AMS 14C dating points, isotopic compositions, Mg/Ca ratios and sea surface temperatures of sediment cores GeoB10029-4 and GeoB10038-4

Quantifying the spatial and temporal sea surface temperature (SST) and salinity changes of the Indo-Pacific Warm Pool is essential to understand the role of this region in connection with abrupt climate changes particularly during the last deglaciation. In this study we reconstruct SST and seawater d18O of the tropical eastern Indian Ocean for the past 40,000 years from two sediment cores (GeoB 10029-4, 1°30'S, 100°08'E, and GeoB 10038-4, 5°56'S, 103°15'E) retrieved offshore Sumatra. Our results show that annual mean SSTs increased about 2-3 °C at 19,000 years ago and exhibited southern hemisphere-like timing and pattern during the last deglaciation. Our SST records together with other Mg/Ca-based SST reconstructions around Indonesia do not track the monsoon variation since the last glacial period, as recorded by terrestrial monsoon archives. However, the spatial SST heterogeneity might be a result of changing monsoon intensity that shifts either the annual mean SSTs or the seasonality of G. ruber towards the warmer or the cooler season at different locations. Seawater d18O reconstructions north of the equator suggest fresher surface conditions during the last glacial and track the northern high-latitude climate change during the last deglaciation. In contrast, seawater ?18O records south of the equator do not show a significant difference between the last glacial period and the Holocene, and lack Bølling-Allerød and Younger Dryas periods suggestive of additional controls on annual mean surface hydrology in this part of the Indo-Pacific Warm Pool.

B-isotope and Mg/Ca ratios of planktonic foraminifera from ODP Hole 108-668B and esimates of salinity, alkalinity and pCO2 (Table 1)

Knowledge of past atmospheric pCO2 is important for evaluating the role of greenhouse gases in climate forcing. Ice core records show the tight correlation between climate change and pCO2, but records are limited to the past ~900 kyr. We present surface ocean pH and pCO2 data, reconstructed from boron isotopes in planktonic foraminifera over two full glacial cycles (0-140 and 300-420 kyr). The data co-vary strongly with the Vostok pCO2-record and demonstrate that the coupling between surface ocean chemistry and the atmosphere is recorded in marine archives, allowing for quantitative estimation of atmospheric pCO2 beyond the reach of ice cores.

Stable isotopes, Mg/Ca ratios and sea surface temperatures on foraminifera from sediment cores off equatorial Peru during the last ~17kyr

The complex deglacial to Holocene oceanographic development in the Gulf of Guayaquil (Eastern Equatorial Pacific) is reconstructed for sea surface and subsurface ocean levels from (isotope) geochemical proxies based on marine sediment cores. At sea surface, southern sourced Cold Coastal Water and tropical Equatorial Surface Water/Tropical Surface Water are intimately related. In particular since ~10 ka, independent sea surface temperature proxies capturing different seasons emphasize the growing seasonal contrast in the Gulf of Guayaquil, which is in contrast to ocean areas further offshore. Cold Coastal Water became rapidly present in the Gulf of Guayaquil during the austral winter season in line with the strengthening of the Southeast Trades, while coastal upwelling off Peru gradually intensified and expanded northward in response to a seasonally changing atmospheric circulation pattern affecting the core locations intensively since 4 ka BP. Equatorial Surface Water, instead, was displaced and Tropical Surface Water moved northward together with the Equatorial Front. At subsurface, the presence of Equatorial Under Current-sourced Equatorial Subsurface Water was continuously growing, prominently since ~10-8 ka B.P. During Heinrich Stadial 1 and large parts of the Bølling/Allerød, and similarly during short Holocene time intervals at ~5.1-4 ka B.P. and ~1.5-0.5 ka B.P., the admixture of Equatorial Subsurface Water was reduced in response to both short-term weakening of Equatorial Under Current strength from the northwest and emplacement by tropical Equatorial Surface Water, considerably warming the uppermost ocean layers.

Stable isotopes and Mg/Ca measurements of two sediment cores in the northeastern tropical Atlantic

Two SST records based on Mg/Ca of G. ruber (pink) from the continental slope off West Africa at 15°N and 12°N shed new light on the thermal bipolar seesaw pattern in the northeastern tropical Atlantic during periods of reduced Atlantic Meridional Overturning Circulation (AMOC) associated with Heinrich stadials H1 to H6. The two records indicate that the latitudinal position of the bipolar seesaw's zero-anomaly line, between cooling in the North and warming in the South, gradually shifted southward from H6 to H1. A conceptual model is presented that aims to provide a physically consistent mechanism for the southward migration of the seesaw's fulcrum. The conceptual model suggests latitudinal movements of the Intertropical Convergence Zone, driven by a combination of orbital-forced changes in the meridional temperature gradient within the realm of the Hadley cell and the expansion of the Northern Hemisphere cryosphere, as a major factor.

