Chemistry and stable isotope record of sediment core GeoB4905-4

Evidence of rapid climatic oscillations like those observed in the Greenland ice cores and sediments from high latitudes of the northern Atlantic have been recognized in the pulses of terrigenous material to continental margin sediments off Cameroon. Fe/Ca ratios used as a parameter to quantify the relative proportions of terrigenous fluxes versus marine carbonate monitor the variability of the west African monsoon. They reveal the history of abrupt changes in precipitation over western and central Africa during the past 52 kyr. These rapid changes are particularly pronounced during the last glacial period and occur at timescales of a few thousand years. Stable oxygen isotope (delta18O) records of Globigerinoides ruber (pink) show high negative values reflecting periods of high monsoon precipitation. The Fe/Ca pattern is very similar to the Dansgaard-Oeschger cycles from the Greenland ice cores. The good correspondence between the warm interstadials of the Dansgaard-Oeschger cycles from the GISP2 ice core records and the high pulses of Fe/Ca sedimentation in our core suggest a strong teleconnection between the low-latitude African climate and the high-latitude northern hemisphere climate oscillations during the last glacial. This climatic link is probably vested in the west African monsoonal fluctuation that alters tropical sea surface temperatures, thermohaline circulations and in turn net export of heat from the south to the north Atlantic, coupled with the variability of the low-latitude southeast trade winds.

(Table 1) Radiocarbon dating of a lake sediment core, southern West Greenland

The dominant processes determining biological structure in lakes at millennial timescales are complex. In this study, we used a multi-proxy approach to determine the relative importance of in-lake versus indirect processes on the Holocene development of an oligotrophic lake in SW Greenland (66.99°N, 50.97°W). A 14C and 210Pb-dated sediment core covering approximately 8500 years BP was analyzed for organic-inorganic carbon content, pigments, diatoms, chironomids, cladocerans, and stable isotopes (d13C, d18O). Relationships among the different proxies and a number of independent controlling variables (Holocene temperature, an isotope-inferred cooling period, and immigration of Betula nana into the catchment) were explored using redundancy analysis (RDA) independent of time. The main ecological trajectories in the lake biota were captured by ordination first axis sample scores (18-32% variance explained). The importance of the arrival of Betula (ca. 6500 years BP) into the catchment was indicated by a series of partial-constrained ordinations, uniquely explaining 12-17% of the variance in chironomids and up to 9% in pigments. Climate influences on lake biota were strongest during a short-lived cooling period (identified by altered stable isotopes) early in the development of the lake when all proxies changed rapidly, although only chironomids had a unique component (8% in a partial-RDA) explained by the cooling event. Holocene climate explained less variance than either catchment changes or biotic relationships. The sediment record at this site indicates the importance of catchment factors for lake development, the complexity of community trends even in relatively simple systems (invertebrates are the top predators in the lake) and the challenges of deriving palaeoclimate inferences from sediment records in low-Arctic freshwater lakes.

Lead/Calcium profiles in the common time window 1770-2010 of the three Arctica islandica shells

In the study, we establish centennial records of anthropogenic lead pollution at different locations in the North Atlantic (Iceland, USA, and Europe) by means of lead deposited in shells of the long-lived bivalve Arctica islandica. Due to local oceanographic and geological conditions we conclude that the lead concentrations in the Icelandic shell reflect natural influxes of lead into Icelandic waters. In comparison, the lead profile of the US shell is clearly driven by anthropogenic lead emissions transported from the continent to the ocean by westerly surface winds. Lead concentrations in the European North Sea shell, in contrast, are dominantly driven by local lead sources resulting in a much less conspicuous 1970s gasoline lead peak. In conclusion, the lead profiles of the three shells are driven by different influxes of lead, and yet, all support the applicability of Pb/Ca analyses of A. islandica shells to reconstruct location specific anthropogenic lead pollution.

(Table 1) Stable isotope records of clathrite and water

Aragonitic clathrites are methane-derived precipitates that are found at sites of massive near-seafloor gas hydrate (clathrate) accumulations at the summit of southern Hydrate Ridge, Cascadia margin. These platy carbonate precipitates form inside or in proximity to gas hydrate, which in our study site currently coexists with a fluid that is highly enriched in dissolved ions as salts are excluded during gas hydrate formation. The clathrites record the preferential incorporation of 18O into the hydrate structure and hence the enrichment of 16O in the surrounding brine. We measured d18O values as high as 2.27 per mil relative to Peedee belemnite that correspond to a fluid composition of -1.18 per mil relative to standard mean ocean water. The same trend can be observed in Ca isotopes. Ongoing clathrite precipitation causes enrichment of the 44Ca in the fluid and hence in the carbonates. Carbon isotopes confirm a methane source for the carbonates. Our triple stable isotope approach that uses the three main components of carbonates (Ca, C, O) provides insight into multiple parameters influencing the isotopic composition of the pore water and hence the isotopic composition of the clathrites. This approach provides a tool to monitor the geochemical processes during clathrate and clathrite formation, thus recording the evolution of the geochemical environment of gas hydrate systems.

