Sedimentology, age models and stable isotope ratios of sediment cores from the equatorial Pacific

Based on detailed reconstructions of global distribution patterns, both paleoproductivity and the benthic d13C record of CO2, which is dissolved in the deep ocean, strongly differed between the Last Glacial Maximum and the Holocene. With the onset of Termination I about 15,000 years ago, the new (export) production of low- and mid-latitude upwelling cells started to decline by more than 2-4 Gt carbon/year. This reduction is regarded as a main factor leading to both the simultaneous rise in atmospheric CO2 as recorded in ice cores and, with a slight delay of more than 1000 years, to a large-scale gradual CO2 depletion of the deep ocean by about 650 Gt C. This estimate is based on an average increase in benthic d13C by 0.4-0.5 per mil. The decrease in new production also matches a clear 13C depletion of organic matter, possibly recording an end of extreme nutrient utilization in upwelling cells. As shown by Sarnthein et al., [1987], the productivity reversal appears to be triggered by a rapid reduction in the strength of meridional trades, which in turn was linked via a shrinking extent of sea ice to a massive increase in high-latitude insolation, i.e., to orbital forcing as primary cause.

The South Atlantic carbon isotope record of planktic foraminifera

We reviewed the paleoceanographic application of the carbon isotope composition of planktic foraminifera. Major controls on the distribution of d13C of dissolved CO2 (d13CSCO2) in the modern ocean are photosynthesis-respiration cycle, isotopic fractionation during air-sea exchange, and circulation. The carbon isotope composition of surface waters is not recorded without perturbations by planktic foraminifera. Besides d13CSCO2 of the surrounding seawater, the d13C composition of planktic foraminifera is affected by vital effects, the water depth of calcification and postdepositional dissolution. We compared several high-resolution (>10cm/ka) carbon isotope records from the Southern Ocean, the Benguela upwelling system, and the tropical Atlantic. In the Southern Ocean, carbon isotope values are about 1.2 per mil lower during the LGM and up to 1.7 per mil lower during the last deglaciation, when compared to the Holocene. These depletions might be explained with a combination of a subsurface nutrient enrichment and reduced air-sea exchange due to an increased stratification of surface waters. In the Benguela Upwelling system, waters originating in the south are upwelled. While the deglacial minimum is transferred and recorded in its full extent in the d13C record of Globigerina bulloides, glacial values show only little changes. This might suggest, that the lower glacial d13C values of high-latitude surface waters are not upwelled off Namibia, or that G. bulloides records post-upwelling conditions, when increased seasonal production has already increased surface-water d13C. Synchronous to the d13C depletions in high latitudes, low d13C values were recorded in Globigerinoides sacculifer during the LGM and during the last deglaciation in the nutrient-depleted western equatorial Atlantic. Hence, part of the glacial-interglacial variability presumably transferred from high to low latitudes seems to be related to changes in thermodynamic fractionation. The variability in d13C is lowest in the northernmost core M35003-4 from the eastern Caribbean, implying that the Antarctic Intermediate Water might have acted as a conduit to transfer the deglacial minimum to tropical surface waters.

Boron isotope and B/Ca ratios of planktonic foraminifera

Here a new analytical methodology is described for measuring the isotopic composition of boron in foraminifera using multicollector inductively coupled plasma mass spectrometry (MC-ICPMS). This new approach is fast (~10 samples analysed in duplicate per analytical session) and accurate (to better than 0.25 per mil at 95% confidence) with acceptable sample size requirements (1-3 mg of carbonate). A core top calibration of several common planktic and two benthic species from geographically widespread localities shows a very close agreement between the isotopic composition measured by MC-ICPMS and the isotopic composition of B(OH)-4 in seawater (as predicted using the recently measured isotopic equilibrium factor of 1.0272) at the depth of habitat. A down core and core top investigation of boron concentration (B/Ca ratio) shows that the partition coefficient is influenced by [CO2-3] complicating the application of this proxy. Nevertheless, it is demonstrated that these two proxies can be used to fully constrain the carbonate system of surface water in the Caribbean Sea (ODP Site 999A) over the last 130 kyr. This reconstruction shows that during much of the Holocene and the last interglacial period surface water at Site 999A was in equilibrium with the atmosphere with respect to CO2. During the intervening colder periods although the surface water pCO2 was lower than the Holocene, it was a minor to significant source of CO2 to the atmosphere possibly due to either an expansion of the eastern equatorial Atlantic upwelling zone, or a more local expansion of coastal upwelling in the southern Caribbean. Such reorganisation of the oceanic carbonate system in favour of a larger source of CO2 to the atmosphere from the equatorial ocean may require mechanisms responsible for lowering atmospheric CO2 during glacial periods to be more efficient than previously supposed.

