Stable oxygen isotope and Mg/Ca ratios on Globorotalia inflata

We present a species-specific Mg/Ca-calcification temperature calibration for Globorotalia inflata from a suite of 38 core top samples from the South Atlantic (from 8° to 49°S). G. inflata is a deep-dwelling planktonic foraminifer commonly occurring in subtropical to subpolar conditions, which qualifies it for reconstructions of the permanent thermocline. Apparent calcification depths and calcification temperatures were determined by comparing measured d18O with equilibrium d18O of calcite based on water column properties. Based on our core top samples, G. inflata apparent calcification depth is constant throughout the South Atlantic mid-latitudes with a depth of 350-400 m within the permanent thermocline. The resulting Mg/Ca-calcification temperature calibration is Mg/Ca = 0.72 +/-0.045/0.042 exp (0.076 +0.006 calcification 2 temperature) (r2 = 0.81) and covers the temperature range 3.1-16.5°C. We applied our Mg/Ca calibration to gravity core PS2495-3 from the Mid-Atlantic Ridge at ca. 41°S to test its validity by reconstructing a low-resolution record covering the last two glacial-interglacial cycles. Our paleotemperature record reveals large changes in temperature for Terminations I and II, when permanent thermocline temperature increased by as much as 8°C. The G. inflata paleotemperature record suggests that oceanic fronts repeatedly migrated over the location of site PS2495-3 during the last 160 kyr. This study shows the potential of G. inflata Mg/Ca to reconstruct paleotemperatures in the permanent thermocline.

Biomarker distributions in sediment core PS2767-4

Here, we present a first (low-resolution) biomarker sea-ice proxy record from the High Arctic (southern Lomonosov Ridge), going back in time to about 60 ka (MIS 3 to MIS 1). Variable concentrations of the sea-ice diatom specific highly branched isoprenoid (HBI) with 25 carbon atoms ("IP25"), in combination with the phytoplankton biomarker brassicasterol, suggest variable seasonal sea-ice coverage and open-water productivity during MIS 3. During most of MIS 2, the spring to summer sea-ice margin significantly extended towards the south, resulting in a drastic decrease in phytoplankton productivity. During the Early Holocene Climate Optimum, brassicasterol reached its maximum, interpreted as signal for elevated phytoplankton productivity due to a significantly reduced sea-ice cover. During the mid-late Holocene, IP25 increased and brassicasterol decreased, indicating extended sea-ice cover and reduced phytoplankton productivity, respectively. The HBI diene/IP25 ratios probably reached maximum values during the Bølling-Allerød warm period and decreased during the Holocene, suggesting a correlation with sea-surface temperature.

High-resolution stratigraphic framework for Mediterranean sapropel S5

A high-resolution stratigraphic framework is presented for sapropel S5, which represents the low-mid latitude climate optimum of the previous interglacial period (Eemian). The framework is based on three sites along a transect from west to east through the eastern Mediterranean, and is further validated using a fourth site. This method allows expression of S5-based proxy records of Eemian climate variability along a standardised depth scale that offers unprecedented possibilities for assessment of spatial gradients and signal leads and lags in an interval where highresolution (radiocarbon-style) dating cannot be performed. Our lateral comparison of S5 sapropels suggests that the onset of S5 in ODP site 967C (Eratosthenes seamount) was 1-6 centuries delayed relative to the onsets in more westerly sites.

A low-latitude Upper Pleistocene oxygen isotope stack

Below oxygen isotope stage 16, the orbitally derived time-scale developed by Shackleton et al. (1990) from ODP site 677 in the equatorial Pacific differs significantly from previous ones (e.g. Kominz and Pisias, 1979 doi:10.1126/science.204.4389.171; Morley and Hays, 1981 doi:10.1016/0012-821X(81)90034-0, Imbrie et al. 1984), yielding estimated ages for the last Earth magnetic reversals that are 5-7% older than the K/Ar values (Mankinen and Dalrymple, 1979 doi:10.1029/JB084iB02p00615; Berggren et al., 1985; Harland and Armstrong, 1989) but are in good agreement with recent Ar/Ar dating (Baksi et al., 1991; 1992 doi:10.1126/science.256.5055.356; Spell and McDougall, 1992 doi:10.1029/92GL01125). These results suggest that in the lower Brunhes and upper Matuyama chronozones most deep-sea climatic records retrieved so far apparently missed or misinterpreted several oscillations predicted by the astronomical theory of climate. To test this hypothesis, we studied a high-resolution oxygen isotope record from giant piston core MD900963 (Maldives area, tropical Indian Ocean) in which precession-related oscillations in delta18O are particularly well expressed, owing to the superimposition of a local salinity signal on the global ice volume signal (Rostek et al., 1993 doi:10.1038/364319a0). Three additional precession-related cycles are observed in oxygen isotope stages 17 and 18 of core MD900963, compared to the SPECMAP composite curves (Imbrie et al., 1984; Prell et al., 1986 doi:10.1029/PA001i002p00137), and stage 21 clearly presents three precession oscillations, as predicted by Shackleton et al. (1990). The precession peaks found in the delta18O record from core MD900963 are in excellent agreement with climatic oscillations predicted by the astronomical theory of climate. Our delta18O record therefore permits the development of an accurate astronomical time-scale. Based on our age model, the Brunhes-Matuyama reversal is dated at 775 +/- 10 ka, in good agreement with the age estimate of 780 ka obtained by Shackleton et al. (1990) and recent radiochronological Ar/Ar datings on lavas (Baksi et al., 1991; 1992; Spell and McDougall, 1992). We developed a new low-latitude, Upper Pleistocene delta18O reference record by stacking and tuning the delta18O records from core MD900963 and site 677 to orbital forcing functions.

