(Table S1) Stable carbon and oxygen isotope ratios of benthic foraminifera of the western Atlantic Ocean

Oxygen and carbon isotopic data were produced on the benthic foraminiferal taxa Cibicidoides and Planulina from 25 new piston cores, gravity cores, and multicores from the Brazil margin. The cores span water depths from about 400 to 3000 m and intersect the major water masses in this region. These new data fill a critical gap in the South Atlantic Ocean and provide the motivation for updating the classic glacial western Atlantic d13C transect of Duplessy et al. (1988). The distribution of 13C of SumCO2 requires the presence of three distinct water masses in the glacial Atlantic Ocean: a shallow (~1000 m), southern source water mass with an end-member d13C value of about 0.3-0.5 per mil VPDB, a middepth (~1500 m), northern source water mass with an end-member value of about 1.5 per mil, and a deep (>2000 m), southern source water with an end-member value of less than -0.2 per mil, and perhaps as low as the -0.9 per mil values observed in the South Atlantic sector of the Southern Ocean (Ninnemann and Charles, 2002, doi:10.1016/S0012-821X(02)00708-2). The origins of the water masses are supported by the meridional gradients in benthic foraminiferal d18O. A revised glacial section of deep water d13C documents the positions and gradients among these end-member intermediate and deep water masses. The large property gradients in the presence of strong vertical mixing can only be maintained by a vigorous overturning circulation.

Miocene stable isotope record of benthic foraminifera from IODP Site 320-U1336

Stable carbon and oxygen isotopes (d13C and d18O) of foraminiferal tests are amongst the most important tools in paleoceanography but the extent to which recrystallization can alter the isotopic composition of the tests is not well known. Here, we compare three middle Miocene (16-13 Ma) benthic foraminiferal stable isotope records from eastern equatorial Pacific sites with different diagenetic histories to investigate the effect of recrystallization. To test an extreme case, we analyzed stable isotope compositions of benthic foraminifera from Integrated Ocean Drilling Program Site U1336, for which the geochemistry of bulk carbonates and associated pore waters indicate continued diagenetic alteration in sediments > 14.7 Ma. Despite this diagenetic overprinting, the amplitudes and absolute values of the analyzed U1336 stable isotopes agree well with high resolution records from better preserved Sites U1337 and U1338 nearby. Our results suggest that although benthic foraminiferal tests of all three sites show some degree of textural changes due to recrystallization, they have retained their original stable isotope signatures. The good agreement of the benthic foraminiferal stable isotope records demonstrates that recrystallization occurred extremely rapidly (<100 kyr) after deposition. This is confirmed by the preservation of orbital cyclicities in U1336 stable isotope data and d18O values being different to inorganic calcite that would precipitate from U1336 pore waters during late recrystallization. The close similarity of the benthic foraminiferal stable isotope records between the sites allows the well resolved paleo-magnetic results of Site U1336 to be transferred to Sites U1337 and U1338 improving the global Geological Timescale.

Radiogenic neodymium, strontium and lead isotopes of authigenic and detrital sedimentary phases and stable oxygen and carbon isotopes of benthic foraminifera from gravity cores SO213-59-2 and SO213-60-1 (central South Pacific).

The South Pacific is a sensitive location for the variability of the global oceanic thermohaline circulation given that deep waters from the Atlantic Ocean, the Southern Ocean, and the Pacific Basin are exchanged. Here we reconstruct the deep water circulation of the central South Pacific for the last two glacial cycles (from 240,000 years ago to the Holocene) based on radiogenic neodymium (Nd) and lead (Pb) isotope records complemented by benthic stable carbon data obtained from two sediment cores located on the flanks of the East Pacific Rise. The records show small but consistent glacial/interglacial changes in all three isotopic systems with interglacial average values of -5.8 and 18.757 for epsilon Nd and 206Pb/204Pb, respectively, whereas glacial averages are -5.3 and 18.744. Comparison of this variability of Circumpolar Deep Water (CDW) to previously published records along the pathway of the global thermohaline circulation is consistent with reduced admixture of North Atlantic Deep Water to CDW during cold stages. The absolute values and amplitudes of the benthic delta13C variations are essentially indistinguishable from other records of the Southern Hemisphere and confirm that the low central South Pacific sedimentation rates did not result in a significant reduction of the amplitude of any of the measured proxies. In addition, the combined detrital Nd and strontium (87Sr/86Sr) isotope signatures imply that Australian and New Zealand dust has remained the principal contributor of lithogenic material to the central South Pacific.

