene, a strong correlation exists between the high-amplitude signal in the LR04 benthic stack and IRD MAR, suggesting linkages between East Antarctic ice extent, global ice volume and deep-water temperatures. The IRD record at Site 1165 provides evidence of greater sensitivity of the Lambert Glacier-Amery Ice Shelf system to Southern Ocean warming than is currently predicted by ice sheet models, which may relate to uncertainties in the understanding of ocean heat uptake, poleward heat transport and ice sheet-ocean interactions.

Geochemistry and diatom proxy record of ODP Site 127-797

Late Quaternary sediments of the Japan Sea are characterized by centimeter- to meter-scale alternations of dark and light layers which are synchronous basinwide. High-resolution analyses of the sediments from Ocean Drilling Program site 797 reveal that deposition of the meter-scale alternations reflect variations in paleoceanographic conditions which were closely associated with glacio-eustatic sea level changes through the modulation of the volume and character of the influx to the sea through the Tsushima Strait. The centimeter- to decimeter-scale alternations reflect millennial-scale variations which are possibly associated with Dansgaard-Oeschger (D-O) cycles, with each dark layer appearing to correspond to an interstadial. This variability is attributed to the development of a humid climate in central to eastern Asia and the consequent increase in discharge from the Huanghe and Changjiang Rivers during interstadials. This caused expansion of the East China Sea coastal water (ECSCW), which penetrated more strongly into the Japan Sea. The increased influence of the lower-salinity, nutrient-enriched ECSCW reduced deep water ventilation and enhanced the surface productivity, leading to the development of anoxic bottom waters and deposition of the dark layers. Thus the centimeter- to decimeter-scale alternations of the dark and light layers record wet and dry cycles in central to eastern Asia possibly associated with D-O cycles.

Diatom studies in surface and downcore sediments off southern Sumatra and Java

A wealth of sedimentary records aimed at reconstructing late Quaternary changes in productivity and temperature have been devoted to understanding linkages between the Indo-Pacific Warm Pool (IPWP) and other distant oceanic areas. Most of these reconstructions are based, however, on biogeochemical and sedimentological proxies, with comparatively less attention devoted to microfossils. A high-resolution (<1 ka) study of diatom concentrations and the community at site GeoB10038-4, recovered off southern Sumatra (ca. 6°S, 103°E), closely tracks the variations of diatom concentrations in the westernmost IPWP during the last glacial-interglacial cycle. The diatom record provides evidence that diatom paleoproductivity was highest during interglacials, primarily due to the input of lithogenics and nutrients following the rise in sea level after full glacials. In addition, the co-variation of total diatom concentration and Northern Hemisphere forcing for Marine Isotope Stage 5 suggests a direct response of diatom productivity and upwelling intensity to boreal summer insolation. Temporal shifts of the diverse diatom community at site GeoB10038-4 correspond well with the present-day seasonal monsoon pattern and the strengthening and weakening phases of upwelling along the southern coast of Sumatra. Resting spores of Chaetoceros, typical of nutrient-rich waters, were dominant during periods of highest diatom paleoproductivity and responded to the strengthening of the SE monsoon, while diatoms of oligotrophic to mesotrophic waters characterized intermonsoon periods. The close correspondence between the dominance of upwelling diatoms and the boreal summer insolation resembles the present-day dynamics of diatom production. The observed interglacial highs and glacial lows of diatom productivity at site GeoB10038-4 is a unique pattern in the late Quaternary tropics.

