Stable oxygen isotope record and Sr/Ca ratios of corals from IODP Holes M0009D and M0023A

We present monthly resolved records of strontium/calcium (Sr/Ca) and oxygen isotope (d18O) ratios from well-preserved fossil corals drilled during the Integrated Ocean Drilling Program (IODP) Expedition 310 'Tahiti Sea Level' and reconstruct sea surface conditions in the central tropical South Pacific Ocean during two time windows of the last deglaciation. The two Tahiti corals examined here are uranium/thorium (U/Th)-dated at 12.4 and 14.2 ka, which correspond to the Younger Dryas (YD) cold reversal and the Bølling-Allerød (B-A) warming of the Northern Hemisphere, respectively. The coral Sr/Ca records indicate that annual average sea surface temperature (SST) was 2.6-3.1 °C lower at 12.4 ka and 1.0-1.6 °C lower at 14.2 ka relative to the present, with no significant changes in the amplitude of the seasonal SST cycle. These cooler conditions were accompanied by seawater d18O (d18Osw) values higher by ~0.8 per mill and ~0.6 per mill relative to the present at 12.4 and 14.2 ka, respectively, implying more saline conditions in the surface waters. Along with previously published coral Sr/Ca records from the island [Cohen and Hart (2004), Deglacial sea surface temperatures of the western tropical Pacific: A new look at old coral. Paleoceanography 19, PA4031, doi:10.1029/2004PA001084], our new Tahiti coral records suggest that a shift toward lower SST by ~1.5 °C occurred from 13.1 to 12.4 ka, which was probably associated with a shift toward higher d18Osw by ~0.2 per mill. Along with a previously published coral Sr/Ca record from Vanuatu [Corrège et al. (2004), Interdecadal variation in the extent of South Pacific tropical waters during the Younger Dyras event. Nature 428, 927-929], the Tahiti coral records provide new evidence for a pronounced cooling of the western to central tropical South Pacific during the Northern Hemisphere YD event.

Stable oxygen isotope record and Mg/Ca ratios at the Mid-Pleistocene Climate Transition, ODP Site 181-1123

Earth's climate underwent a fundamental change between 1250 and 700 thousand years ago, the Mid-Pleistocene Transition (MPT), when the dominant periodicity of climate cycles changed from 41,000 to 100,000 years in the absence of significant change in orbital forcing. Over this time, an increase occurred in the amplitude of change of deep ocean foraminiferal oxygen isotopic ratios, traditionally interpreted as defining the main rhythm of ice ages although containing large effects of changes in deep-ocean temperature. We have separated the effects of decreasing temperature and increasing global ice volume on oxygen isotope ratios. Our results suggest that the MPT was initiated by an abrupt increase in Antarctic ice volume at 900 ka. We see no evidence of a pattern of gradual cooling but near-freezing temperatures occur at every glacial maximum.

Age models and stabile isotope ratios from SO35 cores

Stable isotope measurements on the planktonic foraminifer Globigerinoides ruber (white) have been carried out on a number of selected deep-seas sediment cores from the South Lau and Norlh Fiji Basins. The d18O-curves show good correlation with the inter-ocean oraphic correlation composite d18O-record of the standard reference section (Prell et al. 1986), which, in combination with the chronostratigraphic classifications of Herterich & Sarnthein (1984, modified) and Imbrie et al. 1984), allows a detailed dating of the sedimentary sequences. The deepest layers in core no. 119 (southern Lau Basin) could be assigned to Isotope Stage 24. Measurements made on bulk carbonate in two cores show a much higher glacial-interglacial amplitude, allowing the general identification of the conventional oxygen isotope stages. The d13C-values of the benthic foraminifer Cibicidoides wuellerstorfi show progressively lighter values northwards reflecting an increasing contribution of the isotopically lighter CO2 from the remineralisation of organic matter during the general northward movement of the deep water masses. Cyclicities in the sedimentation rates were observed in core nos. 117 and 119 (both southern Lau Basin) where the interglacials exhibit higher levels than the glacials. Calculated new or export paleoproductivity show that the glacials had higher productivity in the euphotic zone. From the oxygen isotope stratigraphy, the five ash layers in core nos. 117 and 119 could be dated as about 530 ka B.P. in Stage 14, 695 ka B.P. in Stage 18, 775 ka B.P. in Stage 21, 790 ka B.P. and 825 ka B.P. in Stage 22. Carbonate dissolution occurred during stages 5, 8 and 10 to 12.