Termination II record, stable isotopes and trace elements of Stagamite MF-3 from Schafsloch Cave

The timing and nature of the penultimate deglaciation, also known as Termination II (T-II), is subject of controversial discussions due to the scarcity of precisely-dated palaeoclimate records. Here we present a new precisely-dated and highly-resolved multi-proxy stalagmite record covering T-II from the high alpine Schafsloch Cave in Switzerland, an area where climate is governed by the North Atlantic. The inception of stalagmite growth at 137.4 ± 1.4 kyr before present (BP) indicates the presence of drip water and cave air temperatures of above 0 °C, and is related to a climate-induced change in the thermal state (from cold-to warm-based) of the glacier above the cave. The cessation of stalagmite growth between 133.1 ± 0.7 and 131.9 ± 0.6 kyr BP is most likely related to distinct drop in temperature associated with Heinrich stadial 11. The resumption of stalagmite growth at 131.9 ± 0.6 kyr BP is accompanied by an abrupt increase in temperature and precipitation as indicated by distinct shifts in the oxygen and carbon isotopic composition as well as in trace element concentrations. The mid-point of T-II is around 131.8 ± 0.6 kyr BP in the Schafsloch Cave record is significantly earlier compared to the age of 129.1 ± 0.1 kyr BP in the Sanbao Cave record from China. The different ages between both records can be best explained by the competing effects of insolation and glacial boundary forcing on seasonality and snow cover extent in Eurasia.

Age models and stable isotopes of sediment cores from the northern seas

Oxygen and carbon isotope measurements were carried out on tests of planktic foraminifers N. pachyderma (sin.) from eight sediment cores taken from the eastern Arctic Ocean, the Fram Strait, and the lceland Sea, in order to reconstruct Arctic Ocean and Norwegian-Greenland Sea circulation patterns and ice covers during the last 130,000 years. In addition, the influence of ice, temperature and salinity effects on the isotopic signal was quantified. Isotope measurements on foraminifers from sediment surface samples were used to elucidate the ecology of N. pachyderma (sin.). Changes in the oxygen and carbon isotope composition of N. pachyderma (sin.) from sediment surface samples document the horizontal and vertical changes of water mass boundaries controlled by water temperature and salinity, because N. pachyderma (sin.) shows drastic changes in depth habitats, depending on the water mass properties. It was able to be shown that in the investigated areas a regional and spatial apparent increase of the ice effect occurred. This happened especially during the termination I by direct advection of meltwaters from nearby continents or during the termination and in interglacials by supply of isotopically light water from rivers. A northwardly proceeding overprint of the 'global' ice effect, increasing from the Norwegian-Greenland Sea to the Arctic Ocean, was not able to be demonstrated. By means of a model the influence of temperature and salinity on the global ice volume signal during the last 130,000 years was recorded. In combination with the results of this study, the model was the basis for a reconstruction of the paleoceanographic development of the Arctic Ocean and the Norwegian-Greenland Sea during this time interval. The conception of a relatively thick and permanent sea ice cover in the Nordic Seas during glacial times should be replaced by the model of a seasonally and regionally highly variable ice cover. Only during isotope stage 5e may there have been a local deep water formation in the Fram Strait.

Isotopic data of atmospheric methane from EDML and Vostok ice cores over a full glacial cycle

The response of natural CH4 sources to climate changes will be an important factor to consider as concentrations of this potent greenhouse gas continue to increase. Polar ice cores provide the means to assess this sensitivity in the past and have shown a close connection between CH4 levels and northern hemisphere temperature variability over the last glacial cycle. However, the contribution of the various CH4 sources and sinks to these changes is still a matter of debate. Contemporaneous stable CH4 isotope records in ice cores provide additional boundary conditions for assessing changes in the CH4 sources and sinks. Here we present new ice core CH4 isotope data covering the last 160,000 years, showing a clear decoupling between CH4 loading and carbon isotopic variations over most of the record. We suggest that d13CH4 variations were not dominated by a change in the source mix but rather by climate- and CO2-related ecosystem control on the isotopic composition of the methane precursor material, especially in seasonally inundated wetlands in the tropics. In contrast, relatively stable d13CH4 intervals occurred during large CH4 loading changes concurrently with past climate changes implying that most CH4 sources (most notably tropical wetlands) responded simultaneously.