Amino acid in Deep Sea Drilling Project cores

Several amino acid diagenetic reactions, which take place in the deep-sea sedimentary environment, were investigated, using various Deep Sea Drilling Project (DSDP) cores. Initially it was found that essentially all the amino acids in sediments are bound in peptide linkages; but, with increasing age, the peptide bonds undergo slow hydrolysis that results in an increasingly larger fraction of amino acids in the free state. The hydrolysis half-life in calcareous sediments was estimated to be ~1-2 million years, while in non-carbonate sediment the hydrolysis rate may be considerably slower. The amino acid compositions and the extent of racemization of several amino acids were determined in various fractions isolated from the sediments. These analyses demonstrated that the mechanism, kinetics, and rate of amino acid diagenesis are highly dependent upon the physical state (i.e., free, bound, etc.) in which the amino acids exist in the sedimentary environment. In the free state, serine and threonine were found to decompose primarily by a dehydration reaction, while in the bound state (residue or HCl-insoluble fraction) a reversible aldol-cleavage reaction is the main decomposition pathway of these amino acids. The change in amino acid composition of the residue fraction with time was suggested to be due to the hydrolysis of peptide bonds, while in foraminiferal tests the compositional changes over geological time are the result of various decomposition reactions. Reversible first-order racemization kinetics are not observed for free amino acids in sediments. The explanation for these anomalous kinetics involves a complex reaction series which includes the hydrolysis of peptide bonds and the very rapid racemization of free amino acids. The racemization rates of free amino acids in sediments were found to be many orders of magnitude faster than those predicted from elevated temperature experiments using free amino acids in aqueous solution. The racemization rate enhancement of free amino acids in sediments may be due to the catalysis of the reaction by trace metals. Reversible first-order kinetics are followed for amino acids in the residue fraction isolated from sediments; the rate of racemization in this fraction is slower than that predicted for protein-bound amino acids. Various applications of amino acid diagenetic reactions are discussed. Racemization and the decomposition reaction of serine and threonine can both be used, with certain limitations, to make rough age estimates of deep-sea sediments back to several million years. The extent of racemization in foraminiferal tests which have been dated by some other independent technique can be used to estimate geothermal gradients, and thus heat flows, and to evaluate the bottom water temperature history in certain oceanic areas.

Distribution of pollen and spores in sediments of ODP Hole 175-1078C

The distribution of pollen in marine sediments is used to record vegetation change on the continent. Generally, a good latitudinal correspondence exists between the distribution patterns of pollen in the marine surface sediments and the occurrence of the source plants on the adjacent continent. To investigate land-sea interactions during deglaciation, we compare proxies for continental (pollen assemblages) and marine conditions (alkenone-derived sea surface temperatures) of two high-resolution, radiocarbon-dated sedimentary records from the tropical southeast Atlantic. The southern site is located West of the Cunene River mouth; the northern site is located West of the Angolan Huambe Mountains. It is inferred that the vegetation in Angola developed from Afroalpine and open savannah during the last Glacial maximum (LGM) via Afromontane Podocarpus forest during Heinrich Event 1 (H1), to an early increase of lowland forest after 14.5 ka. The vegetation record indicates dry and cold conditions during the LGM, cool and wet conditions during H1 and a gradual rise in temperature starting well before the Younger Dryas (YD) period. Terrestrial and oceanic climate developments seem largely running parallel, in contrast to the situation ca. 5° further South, where marine and terrestrial developments diverge during the YD. The cool and wet conditions in tropical West Africa, South of the equator, during H1 suggest that low-latitude insolation variation is more important than the slowdown of the thermohaline circulation for the climate in tropical Africa.

Neodymium isotope record of ODP Site 177-1090

Age estimates for the opening of Drake Passage range from 49 to 17 million years ago (Ma), complicating interpretations of the relationship between ocean circulation and global cooling. Secular variations of neodymium isotope ratios at Agulhas Ridge (Southern Ocean, Atlantic sector) suggest an influx of shallow Pacific seawater approximately 41 Ma. The timing of this connection and the subsequent deepening of the passage coincide with increased biological productivity and abrupt climate reversals. Circulation/productivity linkages are proposed as a mechanism for declining atmospheric carbon dioxide. These results also indicate that Drake Passage opened before the Tasmanian Gateway, implying the late Eocene establishment of a complete circum-Antarctic pathway.