Planktonic foraminifera Mg/Ca-based temperatures and planktonic foraminiferal cenus counts of core GeoB10065-7 (Lombok Basin, Indonesia)

Modern variability in upwelling off southern Indonesia is strongly controlled by the Australian-Indonesian monsoon and the El Niño-Southern Oscillation, but multi-decadal to centennial-scale variations are less clear. We present high-resolution records of upper water column temperature, thermal gradient and relative abundances of mixed layer- and thermocline-dwelling planktonic foraminiferal species off southern Indonesia for the past two millennia that we use as proxies for upwelling variability. We find that upwelling was generally strong during the Little Ice Age (LIA) and weak during the Medieval Warm Period (MWP) and the Roman Warm Period (RWP). Upwelling is significantly anti-correlated to East Asian summer monsoonal rainfall and the zonal equatorial Pacific temperature gradient. We suggest that changes in the background state of the tropical Pacific may have substantially contributed to the centennial-scale upwelling trends observed in our records. Our results implicate the prevalence of an El Niño-like mean state during the LIA and a La Niña-like mean state during the MWP and the RWP.

Mineralogy and geochemistry of Mg-phyllosilicates from Middle Valley, northern Juan de Fuca Ridge

We present results of a detailed mineralogical and geochemical study of the progressive hydrothermal alteration of clastic sediments recovered at ODP Site 858 in an area of active hydrothermal venting at the sedimented, axial rift valley of Middle Valley (northern Juan de Fuca Ridge). These results allow a characterization of newly formed phyllosilicates and provide constraints on the mechanisms of clay formation and controls of mineral reactions on the chemical and isotopic composition of hydrothermal fluids. Hydrothermal alteration at Site 858 is characterized by a progressive change in phyllosilicate assemblages with depth. In the immediate vent area, at Hole 858B, detrital layers are intercalated with pure hydrothermal precipitates at the top of the section, with a predominance of hydrothermal phases at depth. Sequentially downhole in Hole 858B, the clay fraction of the pure hydrothermal layers changes from smectite to corrensite to swelling chlorite and finally to chlorite. In three pure hydrothermal layers in the deepest part of Hole 858B, the clay minerals coexist with neoformed quartz. Neoformed and detrital components are clearly distinguished on the basis of morphology, as seen by SEM and TEM, and by their chemical and stable isotope compositions. Corrensite is characterized by a 24 Å stacking sequence and high Si- and Mg-contents, with Fe/(Fe+Mg) ratio of = 0.08. We propose that corrensite is a unique, possibly metastable, mineralogical phase and was precipitated directly from seawater-dominated hydrothermal fluids. Hydrothermal chlorite in Hole 858B has a stacking sequence of 14 Å with Fe/(Fe+Mg) ratios of ? 0.35. The chemistry and structure of swelling chlorite suggest that it is a corrensiteychlorite mixed-layer phase. The mineralogical zonation in Hole 858B is accompanied by a systematic decrease in d18O, reflecting both the high thermal gradients that prevail at Site 858 and extensive sediment-fluid interaction. Precipitation of the Mg-phyllosilicates in the vent region directly controls the chemical and isotopic compositions of the pore fluids. This is particularly evident by decreases in Mg and enrichments in deuterium and salinity in the pore fluids at depths at which corrensite and chlorite are formed. Structural formulae calculated from TEM-EDX analyses were used to construct clay-H2O oxygen isotope fractionation curves based on oxygen bond models. Our results suggest isotopic disequilibrium conditions for corrensite-quartz and swelling chlorite-quartz precipitation, but yield an equilibrium temperature of 300° C ± 30° for chlorite-quartz at 32 m below the surface. This estimate is consistent with independent estimates and indicates steep thermal gradients of 10-11°/m in the vent region.