Stable carbon and oxygen isotope composition of Recent, Tertiary and Cretaceous foraminifera (Table III)

Oxygen isotope analyses of Tertiary and Cretaceous planktic foraminifera indicate that species have been stratified with respect to depth in the water column at least since Albian time. There is a relationship between morphology and depth habitat. Species with globigerine morphology have consistently occupied shallower depths than have species with globorotalid morphology. Biserially arranged species occupied both shallow and deep levels in the water column. On the average, it appears that ancient species with shallow habitats have been more susceptible to dissolution and have been preserved less well than species dwelling in deeper habitats. This relationship is similar to that observed for Recent planktic foraminifera. Comparison of carbon isotope ratios of adult and juvenile forms indicates that either the source of the carbon found in the shell or the carbon isotopic fractionations which occur during calcite secretion change during the development of individual foraminifera. The carbon isotopic ratios do not provide a reliable means for reconstructing the depth habitats of ancient species. Temperature-depth profiles for tropical Tertiary oceans have been reconstructed from the isotopic temperatures of planktic and benthic foraminifera. The vertical thermal structure of Oligocene oceans resembled that of modern oceans most closely. Those of Paleocene and Maastrichtian times differed most from that of modern oceans.

Stable carbon and oxygen isotope ratios of benthic foraminifera

Carbon isotopic measurements on the benthic foraminiferal genus Cibicidoides document that mean deep ocean delta13C values were 0.46 per mil lower during the last glacial maximum than during the Late Holocene. The geographic distribution of delta13C was altered by changes in the production rate of nutrient-depleted deep water in the North Atlantic. During the Late Holocene, North Atlantic Deep Water, with high delta13C values and low nutrient values, can be found throughout the Atlantic Ocean, and its effects can be traced into the southern ocean where it mixes with recirculated Pacific deep water. During the glaciation, decreased production of North Atlantic Deep Water allowed southern ocean deep water to penetrate farther into the North Atlantic and across low-latitude fracture zones into the eastern Atlantic. Mean southern ocean delta13C values during the glaciation are lower than both North Atlantic and Pacific delta13C values, suggesting that production of nutrient-depleted water occurred in both oceans during the glaciation. Enriched 13C values in shallow cores within the Atlantic Ocean indicate the existence of a nutrient-depleted water mass above 2000 m in this ocean.

Biogenic opal, carbonat concentrations and stable oxygen isotope ratios of foraminifera from sediment cores of the Southern Ocean

We present records of biogenic opal percentage and burial rate in 12 piston cores from the Atlantic and Indian sectors of the Southern Ocean. These records provide a detailed, quantitative description of changing patterns of opal deposition over the last 450 kyr. The striking regional coherence of these records suggests that dissolution in the deep sea and sediment pore waters does not obscure the surface productivity signal, and therefore these opal time series can be used in combination with other surface water tracers to make inferences about the chemistry and circulation of the Southern Ocean under different global climate conditions. Three broad depositional patterns can be distinguished. Northernmost records (39°-42°S latitude) are characterized by enhanced opal burial during glacial periods and strong 41 kyr periodicity. Records from cores just north of the present Antarctic Polar Front (46°-49°S) show even larger increases in opal burial rate during glacial intervals, but have variance concentrated in the 100 and 23 kyr bands. Southernmost records (51°-55°S) are completely out of phase with those to the north, with greatly reduced opal burial rates during glacial periods. Taken as a whole, the opal records show no evidence for the increased total Antarctic productivity predicted by recent geochemical models of atmospheric CO2 variability. The areal expansion of Southern Ocean sea ice over the present zone of high siliceous productivity provides one plausible explanation for the glacial-interglacial opal patterns. The excess silica not taken up in this zone during glacial periods would contribute to greater nutrient availability and thus higher productivity in the subantarctic region. However, local circulation changes may act to modify this basic signal, possibly accounting for the observed differences in the opal variance spectra.