High-resolution multi-proxy record of the last glacial period from Lake Van, eastern Anatolian high plateau, Turkey

Detailed analyses of the Lake Van pollen, Ca/K ratio and stable oxygen isotope record allow the identification of millennial-scale vegetation and environmental changes in eastern Anatolia throughout the last glacial (~75-15 ka BP). The climate within the last glacial was cold and dry, with low arboreal pollen (AP) levels. The driest and coldest period corresponds to Marine Isotope Stage (MIS) 2 (~28-14.5 ka BP) dominated by the highest values of xerophytic steppe vegetation. Our high-resolution multi proxy record shows rapid expansions and contractions of tree populations that reflects variability in temperature and moisture availability. This rapid vegetation and environmental changes can be linked to the stadial-interstadial pattern of the Dansgaard-Oeschger (DO) events as recorded in the Greenland ice cores. Periods of reduced moisture availability were characterized by enhanced xerophytic species and high terrigenous input from the Lake Van catchment area. Furthermore, comparison with the marine realm reveals that the complex atmosphere-ocean interaction can be explained by the strength and position of the westerlies, which is responsible for the supply of humidity in eastern Anatolia. Influenced by diverse topography of the Lake Van catchment, larger DO interstadials (e.g. DO 19, 17-16, 14, 12 and 8) show the highest expansion of temperate species within the last glacial. However, Heinrich events (HE), characterized by highest concentrations of ice-rafted debris (IRD) in marine sediments, are identified in eastern Anatolia by AP values not lower and high steppe components not more abundant than during DO stadials. In addition, this work is a first attempt to establish a continuous microscopic charcoal record over the last glacial in the Near East, which documents an initial immediate response to millennial-scale climate and environmental variability and enables us to shed light on the history of fire activity during the last glacial.

High-resolution multi-proxy record of the last interglacial period from Lake Van, eastern Anatolian high plateau, Turkey

A high-resolution multi-proxy record from Lake Van, eastern Anatolia, derived from a lacustrine sequence cored at the 357 m deep Ahlat Ridge (AR), allows a comprehensive view of paleoclimate and environmental history in the continental Near East during the last interglacial (LI). We combined paleovegetation (pollen), stable oxygen isotope (d18Obulk) and XRF data from the same sedimentary sequence, showing distinct variations during the period from 135 to 110 ka ago leading into and out of full interglacial conditions. The last interglacial plateau, as defined by the presence of thermophilous steppe-forest communities, lasted ca. 13.5 ka, from ~129.1-115.6 ka BP. The detailed palynological sequence at Lake Van documents a vegetation succession with several climatic phases: (I) the Pistacia zone (ca. 131.2-129.1 ka BP) indicates summer dryness and mild winter conditions during the initial warming, (II) the Quercus-Ulmus zone (ca. 129.1-127.2 ka BP) occurred during warm and humid climate conditions with enhanced evaporation, (III) the Carpinus zone (ca. 127.2-124.1 ka BP) suggest increasingly cooler and wetter conditions, and (IV) the expansion of Pinus at ~124.1 ka BP marks the onset of a colder/drier environment that extended into the interval of global ice growth. Pollen data suggest migration of thermophilous trees from refugial areas at the beginning of the last interglacial. Analogous to the current interglacial, the migration documents a time lag between the onset of climatic amelioration and the establishment of an oak steppe-forest, spanning 2.1 ka. Hence, the major difference between the last interglacial compared to the current interglacial (Holocene) is the abundance of Pinus as well as the decrease of deciduous broad-leaved trees, indicating higher continentality during the last interglacial. Finally, our results demonstrate intra-interglacial variability in the low mid-latitudes and suggest a close connection with the high-frequency climate variability recorded in Greenland ice cores.

