Oxygen and carbon isotope ratios for six planktonic foraminifer species from different water depth, Ontong-Java Plateau, Pacific (Table 2)

Stable isotope analyses and scanning electron micrographs have been carried out on six planktonic forminifera species, Pulleniatina obliquiloculata, Globorotalia tumida, Sphaeroidinella dehiscens, Globigerinoides ruber, Globigerinoides sacculifer and Globigerinoides quadrilobatus from eleven box-cores taken at increasing depths in the equatorial Ontong-Java Plateau (Pacific). This allows us to describe the way dissolution affects the microstructures of the tests of the different species and to quantify the changes of isotopic composition. We may conclude that: 1) dissolution effects on test morphology and stable isotope compositions are species dependent, species with a similar habitat showing a similar trend; 2) the shallow water, thin-shelled species are the first to disappear: scanning electron microscope (SEM) work shows alteration of outer layers. Deep water, thick-shelled species are present in all samples: SEM work shows breakdown and disparition of inner layers; 3) for all species there is a similar trend towards increasing delta18O values with increasing water depths and increasing dissolution. This effect may be as high as 0.6 ? per thousand meters for Globorotalia tumida; 4) below the lysocline, around 3500 m, it appears that 13C/12C ratios slightly increase towards equilibrium values for thick shelled species: G. tumida, P. obliquiloculata and S. dehiscens. 14C dates and isotope stratigraphy of two box-cores show that all samples are recent in age, and exclude upward mixing of glacial deposits as an important factor.

Stable isotopes and Mg/Ca ratios on foraminifera and Ba/Ca ratios of sediment core SK168/GC-1

The past variability of the South Asian Monsoon is mostly known from records of wind strength over the Arabian Sea while high-resolution paleorecords from regions of strong monsoon precipitation are still lacking. Here, we present records of past monsoon variability obtained from sediment core SK 168/GC-1, which was collected at the Alcock Seamount complex in the Andaman Sea. We utilize the ecological habitats of different planktic foraminiferal species to reconstruct freshwater-induced stratification based on paired Mg/Ca and d18O analyses and to estimate seawater d18O (d18Osw). The difference between surface and thermocline temperatures (delta T) and d18Osw (delta d18Osw) is used to investigate changes in upper ocean stratification. Additionally, Ba/Ca in G. sacculifer tests is used as a direct proxy for riverine runoff and sea surface salinity (SSS) changes related to monsoon precipitation on land. Our delta d18Osw time series reveals that upper ocean salinity stratification did not change significantly throughout the last glacial suggesting little influence of NH insolation changes. The strongest increase in temperature gradients between the mixed layer and the thermocline is recorded for the mid-Holocene and indicate the presence of a significantly shallower thermocline. In line with previous work, the d18Osw and Ba/Ca records demonstrate that monsoon climate during the LGM was characterized by a significantly weaker southwest monsoon circulation and strongly reduced runoff. Based on our data the South Asian Summer Monsoon (SAM) over the Irrawaddyy strengthened gradually after the LGM beginning at ~18 ka. This is some 3 kyrs before an increase of the Ba/Ca record from the Arabian Sea and indicates that South Asian Monsoon climate dynamics are more complex than the simple N-S displacement of the ITCZ as generally described for other regions. Minimum d18Osw values recorded during the mid-Holocene are in phase with Ba/Ca marking a stronger monsoon precipitation, which is consistent with model simulations.

Depth, age, strontium isotopic ratios and trace elemental ratios of samples from thirteen DSDP and ODP holes

Large variations exist between published mid-Cretaceous (late Barremian to early Turonian stages) seawater Sr-isotope stratigraphies; this has resulted in disparate interpretations of crustal production rates. We report on a detailed investigation of seawater Sr-isotope stratigraphy based on foraminifers and, where available, on inoceramid bivalves from 12 mid-Cretaceous Deep Sea Drilling Project and Ocean Drilling Program sections. The effects of diagenesis are assessed using scanning electron microscope observations and trace-elemental analyses, but are best distinguished by comparing the 87Sr/86Sr values of similar-age samples from different sites. Strontium-isotope analyses compiled from 9 of 12 sites that have detailed age control define one band of common values. This band is used as a composite curve, which presumably represents seawater 87Sr/86Sr values. The composite curve shows a "trough" of markedly lower 87Sr/86Sr values in the Aptian and early Albian stages, higher but constant values for the middle Albian-Cenomanian stages, followed by a decrease in 87Sr/86Sr values in the early Turonian. Variations between published mid-Cretaceous Sr-isotope records result from diagenetic alteration, analytical problems, and the diverse biostratigraphic approaches and assumptions used to estimate sample ages. When preexisting age data are made consistent, the composite record shows close similarities with data sets derived from measurements of macrofossils in land sections of Europe and North America. The interval of decreased 87Sr/86Sr values in the Aptian-Albian stages overlaps with the pulse of mid-plate volcanic activity that produced the Ontong Java, Manihiki, and Kerguelen Plateaus. The exact age and the shape of the trough, however, are consistent with increased spreading rates at oceanic ridges, given the existing data on the timing of mid-plate volcanic activity.