Organic matter C and N composition and N. pachyderma stable isotope ratios of ODP Hole 188-1166A sediments

We report the results of downhole stable isotopic (d13Corg [organic carbon] and d15N) and elemental measurements (total organic carbon [TOC], total nitrogen [TN], and carbon/nitrogen [C/N]) of sedimentary organic matter (SOM) along with stable isotopic measurements (d18O and d13C) of left-coiling Neogloboquadrina pachyderma planktonic foraminifers from Ocean Drilling Program Site 1166. TOC and TN measurements indicate a large change from organic-rich preglacial sediments with primary organic matter to organic-poor early glacial and glacial sediments, with mainly recycled organic matter. Results of the stable isotopic measurements of SOM show a range of values that are typical of both marine and terrestrial organic matter, probably reflecting a mixture of the two. However, C/N values are mostly high (>15), suggesting greater input and/or preservation of terrestrial organic matter. Foraminifers are only present in glacial/glaciomarine sediments of latest Pliocene to Pleistocene age at Site 1166 (lithostratigraphic Unit I). The majority of this unit has d13Corg and TOC values that are similar to those of glacial sediments recovered at Site 1167 (lithostratigraphic Unit II) on the slope and may have the same source(s). Although the low resolution of the N. pachyderma (s.) d18O and d13C data set precludes any specific paleoclimatic interpretation, downcore variations in foraminifer d18O and d13C values of 0.5 per mil to 1 per mil amplitude may indicate glacial-interglacial changes in ice volume/temperature in the Prydz Bay region.

Feldspar Pb-isotope ratios for earliest Pleistocene sediments of the sub-polar North Atlantic Ocean

Relatively little is known in detail about the locations of the early Pleistocene ice-sheets responsible for ice-rafted debris (IRD) inputs to the sub-polar North Atlantic Ocean during intensification of northern hemisphere glaciation (iNHG). To shed new light on this problem, we present the first combined in-depth analysis of IRD flux and geochemical provenance of individual sand-sized IRD deposited in the sub-polar North Atlantic Ocean during the earliest large amplitude Pleistocene glacial, marine isotope stage (MIS) 100 (~2.52 Ma), arguably the key glacial during iNHG. IRD provenance is assessed using laser ablation lead (Pb) isotope analyses of single feldspar grains. We find that the Pb-isotope composition (206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb) of individual ice-rafted (>150 µm) feldspars deposited at DSDP Site 611A, ODP Site 981 and IODP Site U1308 during MIS 100 records a shift from predominantly Archaean-aged circum-North Atlantic Ocean continental sources during early glacial ice-rafting events to dominantly Palaeozoic and Proterozoic-aged sources during full glacial conditions. The distribution of feldspars in Pb-Pb space for full glacial MIS 100 more closely resembles that documented for feldspars deposited at the centre of the last glacial IRD belt (at IODP/DSDP Site U1308/609) during ambient (non-Heinrich-event) ice-rafting episodes of MIS 2 (~23.8 ka) than that documented for MIS 5d (~106 ka). Comparison of our early Pleistocene and last glacial cycle datasets suggests that MIS 100 was characterised by abundant iceberg calving from large ice-sheets on multiple continents in the high northern latitudes (not just on Greenland).