Mid-Pliocene deep-sea bottom water temperatures based on ostracode Mg/Ca ratios

We studied magnesium:calcium (Mg/Ca) ratios in shells of the deep-sea ostracode genus Krithe from a short interval in the middle Pliocene between 3.29 and 2.97 Ma using deep-sea drilling sites in the North and South Atlantic in order to estimate bottom water temperatures (BWT) during a period of climatic warmth. Results from DSDP and ODP Sites 552A, 610A, 607, 658A, 659A, 661A and 704 for the period Ma reveal both depth and latitudinal gradients of mean Mg/Ca values. Shallower sites (552A, 610A and 607) have higher mean Mg/Ca ratios (10.3, 9.7, 10.1 mmol/mol) than deeper sites (661A, 6.3 mmol/mol), and high latitude North Atlantic sites (552A, 610 and 607) have higher Mg/Ca ratios than low latitude (658A: 9.8 mmol/mol, 659A: 7.7 mmol/mol, 661A: 6.3 mmol/mol) and Southern Ocean (704: 8.0 mmol/mol) sites. Converting Mg/Ca ratios into estimated temperatures using the calibration of Dwyer et al. (1995) [Dwyer, G.S., Cronin, T.M., Baker, P.A., Raymo, M.E., Buzas, J.S., Corrège, T., 1995. North Atlantic deepwater temperature change during late Pliocene and late Quaternary climatic cycles. Science 270, 1347-1351] suggests that mean middle Pliocene bottom water temperatures at the study sites in the deep Atlantic were about the same as modern temperatures. However, brief pulses of elevated BWT occurred several times between 3.29 and 2.97 Ma in both the North and South Atlantic Ocean suggesting short-term changes in deep ocean circulation.

Pore water (SO4, CH4, alkalinity, HS-, Ca, Sr, Mg, Ba) and solid phase (Ca, Sr, Mg, Ba) data measured in pockmark sediments of the Northern Congo Fan

This study focuses on the vertical distribution of authigenic carbonates (aragonite and high Mg-calcite) in the form of finely disseminated precipitates as well as massive carbonate concretions present in and above gas hydrate bearing sediments of the Northern Congo Fan. Analyses of Ca, Mg, Sr and Ba in pore water, bulk sediments and authigenic carbonates were carried out on gravity cores taken from three pockmark structures (Hydrate Hole, Black Hole and Worm Hole). In addition, a background core was retrieved from an area not influenced by fluid seepage. Pore water Sr/Ca and Mg/Ca ratios are used to reveal the current depths of carbonate formation as well as the mineralogy of the authigenic precipitates. The Sr/Ca and Mg/Ca ratios of bulk sediments and massive carbonate concretions were applied to infer the presence and depth distribution of authigenic aragonite and high Mg-calcite, based on the approach presented by Bayon et al. [Bayon et al. (2007). Sr/Ca and Mg/Ca ratios in Niger Delta sediments: Implications for authigenic carbonate genesis in cold seep environments. Marine Geology 241(1-4), 93-109, doi:10.1016/j.margeo.2007.03.007]. We show that the approach developed by Bayon et al. (2007) for sediments of cold seeps of the Niger Delta is also suitable to identify the mineralogy of authigenic carbonates in pockmark sediments of the Congo Deep-Sea Fan. We expand this approach by combining interstitial with solid phase Sr/Ca and Mg/Ca ratios, which demonstrate that high Mg-calcite is the predominant authigenic carbonate that currently forms at the sulfate/methane reaction zone (SMRZ). This is the first study which investigates both solid phase and pore water signatures typical for either aragonite or high Mg-calcite precipitation for the same sediment cores and thus is able to identify active and fossil carbonate precipitation events. At all investigated pockmark sites fossil horizons of the SMRZ were deduced from high Mg-calcite located above and below the current depths of the SMRZ. Additionally, aragonite enrichments typical for high seepage rates were detected close to the sediment surface at these sites. However, active precipitation of aragonite as indicated by pore water characteristics only occurs at the Black Hole site. Dissolved and solid phase Ba concentrations were used to estimate the time the SMRZ was fixed at the current depths of the diagenetic barite fronts. The combined pore water and solid phase elemental ratios (Mg/Ca, Sr/Ca) and Ba concentrations allow the reconstruction of past changes in methane seepage at the investigated pockmark sites. At the Hydrate Hole and Worm Hole sites the time of high methane seepage was estimated to have ceased at least 600 yr BP. In contrast, a more recent change from a high flux to a more dormant stage must have occurred at the Black Hole site as evidenced by active aragonite precipitation at the sediment surface and a lack of diagenetic Ba enrichments.

Mid-Pleistocene Mg/Ca, temperature and stable isotopes from Globigerinoides ruber white and Globorotalia inflata of sediment core GeoB3801-6 from the subtropical South Atlantic