Geochemistry of low-temperatuer altered basalts of ODP Hole 136-843B

The mineralogy and chemistry of altered basalts and the stable isotopic compositions of secondary vein carbonates were studied in cores from Ocean Drilling Program Hole 843B, located in 95-Ma crust of the Hawaiian Arch. Millimeter- to centimeter-sized dark alteration halos around veins are 5%-15% altered to celadonite and Fe-oxyhydroxides, plus minor saponite and calcite. Adjacent gray host rocks are about 15% altered to saponite and calcite. The dark halos are enriched in H2O+, CO2, FeT, K2O, MnO, and Fe3+/FeT and depleted in SiO2, Al2O3, MgO, and TiO2 relative to gray host rocks. Brown alteration halos occur around veins where veins are more abundant, and are similar to dark halos, but contain more Fe-oxyhydroxides and exhibit greater Fe2O3T contents and higher Fe3+/FeT. Stable isotopic compositions of vein carbonates are consistent with their precipitation from seawater at temperatures of 5°-40°C. Crosscutting relationships of veins and zoned vein and vesicle fillings reveal a sequence of secondary mineral formation and alteration conditions. Celadonite and Fe-oxyhydroxides formed and dark alteration halos developed relatively early, under oxidizing conditions at low temperatures (<50°C). Saponite formed later at lower seawater/rock ratios and under more reducing conditions. Calcite and pyrite formed last in veins and vesicles from more evolved, seawaterderived fluids at temperatures of 5°-40°C. A second stage of celadonite, with compositions distinct from the early celadonite, also occurred relatively late (within the "calcite stage"), and may be related to refracturing of the crust and introduction of less-evolved seawater solutions into the rocks. Trends to higher K2O contents are attributed to alteration, but high K/Ti, Ba, and Zr contents indicate the presence of enriched or transitional MORB. CO2 contents of Pacific ODP cores exhibit a general increase with age suggesting progressive fixation of CO2 as calcite in the crust, but this could be complicated by local heterogeneities in fracturing and calcite formation in the crust.

Chemistry of low-temperature hydrothermal altered basement of ODP Site 129-801

Low-temperature hydrothermal alteration of basement from Site 801 was studied through analyses of the mineralogy, chemistry, and oxygen isotopic compositions of the rocks. The more than 100-m section of 170-Ma basement consists of 60 m of tholeiitic basalt separated from the overlying 60 m of alkalic basalts by a >3-m-thick Fe-Si hydrothermal deposit. Four alteration types were distinguished in the basalts: (1) saponite-type (Mg-smectite) rocks are generally slightly altered, exhibiting small increases in H2O, d18O, and oxidation; (2) celadonite-type rocks are also slightly altered, but exhibit uptake of alkalis in addition to hydration and oxidation, reflecting somewhat greater seawater/rock ratios than the saponite type; (3) Al-saponite-type alteration resulted in oxidation, hydration, and alkali and 18O uptake and losses of Ca and Na due to the breakdown of plagioclase and clinopyroxene; and (4) blue-green rocks exhibit the greatest chemical changes, including oxidation, hydration, alkali uptake, and loss of Ca, Na, and Mg due to the complete breakdown of plagioclase and olivine to K-feldspar and phyllosilicates. Saponite- and celadonite-type alteration of the tholeiite section occurred at a normal mid-ocean ridge basalt spreading center at temperatures <20°C. Near- or off-axis intrusion of an alkali basalt magma at depth reinitiated hydrothermal circulation, and the Fe-Si hydrothermal deposit formed from cool (<60°C) distal hydrothermal fluids. Focusing of fluid flow in the rocks immediately underlying the deposit resulted in the extensive alteration of the blue-green rocks at similar temperatures. Al-saponite alteration of the subsequent alkali basalts overlying the deposit occurred at relatively high water/rock ratios as part of the same low-temperature circulation system that formed the hydrothermal deposit. Abundant calcite formed in the rocks during progressive "aging" of the crust during its long history away from the spreading center.