Foraminiferal isotope ratios from IODP Site U1313

Large-amplitude millennial-scale climate oscillations have been identified in late Pleistocene climate archives from around the world. These oscillations appear to be of larger amplitude during times of enlarged ice sheets. This observation suggests the existence of a relationship between large-amplitude millennial variations in climate and extreme glacial conditions and therefore that the emergence of millennial-scale climate variability may be linked to the Pliocene intensification of northern hemisphere glaciation (iNHG). Here we test this hypothesis using new late Pliocene high-resolution (ab. 400 year) records of ice-rafted debris deposition and stable isotopes in planktic foraminiferal calcite (Globigerinoides ruber) generated from Integrated Ocean Drilling Program Site U1313 in the subpolar North Atlantic (a reoccupation of the classic Deep Sea Drilling Project Site 607). Our records span marine oxygen isotope stages (MIS) 103-95 (ab. 2600 to 2400 ka), the first interval during iNHG (ab. 3.5 to 2.5 Ma) in which large-amplitude glacial-interglacial cycles and inferred sea level changes occur. Our records reveal small-amplitude variability at periodicities of ab. 1.8 to 6.2 kyr that prevails regardless of (inter)glacial state with no significant amplification during the glacials MIS 100, 98, and 96. These findings imply that the threshold for the amplification of such variability to the proportions seen in the marine archive of the last glacial was not crossed during the late Pliocene and, in view of all available data, likely not until the Mid-Pleistocene Transition.

(Table S3) Benthic foraminiferal Mg/Ca, Li/Ca and stable isotope ratios of ODP Site 122-761

The sensitivities of benthic foraminiferal Mg/Ca and Li/Ca to bottom water temperature and carbonate saturation state have recently been assessed. Here we present a new approach that uses paired Mg/Ca and Li/Ca records to calculate simultaneous changes in temperature and saturation state. Using previously published records, we first use this approach to document a cooling of deep ocean waters associated with the establishment of the Antarctic ice sheet at the Eocene-Oligocene climate transition. We then apply this approach to new records of the Middle Miocene Climate Transition from ODP Site 761 to estimate variations in bottom water temperature and the oxygen isotopic composition of seawater. We estimate that the oxygen isotopic composition of seawater varied by ~1 per mil between the deglacial extreme of the Miocene Climatic Optimum and the glacial maximum following the Middle Miocene Climate Transition, indicating large amplitude variations in ice volume. However, the longer-term change between 15.3 and 12.5 Ma is marked by a ~1°C cooling of deep waters, and an increase in the oxygen isotopic composition of seawater of ~0.6 per mil. We find that bottom water saturation state increased in the lead up to the Middle Miocene Climate Transition and decreased shortly after. This supports decreasing pCO2 as a driver for global cooling and ice sheet expansion, in agreement with existing boron isotope and leaf stomatal index CO2 records but in contrast to the published alkenone CO2 records.

(Table 1) Th and U concentrations and activity ratios in deep-sea sediments at ODP Hole 105-646B

The Labrador Sea is a particularly suitable high-latitude basin for investigating U and Th behavior in deep-sea sediments. During the late Quaternary, the cyclic development and decay of huge ice sheets on adjacent land masses resulted in large-amplitude changes in sedimentation rates and organic paleoproductivities. The resulting magnification of U and Th response is well illustrated by high-resolution studies on piston-cored sediments from the Greenland continental rise at Ocean Drilling Program Leg 105 Site 646 spanning isotopic stages 8 to 1. Our results show a clear positive correlation of 238U/232Th ratios with organic paleoproductivity indicators (e.g., dinocyst) due to U uptake in the water column and/or during the early early diagenesis of organic matter responding to carbon fluxes and to their climate forcing. 230Th excesses over 234U exceed the theoretical value of the 230Th rain from the overlying water column, indicating lateral input possibly from the Greenland slope and shelf. Because these horizontal fluxes of 230Th may be partly controlled by physical parameters, 230Th excesses cannot be unequivocally correlated with sedimentation rates and/or productivity as reported elsewhere. In this subarctic basin characterized by low overall organic carbon burial, the 238U/232Th ratio appears to be a sensible geochemical indicator of organic activity and paleoproductivity.

Age determination and stable carbon isotope ratios of Neogloboquadrina pachyderma of IODP Hole 302-M0004C