The glacial marine isotope stage 14 (MIS 14) appears in many climate records as an unusually warm glacial. During this period an almost monospecific, up to 1.5 m thick, laminated layer of the giant diatom Ethmodiscus rex has been deposited below the South Atlantic Subtropical Gyre. This oligotrophic region is today less favorable for diatom growth with sediments typically consisting of calcareous nannofossil oozes. We have reconstructed temperatures and the stable oxygen isotopic compositions of sea surface and thermocline water (d18Ow) from planktonic foraminiferal (Globigerinoides ruber and Globorotalia inflata) Mg/Ca and stable oxygen isotopes to test whether perturbations in surface ocean conditions contributed to the deposition of the diatom layer at ~530 kyr B.P. Temperatures and d18Ow values reconstructed from this diatom ooze interval are highly variable, with maxima similar to interglacial values. Since the area of the Ethmodiscus oozes resembles the region where Agulhas rings are present, we interpret these hydrographic changes to reflect the varying influence of warm and saline water of Indian Ocean origin that entered the Subtropical Gyre trapped in Agulhas rings. The formation of the Ethmodiscus oozes is associated with a period of maximum Agulhas leakage and a maximum frequency of Agulhas ring formation caused by a termination-type position of the Subtropical Front during the unusual warm MIS 14. The input of silica through the Agulhas rings enabled the shift in primary production from calcareous nannoplankton to diatoms, leading to the deposition of the massive diatom oozes.

High resolution isotope and Mg/Ca record of sediment core GeoB12615-4

The importance of intermediate water masses in climate change and ocean circulation has been emphasized recently. In particular, Southern Ocean Intermediate Waters (SOIW), such as Antarctic Intermediate Water and Subantarctic Mode Water, are thought to have acted as active interhemispheric transmitter of climate anomalies. Here we reconstruct changes in SOIW signature and spatial and temporal evolution based on a 40 kyr time series of oxygen and carbon isotopes as well as planktic Mg/Ca based thermometry from Site GeoB12615-4 in the western Indian Ocean. Our data suggest that SOIW transmitted Antarctic temperature trends to the equatorial Indian Ocean via the "oceanic tunnel" mechanism. Moreover, our results reveal that deglacial SOIW carried a signature of aged Southern Ocean deep water. We find no evidence of increased formation of intermediate waters during the deglaciation.

High resolution stable isotope and Mg/Ca record of sediment core MD02-2550C2

An early Holocene record from the Gulf of Mexico (GOM) reveals climatic and hydrologic changes during the interval from 10.5 to 7 thousand calendar years before present from paired analyses of Mg/Ca and d18O on foraminiferal calcite. The sea surface temperature record based on foraminiferal Mg/Ca contains six oscillations and an overall ~1.5°C warming that appears to be similar to the September-March insolation difference. The d18O of seawater in the GOM (d18OGOM) record contains six oscillations, including a -0.8 per mil excursion that may be associated with the "8.2 ka climate event" or a broader climate anomaly. Faunal census records from three GOM cores exhibit similar changes, suggesting subcentennial-scale variability in the incursions of Caribbean waters into the GOM. Overall, our results provide evidence that the subtropics were characterized by decadal- to centennial-scale climatic and hydrologic variability during the early Holocene.

Radiocarbon dataing, stable oxygen isotopes, and Mg/Ca ratios in surface sediment samples of the tropical eastern Indian Ocean

Shell chemistry of planktic foraminifera and the alkenone unsaturation index in 69 surface sediment samples in the tropical eastern Indian Ocean off West and South Indonesia were studied. Results were compared to modern hydrographic data in order to assess how modern environmental conditions are preserved in sedimentary record, and to determine the best possible proxies to reconstruct seasonality, thermal gradient and upper water column characteristics in this part of the world ocean. Our results imply that alkenone-derived temperatures record annual mean temperatures in the study area. However, this finding might be an artifact due to the temperature limitation of this proxy above 28°C. Combined study of shell stable oxygen isotope and Mg/Ca ratio of planktic foraminifera suggests that Globigerinoides ruber sensu stricto (s.s.), G. ruber sensu lato (s.l.), and G. sacculifer calcify within the mixed-layer between 20 m and 50 m, whereas Globigerina bulloides records mixed-layer conditions at ~50 m depth during boreal summer. Mean calcifications of Pulleniatina obliquiloculata, Neogloboquadrina dutertrei, and Globorotalia tumida occur at the top of the thermocline during boreal summer, at ~75 m, 75-100 m, and 100 m, respectively. Shell Mg/Ca ratios of all species show a significant correlation with temperature at their apparent calcification depths and validate the application of previously published temperature calibrations, except for G. tumida that requires a regional Mg/Ca-temperature calibration (Mg/Ca = 0.41 exp (0.068*T)). We show that the difference in Mg/Ca-temperatures of the mixed-layer species and the thermocline species, particularly between G. ruber s.s. (or s.l.) and P. obliquiloculata, can be applied to track changes in the upper water column stratification. Our results provide critical tools for reconstructing past changes in the hydrography of the study area and their relation to monsoon, El Niño-Southern Oscillation, and the Indian Ocean Dipole Mode.