(Table 1) Stable oxygen isotope ratios of benthic foraminifera from Pacific Ocean deep-sea sediments

The thermal structure of the Pacific Ocean between water depths of about 1 and 4.5 kilometers is estimated from the oxygen isotopic ratio of benthonic foraminifera from deep-drilled and piston cores of early Pliocene age (about 3 to 5 million years ago). The ratio of oxygen-18 to oxygen-16 in the early Pliocene at each site varies by an average of only ± 0.12 per mil (1 standard deviation). A plot of the oxygen isotopic ratio against modern bottom-water temperature is adequately fit by a line having a slope of - 0.26 per mil per degree Celsius (the equilibrium temperature dependence of calcite-water fractionation), suggesting that the temperature gradient of the Pacific Ocean during the early Pliocene was similar to that of today.

Molar gas ratios and stable oxygen and nitrogen isotopes of air entrapped in ice, North America

The molar ratios of atmospheric gases change during dissolution in water due to differences in their relative solubilities. We exploited this characteristic to develop a tool to clarify the origin of ice formations in permafrost regions. Extracted from ice, molar gas ratios can distinguish buried glacier ice from intrasedimental ground ice formed by freezing groundwaters. An extraction line was built to isolate gases from ice by melting and trapping with liquid He, followed by analysis of N2, O2, Ar, 18O-O2 and 15N-N2, by continuous flow mass spectrometry. The method was tested using glacier ice, aufeis ice (river icing) and intrasedimental ground ice from sites in the Canadian Arctic. O2/Ar and N2/Ar ratios clearly distinguish between atmospheric gas in glacial ice and gases from intrasedimental ground ice, which are exsolved from freezing water. 615NN2 and 618OO2 in glacier ice, aufeis ice and intrasedimental ground ice do not show clear distinguishing trends as they are affected by various physical processes during formation such as gravitational settling, excess air addition, mixing with snow pack, and respiration.

Planktonic foraminiferal biostratigraphy and stable carbon isotope ratios of late middle Eocene sediments from Blake Plateau, West Atlantic Ocean

The muricate planktonic foraminiferal genera Morozovella and Acarinina were abundant and diverse during the upper Palaeocene to middle Eocene and dominated the tropical and subtropical assemblages. A significant biotic turnover in planktonic foraminifera occurred in the latest middle Eocene with a notable reduction in the acarininid lineage and the extinction of the morozovellids. These genera are extensively employed as palaeoclimatic and biostratigraphic markers and, therefore, this turnover episode is an important event in the record of the Cenozoic planktonic foraminifera. Sediments from the western North Atlantic (Ocean Drilling Program Site 1052) were examined in order to investigate these extinction events, in terms of both timing and mechanisms. Biostratigraphic events of the middle and late Eocene have been examined with a sampling resoluti on of approximately 3 kyr. These have been calibrated to the magneto- and astrochronology to accurately define the timing of key biostratigraphic events, particularly the extinction of Morozovella spinulosa which is a distinct biomarker for late middle Eocene sediments. High-resolution biostratigraphy reveals that the extinctions in the muricate group occurred in a stepwise form. The large acarininids (Acarinina praetopilensis) terminate 10 kyr prior to the extinction of M. spinulosa and small acarininids (Acarinina medizzai and Acarinina echinata) continue into the upper Eocene. High-resolution stable isotope analyses have been conducted on planktonic and benthic foraminifera from the western North Atlantic to reconstruct sea surface temperatures (SSTs) and deep water temperatures and the structure of the water column around this major biotic turnover. Whilst the extinctions of M. spinulosa and A. praetopilensis occur during a long-term cooling trend, the biotic turnover in the muricate group does not appear to be related to significant climatic change. Sea surface temperatures decrease slowly prior to the extinction events, and there is no evidence for a large-temperature shift associated with the faunal changes. The turnover event was therefore probably related to the increased surface water productivity and the deterioration of photosymbiotic partnerships with algae.