The Integrated Ocean Drilling Program (IODP) Arctic Coring Expedition (ACEX) Hole 4C from the Lomonosov Ridge in the central Arctic Ocean recovered a continuous 18 m record of Quaternary foraminifera yielding evidence for seasonally ice-free interglacials during the Matuyama, progressive development of large glacials during the mid-Pleistocene transition (MPT) ~1.2-0.9 Ma, and the onset of high-amplitude 100-ka orbital cycles ~500 ka. Foraminiferal preservation in sediments from the Arctic is influenced by primary (sea ice, organic input, and other environmental conditions) and secondary factors (syndepositional, long-term pore water dissolution). Taking these into account, the ACEX 4C record shows distinct maxima in agglutinated foraminiferal abundance corresponding to several interglacials and deglacials between marine isotope stages (MIS) 13-37, and although less precise dating is available for older sediments, these trends appear to continue through the Matuyama. The MPT is characterized by nearly barren intervals during major glacials (MIS 12, 16, and 22-24) and faunal turnover (MIS 12-24). Abundant calcareous planktonic (mainly Neogloboquadrina pachyderma sin.) and benthic foraminifers occur mainly in interglacial intervals during the Brunhes and very rarely in the Matuyama. A distinct faunal transition from calcareous to agglutinated foraminifers 200-300 ka in ACEX 4C is comparable to that found in Arctic sediments from the Lomonosov, Alpha, and Northwind ridges and the Morris Jesup Rise. Down-core disappearance of calcareous taxa is probably related to either reduced sea ice cover prior to the last few 100-ka cycles, pore water dissolution, or both.

Effects of alternating current voltage amplitude and oxide capacitance on mid-gap interface state defect density extractions in In0.53Ga 0.47As capacitors

This work looks at the effect on mid-gap interface state defect density estimates for In0.53Ga0.47As semiconductor capacitors when different AC voltage amplitudes are selected for a fixed voltage bias step size (100 mV) during room temperature only electrical characterization. Results are presented for Au/Ni/Al2O3/In0.53Ga0.47As/InP metal–oxide–semiconductor capacitors with (1) n-type and p-type semiconductors, (2) different Al2O3 thicknesses, (3) different In0.53Ga0.47As surface passivation concentrations of ammonium sulphide, and (4) different transfer times to the atomic layer deposition chamber after passivation treatment on the semiconductor surface—thereby demonstrating a cross-section of device characteristics. The authors set out to determine the importance of the AC voltage amplitude selection on the interface state defect density extractions and whether this selection has a combined effect with the oxide capacitance. These capacitors are prototypical of the type of gate oxide material stacks that could form equivalent metal–oxide–semiconductor field-effect transistors beyond the 32 nm technology node. The authors do not attempt to achieve the best scaled equivalent oxide thickness in this work, as our focus is on accurately extracting device properties that will allow the investigation and reduction of interface state defect densities at the high-k/III–V semiconductor interface. The operating voltage for future devices will be reduced, potentially leading to an associated reduction in the AC voltage amplitude, which will force a decrease in the signal-to-noise ratio of electrical responses and could therefore result in less accurate impedance measurements. A concern thus arises regarding the accuracy of the electrical property extractions using such impedance measurements for future devices, particularly in relation to the mid-gap interface state defect density estimated from the conductance method and from the combined high–low frequency capacitance–voltage method. The authors apply a fixed voltage step of 100 mV for all voltage sweep measurements at each AC frequency. Each of these measurements is repeated 15 times for the equidistant AC voltage amplitudes between 10 mV and 150 mV. This provides the desired AC voltage amplitude to step size ratios from 1:10 to 3:2. Our results indicate that, although the selection of the oxide capacitance is important both to the success and accuracy of the extraction method, the mid-gap interface state defect density extractions are not overly sensitive to the AC voltage amplitude employed regardless of what oxide capacitance is used in the extractions, particularly in the range from 50% below the voltage sweep step size to 50% above it. Therefore, the use of larger AC voltage amplitudes in this range to achieve a better signal-to-noise ratio during impedance measurements for future low operating voltage devices will not distort the extracted interface state defect density.

Middle Eocene Fe and Ca counts, Ca/Fe ratios, revised splices and astronomical age models form different Sites of IODP Exp342