(Table 1) Planktonic foraminifera counts and stable oxygen isotope ratios of Pacific Ocean surface sediments

Core-top samples from the eastern tropical Pacific (10°N to 20°S) were used to test whether the ratio between Globorotalia menardii cultrata and Neogloboquadrina dutertrei abundance (Rc/d) and the oxygen isotope composition (?18O) of planktonic foraminifera can be used as proxies for the latitudinal position of the Equatorial Front. Specifically, this study compares the ?18O values of eight species of planktonic foraminifera (Globigerinoides ruber sensu stricto (ss) and sensu lato (sl), Globigerinoides sacculifer, Globigerinoides triloba, Pulleniatina obliquiloculata, Neogloboquadrina dutertrei, Globorotalia menardii menardii, Globorotalia menardii cultrata and Globorotalia tumida) with the seasonal hydrography of the region, and evaluates the application of each species or combination of species for paleoceanographic reconstructions. The results are consistent with sea surface temperature and water column stratification patterns. We found that in samples north of 1°N, the Rc/d values tend to be higher and d18O values of G. ruber, G. sacculifer, G. triloba, P. obliquiloculata, N. dutertrei, and G. menardii cultrata tend to be lower than those from samples located south of 1°N. We suggest that the combined use of Rc/d and the d18O difference between G. ruber and G. tumida or between P. obliquiloculata and G. tumida are the most suitable tools for reconstructing changes in the latitudinal position of the Equatorial Front and changes in the thermal stratification of the upper water column in the eastern tropical Pacific.

Stable carbon and oxygen isotope ratios of planktonic foraminifera from the equatorial Atlantic

Carbon isotopic records of nutrient-depleted surface water place constraints on the past fertility of the oceans and on past atmospheric pCO2 levels. The best records of nutrient-depleted delta13C are obtained from planktonic foraminifera living in the thick mixed layers of the western equatorial and tropical Atlantic Ocean. We have produced a composite, stacked Globigerinoides sacculifer delta13C record from the equatorial Atlantic, which exhibits significant spectral power at the 100,000- and 41,000-year Milankovitch periods, but no power at the 23,000-year period. Similar to the record presented by Shackleton and Pisias [1985], surface-deep ocean Delta delta13C produced with the G. sacculifer record leads the delta18O ice volume record. However, the glacial-interglacial amplitudes of Delta delta13C differ between our record and Shackleton and Pisias [1985] record. Although large changes in Delta delta13C occur in the equatorial Atlantic during early stages of the last three glacial cycles, surface-deep Delta delta13C at glacial maxima (18O stage 2, late stage 6, and late stage 8) was only about 0.2? greater than during the subsequent interglacial. Our results imply that nutrient-driven pCO2 changes account for about one third of the pCO2 decrease observed in ice cores, and consequently, Delta delta13C should not be used as a proxy pCO2 index. Enough variance in the ice core pCO2 records remains to be explained that conclusions about pCO2 and ice volume phase relationships should also be reexamined. As much as 40 ppm pCO2 change still has not been accounted for by models of past physics and chemistry of the ocean.

Stable isotope record of foraminifera from the Southern Ocean

Sediment cores from the southern continental margin of Australia are near the formation region of Antarctic Intermediate Water (AAIW) and Subantarctic Mode Water and record the changes in these water masses from the last glacial maximum through the present. Carbon and oxygen isotopes were measured on the benthic foraminiferal species Planulina wuellerstrorfi for both the Recent and last glacial maximum sections of the cores and were then used to reconstruct temperature and carbon isotopic water column profiles. The glacial oxygen isotope profile indicates a vertical temperature structure for this region similar to that in today's Subantarctic Zone. Although intermediate water delta13C cannot be used as a nutrient tracer in this region because of the large influence of air-sea carbon isotopic exchange on this water mass, delta13C can be used as a water mass tracer. Today, AAIW properties reflect contributions from cool, fresh Antarctic Surface Waters (2/3) and warm, salty waters from the Indian Ocean (1/3). When examined in conjuction with the glacial delta13C and delta18C data from the north Indian and Southern Oceans, our data suggest a much reduced contribution of North Indian Ocean intermediate water to glacial Antarctic Intermediate Water relative to the contribution of Antarctic Surface Water. This fresher, cooler glacial Antarctic Intermediate Water would be distributed to the intermediate-depth ocean, thus decreasing the transport of salt produced in the North Indian Ocean to the rest of the world's oceans. Combined with evidence for a reduced influence of North Atlantic Deep Water, these results suggest major changes in the pathways for the redistribution of heat and salt in the glacial ocean.