Stable isotope record, opal accumulation rate and geochemistry of middle Miocene sediments of IODP Site 321-U1338

During the middle Miocene, Earth's climate transitioned from a relatively warm phase (Miocene climatic optimum) into a colder mode with re-establishment of permanent ice sheets on Antarctica, thus marking a fundamental step in Cenozoic cooling. Carbon sequestration and atmospheric CO2 drawdown through increased terrestrial and/or marine productivity have been proposed as the main drivers of this fundamental transition. We integrate high-resolution (1-3 k.y.) benthic stable isotope data with XRF-scanner derived biogenic silica and carbonate accumulation estimates in an exceptionally well-preserved sedimentary archive, recovered at Integrated Ocean Drilling Program Site U1338, to reconstruct eastern equatorial Pacific productivity variations and to investigate temporal linkages between high- and low-latitude climate change over the interval 16-13 Ma. Our records show that the climatic optimum (16.8-14.7 Ma) was characterized by high amplitude climate variations, marked by intense perturbations of the carbon cycle. Episodes of peak warmth at (southern hemisphere) insolation maxima coincided with transient shoaling of the carbonate compensation depth and enhanced carbonate dissolution in the deep ocean. A switch to obliquity-paced climate variability after 14.7 Ma concurred with a general improvement in carbonate preservation and the onset of stepwise global cooling, culminating with extensive ice growth over Antarctica at ~13.8 Ma. We find that two massive increases in opal accumulation at ~14.0 and ~13.8 Ma occurred just before and during the final and most prominent cooling step, supporting the hypothesis that enhanced siliceous productivity in the eastern equatorial Pacific contributed to CO2 drawdown.

Aprubt climate change events in the Northeastern Atlantic Ocean

The western Iberian margin has been one of the key locations to study abrupt glacial climate change and associated interhemispheric linkages. The regional variability in the response to those events is being studied by combining a multitude of published and new records. Looking at the trend from Marine Isotope Stage (MIS) 10 to 2, the planktic foraminifer data, conform with the alkenone record of Martrat et al. [2007], shows that abrupt climate change events, especially the Heinrich events, became more frequent and their impacts in general stronger during the last glacial cycle. However, there were two older periods with strong impacts on the Atlantic meridional overturning circulation (AMOC): the Heinrich-type event associated with Termination (T) IV and the one occurring during MIS 8 (269 to 265 ka). During the Heinrich stadials of the last glacial cycle, the polar front reached the northern Iberian margin (ca. 41°N), while the arctic front was located in the vicinity of 39°N. During all the glacial periods studied, there existed a boundary at the latter latitude, either the arctic front during extreme cold events or the subarctic front during less strong coolings or warmer glacials. Along with these fronts sea surface temperatures (SST) increased southward by about 1°C per one degree of latitude leading to steep temperature gradients in the eastern North Atlantic and pointing to a close vicinity between subpolar and subtropical waters. The southern Iberian margin was always bathed by subtropical water masses - surface and/ or subsurface ones -, but there were periods when these waters also penetrated northward to 40.6°N. Glacial hydrographic conditions were similar during MIS 2 and 4, but much different during MIS 6. MIS 6 was a warmer glacial with the polar front being located further to the north allowing the subtropical surface and subsurface waters to reach at minimum as far north as 40.6°N and resulting in relative stable conditions on the southern margin. In the vertical structure, the Greenland-type climate oscillations during the last glacial cycle were recorded down to 2465 m during the Heinrich stadials, i.e. slightly deeper than in the western basin. This deeper boundary is related to the admixing of Mediterranean Outflow Water, which also explains the better ventilation of the intermediate-depth water column on the Iberian margin. This compilation revealed that latitudinal, longitudinal and vertical gradients existed in the waters along the Iberian margin, i.e. in a relative restricted area, but sufficient paleo-data exists now to validate regional climate models for abrupt climate change events in the northeastern North Atlantic Ocean.