Alkenone stable carbon isotopes, carbonate stable carbon and oxygen isotopes, planktic foraminifera boron isotopes and atmospheric CO2 calculations and box model results from Ras il-Pellegrin section, Malta

The development of a permanent, stable ice sheet in East Antarctica happened during the middle Miocene, about 14 million years (Myr) ago. The middle Miocene therefore represents one of the distinct phases of rapid change in the transition from the "greenhouse" of the early Eocene to the "icehouse" of the present day. Carbonate carbon isotope records of the period immediately following the main stage of ice sheet development reveal a major perturbation in the carbon system, represented by the positive d13C excursion known as carbon maximum 6 ("M6"), which has traditionally been interpreted as reflecting increased burial of organic matter and atmospheric pCO2 drawdown. More recently, it has been suggested that the d13C excursion records a negative feedback resulting from the reduction of silicate weathering and an increase in atmospheric pCO2. Here we present high-resolution multi-proxy (alkenone carbon and foraminiferal boron isotope) records of atmospheric carbon dioxide and sea surface temperature across CM6. Similar to previously published records spanning this interval, our records document a world of generally low (~300 ppm) atmospheric pCO2 at a time generally accepted to be much warmer than today. Crucially, they also reveal a pCO2 decrease with associated cooling, which demonstrates that the carbon burial hypothesis for CM6 is feasible and could have acted as a positive feedback on global cooling.

Element analyses of DSDP/ODP Hole 504B basalt and breccia (Table 2)

Geochemical well logs were used to measure the dry weight percent oxide abundances of Si, Al, Ca, Mg, Fe, Ti, and K and the elemental abundances of Gd, S, Th, and U at 0.15-m intervals throughout the basement section of Hole 504B. These geochemical data are used to estimate the integrated chemical exchange resulting from hydrothermal alteration of the oceanic crust that has occurred over the last 5.9 Ma. A large increase in Si in the transition zone between pillows and dikes (Layers 2B and 2C) indicates that mixing of hot, upwelling hydrothermal fluids with cold, downwelling seawater occurred in the past at a permeability discontinuity at this level in the crust, even though the low-to-high permeability boundary in Hole 504B is now 500 m shallower (at the Layer 2A/2B boundary). The observations of extensive Ca loss and Mg gain agree with chemical exchanges recorded in the laboratory in experiments on the reactions that occur between basalt and seawater at high temperatures. The K budget requires significant addition to Layer 2A from both high-temperature depletion in Layers 2B and 2C and low-temperature alteration by seawater. Integrated water/rock ratios are derived for the mass of seawater required to add enriched elements and for the mass of hydrothermal fluid required to remove depleted elements in the crust at Hole 504B.

Pleistocene stable isotope record of planktonic foraminifera of ODP Site 138-847

We present Pleistocene oxygen and carbon isotope records from two planktonic foraminifer species (Globigerinoides sacculifer and Neogloboquadrina dutertrei) from Ocean Drilling Program Site 847 (0°16'N, 95°19'W; 3334 m water depth). An average sample resolution of 4500 yr was obtained by sampling at an interval of 15 cm through a continuous 35-m section from 0 to 1.15 Ma. Our d18O-based chronology is similar to that derived independently by astronomically tuning the gamma-ray attenuation porosity evaluator (GRAPE) record (Shackleton et al., 1995), though offsets as large as ± 30 k.y. occur on occasion. The surface waters at eastern equatorial Pacific Site 847, 380 km west of the Galapagos, are characterized by strong and constant upwelling, elevated nutrient concentrations, and high productivity. The isotopic composition of G. sacculifer (300-355 µm) reflects conditions in the thin-surface mixed layer, and the composition of N. dutertrei (355-425 µm) monitors the subsurface waters of the permanent shallow (10-40 m) thermocline. The Pleistocene d18O difference (N. dutertrei minus G. sacculifer, Dd18Od-s) averages 0.9 per mil and ranges from 0 per mil to 1.7 per mil. Neglecting species effects and shell size, the average Pleistocene d13C difference (G. sacculifer minus N. dutertrei, Dd13Cs-d) is 0.0 per mil and ranges from -0.5 per mil to 0.5 per mil. The Dd18Od-s and Dd13Cs-d records are used to infer vertical contrasts in upper ocean water temperature and nutrient concentration, though d13C may also be influenced by other factors, such as CO2 gas exchange. Variations in the isotopic differences are often synchronous with glacial/interglacial climate change. Glacial periods are characterized by smaller vertical contrasts in both temperature and nutrient concentration, and by notably greater accumulation rates of N. dutertrei and CaCO3. We attribute these responses to greater upwelling at the equatorial divergence. Superimposed on the glacial/interglacial Dd18Od-s pattern is a long-term trend possibly associated with the advection of Peru Current waters. The temporal fluctuations in the isotopic contrasts are strikingly similar to those observed at Site 851 (Ravelo and Shackleton, this volume), suggesting that the inferred changes in thermal and chemical profiles occurred over a broad region in the equatorial Pacific.