Stable isotope ratios of planktonic foraminifera from North Atlantic surface sediments

We measured the oxygen isotopic composition of the deep-dwelling foraminiferal species G. inflata, G. truncatulinoides dextral and sinistral, and P. obliquiloculata in 29 modern core tops raised from the North Atlantic Ocean. We compared calculated isotopic temperatures with atlas temperatures and defined ecological models for each species. G. inflata and G. truncatulinoides live preferentially at the base of the seasonal thermocline. Under temperature stress, i.e., when the base of the seasonal thermocline is warmer than 16°C, G. inflata and G. truncatulinoides live deeper in the main thermocline. P. obliquiloculata inhabits the seasonal thermocline in warm regions. We tested our model using 10 cores along the Mauritanian upwelling and show that the comparison of d18O variations registered by the surficial species G. ruber and G. bulloides and the deep-dwelling species G. inflata evidences significant glacial-interglacial shifts of the Mauritanian upwelling cells.

Chemical composition and stable sulfur isotope record of Black Sea sediments

The main terminal processes of organic matter mineralization in anoxic Black Sea sediments underlying the sulfidic water column are sulfate reduction in the upper 2-4 m and methanogenesis below the sulfate zone. The modern marine deposits comprise a ca. 1-m-deep layer of coccolith ooze and underlying sapropel, below which sea water ions penetrate deep down into the limnic Pleistocene deposits from >9000 years BP. Sulfate reduction rates have a subsurface maximum at the SO4[2-]-CH4 transition where H2S reaches maximum concentration. Because of an excess of reactive iron in the deep limnic deposits, most of the methane-derived H2S is drawn downward to a sulfidization front where it reacts with Fe(III) and with Fe2+ diffusing up from below. The H2S-Fe2+ transition is marked by a black band of amorphous iron sulfide above which distinct horizons of greigite and pyrite formation occur. The pore water gradients respond dynamically to environmental changes in the Black Sea with relatively short time constants of ca. 500 yr for SO4[2-] and 10 yr for H2S, whereas the FeS in the black band has taken ca. 3000 yr to accumulate. The dual diffusion interfaces of SO4[2-]-CH4 and H2S-Fe2+ cause the trapping of isotopically heavy iron sulfide with delta34S = +15 to +33 per mil at the sulfidization front. A diffusion model for sulfur isotopes shows that the SO4[2-] diffusing downward into the SO4[2-]-CH4 transition has an isotopic composition of +19 per mil, close to the +23 per mil of H2S diffusing upward. These isotopic compositions are, however, very different from the porewater SO4[2-] (+43 per mil) and H2S (-15 per mil) at the same depth. The model explains how methane-driven sulfate reduction combined with a deep H2S sink leads to isotopically heavy pyrite in a sediment open to diffusion. These results have general implications for the marine sulfur cycle and for the interpretation of sulfur isotopic data in modern sediments and in sedimentary rocks throughout earth's history.

Table 1. Isotopic composition of hydrated and dehydrated subsamples from sediment core M56_278

Large euhedral crystals of calcium carbonate hexahydrate were recovered from a shelf basin of the Bransfield Strait, Antarctic Peninsula, at a water depth of 1950 meters and sub-zero bottom water temperatures. The chemistry, mineralogy, and stable isotope composition of this hydrated calcium carbonate phase, its environment of formation, and its mode of precipitation confirm the properties variously attributed to hypothetical precursors of the glendonites and thereby greatly expand their use in paleoceanographic interpretation.