A 31,000-year high-resolution record from two sediment cores off northwest Africa

Benthic foraminiferal assemblage compositions and sedimentary geochemical parameters were analyzed in two radiocarbon dated sediment cores from the upwelling area off NW Africa at 12°N, to reconstruct productivity changes during the last 31 kyr. High-latitude cold events and variations in low-latitude summer insolation influenced humidity, wind systems, and the position of the tropical rain belt over this time period. This in turn caused changes in intensity and seasonality of primary productivity off the southern Northwest African continental margin. High accumulation rates of benthic foraminifera, carbonate, and organic carbon during times of north Atlantic melt water events Heinrich 2 (25.4 to 24.3 kyr BP) and 1 (16.8 to 15.8 kyr BP) indicate high productivity. Dominance of infaunal benthic foraminiferal species and high numbers of deep infaunal specimens during that time indicate a strong and sustained supply of refractory organic matter reworked from the upper slope and shelf. A more southerly position of the tropical rainbelt and the Northeast trade wind belt during Heinrich 2 and 1 may have enhanced wind intensity and almost permanent upwelling, driving this scenario. A phytodetritus-related benthic fauna indicates seasonally pulsed input of labile organic matter but generally low year-round productivity during the Last Glacial Maximum (23 to 18 kyr BP). The tropical rainbelt is more expanded to the North than during Heinrich Events, and relatively weak NE trade winds resulted in seasonal and weak upwelling, thus lower productivity. High productivity characterized by a seasonally high input of labile organic matter, is indicated for times of orbital forced warming, such as the African Humid Period (9.8 to 7 kyr BP). An intensified African monsoon during boreal summer and the northernmost position of the tropical rainbelt within the last 31 kyr resulted in enhanced river discharge from the northward-extended drainage area (or river basin) initiating intense phytoplankton blooms. In the late Holocene (4 to 0 kyr BP) strong carbonate dissolution may have been caused by even more enhanced organic matter fluxes to the sea floor. Increasing aridity on the continent and stronger NE trade winds induced intensive, seasonal coastal upwelling.

High resolution study of sediment core GeoB3606-1

Based on a high-resolution analysis of the diatom signal and biogenic bulk components at site GeoB3606-1 (25°S, off Namibia), we describe rapid palaeoceanographic changes in the Benguela Upwelling System (BUS) from early MIS 3 through to the early Holocene (55 000 to 7 000 14C yr BP). Coastal upwelling strongly varied at 25°S from MIS 3 through to MIS 2. The abrupt decrease in the accumulation rate of biogenic silica and diatoms from MIS 3 into MIS 2 records rapid oceanographic changes in the BUS off Namibia. During MIS 3, leakage of excess H4SiO4 acid from the Southern Ocean into low-latitude surface waters, as indicated by the occurrence of Antarctic diatoms, enhanced the production of spores of Chaetoceros at the expense of calcareous phytoplankton. Furthermore, shallower Antarctic Intermediate Water (AAIW) would have enriched the thermocline off Namibia with silicate transported from the Southern Ocean. The strong decrease of the siliceous signal throughout MIS 2 represents a decrease in the nutrient input to the BUS, even though the diatom assemblage is still dominated by spores of the upwelling-associated diatom genus Chaetoceros. Depletion of silicate in the thermocline from the onset of MIS 2 through to the early Holocene reflects the shutdown of AAIW injection from the Southern Ocean into the BUS, causing upwelled waters to become reduced in silicate, hence less favourable for diatom production. The deglaciation and early Holocene are characterised by the replacement of the upwelling-associated flora by a non-upwelling-related diatom community, reflecting weakened upwelling, retraction of the seaward extension of the chlorophyll filament off Lüderitz, and dominance of warmer waters.

Low-molecular-weight hydrocarbons in sediments of Broken Ridge and Ninetyeast Ridge

Core samples taken during Leg 121 drilling aboard the JOIDES Resolution in the central Indian Ocean were analyzed for their low-molecular-weight hydrocarbon contents. Forty-three samples from the Broken Ridge and 39 samples from the Ninetyeast Ridge drill sites, deep-frozen on board immediately after recovery, were studied by a dynamic headspace technique (hydrogen-stripping/thermovaporization). Light hydrocarbons (saturated and olefinic) with two to four carbon atoms, and toluene as a selected aromatic compound, were identified. Total C2-C4 saturated hydrocarbon yields vary considerably from virtually zero in a Paleogene calcareous ooze from Hole 757B to nearly 600 nanogram/gram of dry-weight sediment (parts per billion) in a Cretaceous claystone from Hole 758A. An increase of light-hydrocarbon yields with depth, and hence with sediment temperature, was observed from Hole 758A samples down to a depth of about 500 meters below seafloor. Despite extreme data scatter due to lithological changes over this depth interval, this increased yield indicates the onset of temperature-controlled hydrocarbon formation reactions. Toluene contents are also extremely variable (generally between 10 and 100 ppb) and reach more than 300 ppb in two samples of tuffaceous lithology (Sections 121-755A-17R-4 and 121-758A-48R-4). As for the saturated hydrocarbons, there was also an increase of toluene yields with increasing depth in Hole 758A.