(Table S1) Stable isotope record and growth rates of cultured Mytilus edulis

To study the effects of temperature, salinity, and life processes (growth rates, size, metabolic effects, and physiological/genetic effects) on newly precipitated bivalve carbonate, we quantified shell isotopic chemistry of adult and juvenile animals of the intertidal bivalve Mytilus edulis (Blue mussel) collected alive from western Greenland and the central Gulf of Maine and cultured them under controlled conditions. Data for juvenile and adult M. edulis bivalves cultured in this study, and previously by Wanamaker et al. (2006, doi:10.1029/2005GC001189), yielded statistically identical paleotemperature relationships. On the basis of these experiments we have developed a species-specific paleotemperature equation for the bivalve M. edulis [T °C = 16.28 (±0.10) - 4.57 (±0.15) {d18Oc VPBD - d18Ow VSMOW} + 0.06 (±0.06) {d18Oc VPBD - d18Ow VSMOW}**2; r**2 = 0.99; N = 323; p < 0.0001]. Compared to the Kim and O'Neil (1997) inorganic calcite equation, M. edulis deposits its shell in isotope equilibrium (d18Ocalcite) with ambient water. Carbon isotopes (d13Ccalcite) from sampled shells were substantially more negative than predicted values, indicating an uptake of metabolic carbon into shell carbonate, and d13Ccalcite disequilibrium increased with increasing salinity. Sampled shells of M. edulis showed no significant trends in d18Ocalcite based on size, cultured growth rates, or geographic collection location, suggesting that vital effects do not affect d18Ocalcite in M. edulis. The broad modern and paleogeographic distribution of this bivalve, its abundance during the Holocene, and the lack of an intraspecies physiologic isotope effect demonstrated here make it an ideal nearshore paleoceanographic proxy throughout much of the North Atlantic Ocean.

Distribution of heavy minerals in sediment cores from the Laptev Sea continental margin and the central Arctic Ocean

Focussing on heavy-mineral associations in the Laptev-Sea continental margin area and the eastern Arctic Ocean, 129 surface sediment samples, two short and four long gravity cores have been studied. By means of the accessory components, heavy-mineral associations of surface sediment samples from the Laptev-See continental slope allowed the distinction into two different mineralogical provinces, each influenced by fluvial input of the Siberian river Systems. Transport pathways via sea ice from the shallow shelf areas into the Arctic Ocean up to the final ablation areas of the Fram Strait can be reconstructed by heavy-mineral data of surface sediments from the central Arctic Ocean. The shallow shelf of the Laptev Sea seems to be the most important source area for terrigenous material, as indicated by the abundant occurence of amphiboles and clinopyroxenes. Underneath the mixing Zone of the two dominating surface circulation Systems, the Beaufort- Gyre and Transpolar-Drift system, the imprint of the Amerasian shelf regions up to the Fram Strait is detectable because of a characteristical heavy-mineral association dominated by detrital carbonate and opaque minerals. Based On heavy-mineral characteristics of the potential circum-Arctic source areas, sea-ice drift, origin and distribution of ice-rafted material can be reconstructed during the past climatic cycles. Different factors controlling the transport of terrigenous material into the Arctic Ocean. The entrainment of particulate matter is triggered by the sea level, which flooded during highs and lows different regions resulting in the incorporation of sediment from different source areas into the sea ice. Additionally, the fluvial input even at low stands of sea level is responsible for the delivery of material of distinct sources for entrainment into the sea ice. Glacials and interglacials of climate cycles of the last 780 000 years left a characteristical signal in the central Arctic Ocean sediments caused by the ice- rafted material from different sources in the circum-Arctic regions and its change through time. Changes in the heavy-mineral association from an amphibole-dominated into a garnet-epidote-assemblage can be related to climate-related changes in source areas and directions of geostrophic winds, the dominating drive of the sea-ice drift. During Marine Isotope Stage (MIS) 6, the central Arctic Ocean is marked by an heavy-mineral signal, which occurs in recent sediments of the eastern Kara Sea. Its characteristics are high amounts of epidote, garnet and apatite. On the other hand, during the Same time interval a continuous record of Laptev Sea sediments is documented with high contents of amphiboles on the Lomonosov Ridge near the Laptev Sea continental slope. A nearly similar Pattern was detected in MIS 5 and 4. Small-scale glaciations in the Putorana-mountains and the Anabar-shield may have caused changes in the drainage area of the rivers and therefore a change in fluvial input. During MIS 3, the heavy-mineral association of central Arctic sediments show similar patterns than the Holocene mineral assemblage which consists of amphiboles, ortho- and clinopyroxenes with a Laptev Sea source. These minerals are indicating a stable Transpolar-Drift system similar to recent conditions. An extended influence of the Beaufort Gyre is only recognized, when sediment material from the Amerasian shelf areas reached the core location PS2757-718 during Termination Ib. Based On heavy-mineral data from Laptev-Sea continental slope Core PS2458-4 the paleo-sea-ice drift in the Laptev Sea during 14.000 years was reconstructed. During Holocene sea-level rise, the bathymetrically deeper parts of the Western shelf were flooded first. At the beginning of the Atlantic stage, nearly the entire shelf was marine influenced by fully marine conditions and the recent surface circulation was established.