Barium in sediments off northwest Africa

High-resolution down-core analyses of the solid phase content of total barium (Batot) and total organic carbon (TOC) back to 25 kyr B.P. were performed on a gravity core from the upper continental slope off Cape Yubi (Morocco). The observed discrepancy between the two potential paleoproductivity proxies, Batot and TOC, initiated supplementary examinations of the pore water, the geochemistry of the clay fraction, X-ray diffraction analyses, and the application of a sequential Ba extraction method of selected samples. Additionally, we analyzed down-core samples of the planktonic foraminifera Turborotalita quinqueloba and Globorotalia inflata for their Ba/Ca ratios. These analyses, which were performed for the first time on these species, were used to reconstruct past oceanic Ba concentrations. We suggest that in the study area, which is characterized by high accumulation rates, the preserved TOC content is a valuable proxy for past primary productivity, whereas the solid phase Batot contents appear to be affected by other mechanisms and factors. Peaks of total barium content in the clay fraction and of Ba/Ca ratios in the planktonic foraminifera shells found during the Younger Dryas and the Heinrich 1 event are likely to result from increased meltwater influx into the northern North Atlantic. We suggest that Ba-enriched meltwater was transmitted by the eastern boundary current system from higher latitudes to the region of the Canary Islands. Total barium contents of the clay fraction (Batot,clay) and Ba/Ca in planktonic foraminifera shells seem to be reliable proxies for this discharge of meltwater.

Seawater carbonate chemistry, processes and elements during experiments with planktonic foraminifera Orbulina universa, 2004

We investigate the sensitivity of U/Ca, Mg/Ca, and Sr/Ca to changes in seawater [CO3[2-]] and temperature in calcite produced by the two planktonic foraminifera species, Orbulina universa and Globigerina bulloides, in laboratory culture experiments. Our results demonstrate that at constant temperature, U/Ca in O. universa decreases by 25 +/- 7% per 100 µmol [CO3[2-]] kg**-1, as seawater [CO3[2-]] increases from 110 to 470 µmol kg**-1. Results from G. bulloides suggest a similar relationship, but U/Ca is consistently offset by ~+40% at the same environmental [CO3[2-]]. In O. universa, U/Ca is insensitive to temperature between 15°C and 25°C. Applying the O. universa relationship to three U/Ca records from a related species, Globigerinoides sacculifer, we estimate that Caribbean and tropical Atlantic [CO3[2-]] was 110 +/- 70 µmol kg**-1 and 80 +/- 40 µmol kg**-1 higher, respectively, during the last glacial period relative to the Holocene. This result is consistent with estimates of the glacial-interglacial change in surface water [CO3[2-]] based on both modeling and on boron isotope pH estimates. In settings where the addition of U by diagenetic processes is not a factor, down-core records of foraminiferal U/Ca have potential to provide information about changes in the ocean's carbonate concentration.