Accurate age models are a tool of utmost important in paleoclimatology. Constraining the rate and pace of past climate change are at the core of paleoclimate research, as such knowledge is crucial to our understanding of the climate system. Indeed, it allows for the disentanglement of the various drivers of climate change. The scarcity of highly resolved sedimentary records from the middle Eocene (Bartonian - Lutetian Stages; 47.8 - 37.8 Ma) has led to the existence of the "Eocene astronomical time scale gap" and hindered the establishment of a comprehensive astronomical time scale (ATS) for the entire Cenozoic. Sediments from the Newfoundland Ridge drilled during Integrated Ocean Drilling Program (IODP) Expedition 342 span the Eocene gap at an unprecedented stratigraphic resolution with carbonate bearing sediments. Moreover, these sediments exhibit cyclic lithological changes that allow for an astronomical calibration of geologic time. In this study, we use the dominant obliquity imprint in XRF-derived calcium-iron ratio series (Ca/Fe) from three sites drilled during IODP Expedition 342 (U1408, U1409, U1410) to construct a floating astrochronology. We then anchor this chronology to numerical geological time by tuning 173-kyr cycles in the amplitude modulation pattern of obliquity to an astronomical solution. This study is one of the first to use the 173-kyr obliquity amplitude cycle for astrochronologic purposes, as previous studies primarily use the 405-kyr long eccentricity cycle as a tuning target to calibrate the Paleogene geologic time scale. We demonstrate that the 173-kyr cycles in obliquity's amplitude are stable between 40 and 50 Ma, which means that one can use the 173-kyr cycle for astrochronologic calibration in the Eocene. Our tuning provides new age estimates for magnetochron reversals C18n.1n - C21r and a stratigraphic framework for key sites from Expedition 342 for the Eocene. Some disagreements emerge when we compare our tuning for the interval between C19r and C20r with previous tuning attempts from the South Atlantic. We therefore present a revision of the original astronomical interpretations for the latter records, so that the various astrochronologic age models for the middle Eocene in the North- and South-Atlantic are consistent.

Stable oxygen isotope ratios, calcium carbonate and opal content in late Pliocene sediments of DSDP Hole 75-532 in the Southeast Atlantic (Table 1)

Site 532 on the Walvis Ridge was sampled at 4000- to 800-year intervals from 2.24 to 2.60 Ma, spanning the three large glacial advances of the late Pliocene. An age model was created by correlating the oxygen isotope record to Site 607 with linear interpolations between tie-lines. The resultant age model differs from that in the site reports by more than 800,000 years, due to misidentification of a magnetic boundary. Sedimentation rates varied by an order of magnitude at this site, with minimum accumulation during glacial events. Interglacial intervals were charactrized by high marine production and high summer precipitation on land, while glacials had very low production and arid continental climate. During the large glacial events (Stages 96-100) conditions of low production and continental aridity reached their greatest intensity, but there is no evidence of a permanent mode shift in either marine or terrestrial records. Calcite concentration has a strong variation at obliquity frequencies, with maxima during interglacials, but occasionally shows a large amplitude at precessional frequencies as well, so that high concentrations occur in a few glacial intervals. As a result, color variation is not a reliable guide to glacial-scale cycles at this site. Composition of the phytoplankton assemblage is diverse and highly variable, and we have not been able to distinguish a clear indicator of upwelling-related production. Spectral analysis reveals obliquity and precessional signals in the pollen data, while several diatom records contain combination tones, indicating that these data represent a complicated response to both local and high-latitude forcing.

Stable carbon isotope ratios of n-alkane in ODP Hole 175-1083A in the South Atlantic Ocean (Table 1)

The intensification of Northern Hemisphere Glaciation (iNHG) is one of the critical climate thresholds in the Cenozoic. This study focuses on marine sediments recovered from Marine Isotope Stages 101/100 at the Ocean Drilling Program Site 1083 to assesses the impact of the iNHG on continental southern African vegetation through n-alkane (straight-chain hydrocarbon) abundance and delta13C values. The n-alkane abundance data yield a convoluted signal due to the number of controlling factors such as the source area, transportation routes and vegetation type. The C31 n-alkane delta13C values, however, exhibit a cyclic pattern with a periodicity of c. 20 ka, and are not correlated to the abundance data. It is inferred that the signal does not represent a change in the geographical source of n-alkanes. Instead, we suggest that the variations are caused by water-stress-induced changes in either carbon isotope fractionation during C3 photosynthesis or subtle changes in the proportion of C3 and C4 plants. These changes, unlike variations in oceanographic proxies, closely track precessional forcing factors and are independent of the prevailing obliquity-forced glacial/interglacial cycles. We conclude that the varying monsoon strength, rather than pCO2 or temperature change, forced changes in southern African vegetation during this period.