Zircons, isotope ratios and element analyses from tonalite and oxide gabbro of the mid-ocean ridge from ODP Hole 176-735B

A limiting factor in the accuracy and precision of U/Pb zircon dates is accurate correction for initial disequilibrium in the 238U and 235U decay chains. The longest-lived-and therefore most abundant-intermediate daughter product in the 235U isotopic decay chain is 231Pa (T1/2 = 32.71 ka), and the partitioning behavior of Pa in zircon is not well constrained. Here we report high-precision thermal ionization mass spectrometry (TIMS) U-Pb zircon data from two samples from Ocean Drilling Program (ODP) Hole 735B, which show evidence for incorporation of excess 231Pa during zircon crystallization. The most precise analyses from the two samples have consistent Th-corrected 206Pb/238U dates with weighted means of 11.9325 ± 0.0039 Ma (n = 9) and 11.920 ± 0.011 Ma (n = 4), but distinctly older 207Pb/235U dates that vary from 12.330 ± 0.048 Ma to 12.140 ± 0.044 Ma and 12.03 ± 0.24 to 12.40 ± 0.27 Ma, respectively. If the excess 207Pb is due to variable initial excess 231Pa, calculated initial (231Pa)/(235U) activity ratios for the two samples range from 5.6 ± 1.0 to 9.6 ± 1.1 and 3.5 ± 5.2 to 11.4 ± 5.8. The data from the more precisely dated sample yields estimated DPazircon/DUzircon from 2.2-3.8 and 5.6-9.6, assuming (231Pa)/(235U) of the melt equal to the global average of recently erupted mid-ocean ridge basaltic glasses or secular equilibrium, respectively. High precision ID-TIMS analyses from nine additional samples from Hole 735B and nearby Hole 1105A suggest similar partitioning. The lower range of DPazircon/DUzircon is consistent with ion microprobe measurements of 231Pa in zircons from Holocene and Pleistocene rhyolitic eruptions (Schmitt (2007; doi:10.2138/am.2007.2449) and Schmitt (2011; doi:10.1146/annurev-earth-040610-133330)). The data suggest that 231Pa is preferentially incorporated during zircon crystallization over a range of magmatic compositions, and excess initial 231Pa may be more common in zircons than acknowledged. The degree of initial disequilibrium in the 235U decay chain suggested by the data from this study, and other recent high precision datasets, leads to resolvable discordance in high precision dates of Cenozoic to Mesozoic zircons. Minor discordance in zircons of this age may therefore reflect initial excess 231Pa and does not require either inheritance or Pb loss.

Sr/Ca ratios of coccoliths from the Paleocene-Eocene Thermal Maximum

During the Paleocene-Eocene Thermal Maximum (PETM), rapid release of isotopically light C to the ocean-atmosphere system elevated the greenhouse effect and warmed temperatures by 5-7 °C for 105 yr. The response of the planktic ecosystems and productivity to the dramatic climate changes of the PETM may represent a significant feedback to the carbon cycle changes, but has been difficult to document. We examine Sr/Ca ratios in calcareous nannofossils in sediments spanning the PETM in three open ocean sites as a new approach to examine productivity and ecological shifts in calcifying plankton. The large heterogeneity in Sr/Ca among different nannofossil genera indicates that nannofossil Sr/Ca reflects primary productivity-driven geochemical signals and not diagenetic overprinting. Elevated Sr/Ca ratios in several genera and constant ratios in other genera suggest increased overall productivity in the Atlantic sector of the Southern Ocean during the PETM. Dominant nannofossil genera in tropical Atlantic and Pacific sites show Sr/Ca variations during the PETM which are comparable to background variability prior to the PETM. Despite acidification of the ocean there was not a productivity crisis among calcifying phytoplankton. We use the Pandora ocean box model to explore possible mechanisms for PETM productivity change. If independent proxy evidence for more stratified conditions in the Southern Ocean during the PETM is robust, then maintenance of stable or increased productivity there likely reflects increased nutrient inventories of the ocean. Increased nutrient inventories could have resulted from climatically enhanced weathering and would have important implications for burial rates of organic carbon and stabilization of climate and the carbon cycle.

(Table 1) Calcium isotope composition, Mg/Ca, Sr/Ca and U/Ca ratios of calcareous cysts of Thoracosphaera heimii

We investigated the influences of temperature, salinity and pH on the calcium isotope as well as trace and minor element (uranium, strontium, magnesium) to Ca ratios on calcium carbonate cysts of the calcareous dinoflagellate species Thoracosphaera heimii grown in laboratory cultures. The natural habitat of this species is the photic zone (preferentially at the chlorophyll maximum depth) of temperate to tropical oceans, and it is abundant in deep-sea sediments over the entire Cenozoic. In our experiments, temperatures ranged from 12 to 30 °C, salinity from 36.5 to 38.8 and pH from 7.9 to 8.4. The delta44/40Ca of T. heimii cysts resembles that of other marine calcifiers, including coccolithophores, foraminifers and corals. However, its temperature sensitivity is considerably smaller and statistically insignificant, and T. heimii might serve as a recorder of changes in seawater delta44/40Ca over geologic time. The Sr/Ca ratios of T. heimii cysts show a pronounced temperature sensitivity (0.016 mmol/mol °C**-1) and have the potential to serve as a palaeo-sea surface temperature proxy. No clear temperature- and pH-dependences were observed for Mg/Ca. U/Ca seems to be influenced by temperature and pH, but the correlations change sign at 23 °C and pH 8.2, respectively.