Stable carbon and oxygen isotope record of foraminifera from DSDP Hole 30-289

Sediments accumulate on the sea floor far from land with rates of a few millimetres to a few centimetres per thousand years. Sediments have been accumulating under broadly similar conditions, subject to similar controls, for the past 10 8 years and more. In principle we should be able to study the distribution of climatic variance with frequencies over the range 10**-3 to 10**-7 cycles per year with comparative ease. In fact, nearly all our data are heavily weighted towards the youngest part of the geological record. We study frequencies higher than 10**-4 cycles per year in the special case of a Pleistocene interglacial (the present one), and frequencies in the range 10**-4 to 10**-5 cycles per year in the special case of an ice-age. Although these may be of more direct interest to mankind than earlier periods, it may well be that we will understand the causes of climatic variability better if we can examine their operation over a longer time scale and under different boundary conditions. Rather than review the available data, I have collected some new data to show the feasibility of gathering a data base for examining climatic variability without this usual bias toward the recent. The most widely applicable tool for extracting climatic information from deep-sea sediments is oxygen isotope analysis of calcium carbonate microfossils. It is generally possible to select from the sediment both specimens of benthonic Foraminifera (that is, those that lived in ocean deep water at the sediment-water interface) and specimens of planktonic Foraminifera (that is, those that lived and formed their shells near the ocean surface, and fell to the sediment after death). Thus one is able to monitor conditions at the surface and at depth at simultaneous moments in the geological past. The necessity to analyse calcareous microfossils restricts investigation to calcareous sediments, but even with this restriction in sediment type there are many factors governing the rate of sediment accumulation. On a global scale, sediment accumulates so as to balance the input to the oceans from continental erosion. Even when averaged globally, long-term accumulation rates have varied by almost a factor of ten (Davies et al., 1977, doi:10.1126/science.197.4298.53). At the regional scale, surface productivity and deep-water physical and chemical conditions also affect the sediment accumulation rate. Since all these are susceptible to variation and may well vary in response to climatic change as well as other factors, it is extremely hazardous to attempt to express any climatic variable as a function of time on the basis of measurements originally made as a function of depth in sediment. Although time has been used as a basis for plotting Figs. i-8, these should be regarded as freehand sketches of climatic history rather than as time-series plots.

Isotope record of Nd-Sr-Pb in deep sea sediments from the Pacific (Table 2)

Pelagic clay of the east-central Pacific province is shown to be a mixture of three primary detrital components, reflecting continental source areas in Asia, North America, and Central and South America. Relative contributions from each source area are a function of geography, and this distribution appears to have remained constant over the past five million years, despite changing flux rates. A Q-mode factor analysis of downcore records for Pb, Sr, and Nd isotopes identified three factors that account for 98% of the total variance. These factors represent the radiogenic isotopic signatures of 1) late Cenozoic Asian dust, which dominates in the central North Pacific; 2) North American continental hemipelagic/eolian sources, restricted mainly to the easternmost North Pacific at ~30 °N latitude; and 3) Central and South American sources, restricted to areas east of ~100 °W longitude. South of the Intertropical Convergence Zone (~6 °N), the Asian dust signature diminishes abruptly. We conclude that late Cenozoic Asian dust sources can be isotopically differentiated downcore from both North American and South and Central American sources in the eastcentral Pacific. This approach has a utility for identifying changes in long-term Cenozoic atmospheric circulation patterns.

Strontium isotope and rare earth element geochemistry of basalts from DSDP Leg 37

87Sr/S6Sr ratios have been determined on eleven whole rock basalt samples from DSDP Leg 37. The 87Sr/S6Sr ratios range from 0.70305 +/- 4 to 0.70451 +/- 4 due to alteration and contamination with seawater Sr. Leaching with 5% HF has only a small effect on the 87Sr/86Sr of the samples. However, treatment with 6M HCl in acid digestion bombs at 130°C removes the contaminant more effectively. Altered plagioclase and olivine are dissolved during this process. The mean 87Sr/86Sr of four HCl-treated samples from hole 332A is 0.70299 and that for five samples from hole 332B is 0.70297. The 87Sr/86Sr ratios of treated samples from holes 333A and 335 are 0.70304 +/- 4 and 0.70316 +/- 4, respectively. These 87Sr/86Sr ratios are within the range observed for other basalts elsewhere along the Mid-Atlantic Ridge in the North Atlantic. REE distribution patterns have been determined for four samples, three from hole 332B and one from hole 335. CeN/YbN ratios range from 0.58 to 1.30 and do not correlate with 87Sr/86Sr ratios. The source regions of these basalts appear to have been variable in REE abundances.