Paleotemperature reconstructions on sediment core GIK161603-3

Different proxies for sea surface temperature (SST) often exhibit divergent trends for deglacial warming in tropical regions, hampering our understanding of the phase relationship between tropical SSTs and continental ice volume at glacial terminations. To reconcile divergent SST trends, we report reconstructions of two commonly used paleothermometers (the foraminifera G. ruber Mg/Ca and the alkenone unsaturation index) from a marine sediment core collected in the southwestern tropical Indian Ocean encompassing the last 37,000 years. Our results show that SSTs derived from the alkenone unsaturation index (UK'37) are consistently warmer than those derived from Mg/Ca by ~2-3°C except for the Heinrich Event 1. In addition, the initial timing for the deglacial warming of alkenone SST started at ~15.6 ka, which lags behind that of Mg/Ca temperatures by 2.5 kyr. We argue that the discrepancy between the two SST proxies reflects seasonal differences between summer and winter rather than post-depositional processes or sedimentary biases. The UK'37 SST record clearly mimics the deglacial SST trend recorded in the North Atlantic region for the earlier part of the termination, indicating the early deglacial warming trend attributed to local summer temperatures was likely mediated by changes in the Atlantic Meridional Overturning Circulation at the onset of the deglaciation, In contrast, the glacial to interglacial SST pattern recorded by G. ruber Mg/Ca probably reflects cold season SSTs. This indicates that the cold season SSTs was likely mediated by climate changes in the southern hemisphere, as it closely tracks the Antarctic timing of deglaciation. Therefore our study reveals that the tropical southwestern Indian Ocean seasonal SST was closely linked to climate changes occurring in both hemispheres. The austral summer and winter recorded by each proxy is further supported with seasonal SST trends modeled by AOGCMs for our core site. Our interpretation that the alkenone and Mg/Ca SSTs are seasonally biased may also explain similar proxy mismatches observed in other tropical regions at the onset of the last termination.

Calcium isotopes in planktonic foraminifera - core tops and sediment trap samples

For paleoceanographic studies, it is important to understand the processes that influence the calcium (Ca) isotopic composition of foraminiferal calcite tests preserved in the sediment record. Seven species of planktonic foraminifera from coretop sediments collectively exhibited a Ca temperature dependent fractionation of 0.013 per mil per °C. This is in agreement with previously published estimates for most species of planktonic foraminifera as well as biogenic and inorganic calcite and aragonite. Four species of planktonic foraminifera collected from a sediment trap showed a considerable amount of scatter and no consistent temperature dependent fractionation. Analyzed size fractions of coretop samples show no significant relationship with d44/40Ca. However, preliminary results suggest that the symbiotic and spinose foraminifera G. sacculifer might exhibit a relationship between test size and d44/40Ca. A one-box model in which Ca isotopes are allowed to fractionate by Rayleigh distillation from a biomineralization reservoir (internal pool) was used to constrain the isotopic composition of the original biomineralization Ca reservoir, assuming around 85% of the Ca reservoir is precipitated and the fractionation factor during precipitation is 0.9985 + 0.00002(T ºC). To explain the foraminiferal Ca isotope data, this model indicates that the Ca isotopic composition of the biomineralization reservoir is offset from seawater (approximately -0.8per mil).

Seawater calcium isotope ratios across the Eocene-Oligocene Transition from Pacific Ocean - Marine Barite

During the Eocene-Oligocene transition (EOT, ca. 34 Ma), Earth's climate cooled significantly from a greenhouse to an icehouse climate, while the calcite (CaCO3) compensation depth (CCD) in the Pacific Ocean increased rapidly. Fluctuations in the CCD could result from various processes that create an imbalance between calcium (Ca) sources to, and sinks from, the ocean (e.g., weathering and CaCO3 deposition), with different effects on the isotopic composition of dissolved Ca in the oceans due to differences in the Ca isotopic composition of various inputs and outputs. We used Ca isotope ratios (d44/40Ca) of coeval pelagic marine barite and bulk carbonate to evaluate changes in the marine Ca cycle across the EOT. We show that the permanent deepening of the CCD was not accompanied by a pronounced change in seawater d44/40Ca, whereas time intervals in the Neogene with smaller carbonate depositional changes are characterized by seawater d44/40Ca shifts. This suggests that the response of seawater d44/40Ca to changes in weathering fluxes and to imbalances in the oceanic alkalinity budget depends on the chemical composition of seawater. A minor and transient fluctuation in the Ca isotope ratio of bulk carbonate may reflect a change in isotopic fractionation associated with CaCO3 precipitation from seawater due to a combination of factors, including changes in temperature and/or in the assemblages of calcifying organisms.

Mineralogical composition of the upper 300m of Hole 302-M0002A

During the Arctic Coring Expedition (ACEX), a 428-m-thick sequence of Upper Cretaceous to Quaternary sediments was penetrated. The mineralogical composition of the upper 300 m of this sequence is presented here for the first time. Heavy and clay mineral associations indicate a major and consistent shift in provenance, from the Barents-Kara - western Laptev Sea region, characterized by presence of common clinopyroxene, to the eastern Laptev-East Siberian seas in the upper part of the section, characterized by common hornblende (amphibole). Sea ice originating from the latter source region must have survived at least one summer melt cycle in order to reach the ACEX drill site, if considering modern sea ice trajectories and velocities. This shift in mineral assemblages probably represents the onset of a perennial sea ice cover in the Arctic Ocean, which occurred at about 13 Ma, thus suggesting a coeval freeze in the Arctic and Antarctic regions.