Stable oxygen isotope record of benthic foraminifera from the tropical Atlantic

Benthic foraminiferal oxygen isotope ratios from two sediment cores recovered at 426 and 1299 m water depth in the eastern and western tropical Atlantic show that a slowdown of the thermohaline circulation (THC) during Heinrich event H1 and the Younger Dryas was accompanied by rapid and intense warming of intermediate depth waters. Millennial-scale covariations of low paleosalinities in the subpolar North Atlantic with decreased benthic oxygen isotope ratios in the eastern tropical Atlantic throughout the past 10,000 years suggest that THC weakening might be related to middepth warming during the Holocene period as well. Climate model experiments simulating a strong reduction of the THC in the Atlantic Ocean under present-day and glacial conditions reveal that the increase of temperature in the middepth tropical and South Atlantic is a common feature for both climatic states, caused by a reduced ventilation of cold intermediate and deep waters in conjunction with downward mixing of heat from the thermocline. From the similarity of the paleoclimatic records with the model simulations, we infer that the characteristic pattern of temperature change in the Atlantic Ocean related to weakened thermohaline circulation can serve as an indicator of present-day and future THC slowdown.

(Table 1) Stable carbon isotope ratios of methane and carbon dioxide from ODP Leg 169S holes

Sites 1033 and 1034 of ODP Leg 169S in Saanich Inlet have an unusual diagenetic system, that has the appearance of being depth reversed, i.e. a bacterial methane accumulation zone underlain by a sulphate reduction zone. During the late Pleistocene grey, undifferentiated, glacio-marine clays were deposited with low Corg contents (<0.4 wt.%), and interstitial fluids replete in SO4 (ca. 27 mM), devoid of CH4 and low in nutrients. This indicates oxic conditions are present, reflecting the open exchange of waters with Haro Strait during the Pleistocene before the Saanich Peninsula emerged. In the earliest Holocene (ca. 11,000 years BP) the inlet was formed, severely restricting water circulation, and leading to the presence of anoxic bottom waters. The sediments are laminated and show a dramatic rise to high Corg, Norg and Stot contents (up to 2.5, 0.4, 1.4 wt.%, respectively) over a period of ca. 1000 years. The nutrient concentrations are especially high (TA, NH4, PO4 up to 115 meq/l, 20 mM and 400 µM, respectively), SO4 is exhausted and CH4 is prolific. Stable carbon isotope ratio measurements of CH4 and co-existing CO2 indicate that methanogenesis is via carbonate reduction (delta13C-CH4 ca. -60 to - 70 per mil, delta13C-CO2 ca. +10 per mil). At the sulphate-methane interfaces, both at the near-surface and at 50 mbsf (Site 1033) and 80 mbsf (Site 1034) methane consumption by sulphate reducing bacteria is intensive.

(Table 1) Stable oxygen isotope ratios of interstitial waters from ODP Sites 164-994 and 164-997

The d18O values of interstitial waters from Site 994 and Site 997 sediments, Blake Ridge, western Atlantic, tend to decrease with depth from 0.3 per mil to -0.5 per mil Standard Mean Ocean Water in the upper 200 mbsf, then fluctuate with significant positive spikes of Delta = 0.2 per mil - 0.5 per mil in the gas hydrate zone (200 to 450 mbsf), and finally increase from -0.4 per mil to -0.2 per mil toward 700 mbsf. Positive shifts of d18O IW in the gas hydrate zone are probably caused by the dissociation of gas hydrates originally contained in sediment cores. Gas hydrates recovered from the sites are enriched in 18O, d18O ranging between 2.7 per mil and 3.5 per mil. d18O values of gas hydrates and ambient interstitial waters give an oxygen isotopic fractionation factor of 1.0034-1.0040 at 12°-16°C and ~31 MPa (3 km below sea level). Based on this fractionation and observed isotopic anomalies in the gas hydrate zone, gas hydrates occupy 6% to 12% of pore-space volume within Blake Ridge sediments.

Stable oxygen isotope record of coral core RUS-95 from the Red Sea

A 245-year coral oxygen isotope record from the northern Red Sea (Ras Umm Sidd/Egypt, ~28°N) in bimonthly resolution is presented. The mean annual coral delta18O signal apparently reflects varying proportions of both sea surface temperature and delta18Oseawater variability. In conjunction with instrumental observations of climate the coral record suggests for interannual and longer timescales that colder periods are accompanied by more arid conditions in the northern Red Sea but increased rainfall in the southeastern Mediterranean, whereas warmer periods are accompanied by decreased rainfall in the latter and less arid conditions in the northern Red Sea. A ~70-year oscillation of probably North Atlantic origin dominates the coral time series. Interannual to interdecadal variability is correlated with instrumental indices of the North Atlantic Oscillation (NAO), the El Niño-Southern Oscillation (ENSO), and North Pacific climate variability. The results suggest that these modes contributed consistently to Middle East climate variability since at least 1750, preferentially at a period of ~5.7 years.

Mg/Ca and stable oxygen isotope ratios of Uvigerina spp. from the Southern Ocean

The sensitivity to temperature of Mg/Ca ratios in the shallow-infaunal benthic foraminifera Uvigerina spp. has been assessed. Core-top calibrations over ~1-20 °C show a range in sensitivity of 0.065-0.084 mmol/mol/°C but few data are available spanning the temperature range anticipated in deep-sea records over glacial-interglacial cycles. In contrast to epibenthic foraminiferal species, carbonate ion saturation appears not to affect Mg/Ca significantly. A method based on estimating the ratio of the temperature sensitivity of foraminiferal Mg/Ca to that of d18Ocalcite shows that sensitivity for Mg/Ca at the high end of the observed core-top range (~0.1 mmol/mol/°C) is required for consistency with LGM-Holocene differences in each property as constrained by independent proxy data. This is supported by a Mg/Ca record for Uvigerina spp. generated for the Southern Ocean over the past 440,000 years from Ocean Drilling Program Site 1123 (Chatham Rise, New Zealand). The record shows variability that correlates with climate oscillations. The LGM deep ocean temperature derived from the Mg/Ca record is -1.1 ± 0.3 °C. Transformation to temperature allows estimates to be made of changes in bottom water temperature and seawater d18O and comparison made with literature records. Analysis reveals a ~2.5-kyr lead in the record of temperature over calcite d18O and a longer lead over seawater d18O. This is a reflection of larger phase offsets at eccentricity periods; phase offsets at tilt and precession are within error zero.

Stable carbon isotope ratios of carbon dioxide from EDC and Berkner Island ice cores for 40-50 ka BP

The stable carbon isotopic signature of carbon dioxide (d13CO2) measured in the air occlusions of polar ice provides important constraints on the carbon cycle in past climates. In order to exploit this information for previous glacial periods, one must use deep, clathrated ice, where the occluded air is preserved not in bubbles but in the form of air hydrates. Therefore, it must be established whether the original atmospheric d13CO2 signature can be reconstructed from clathrated ice. We present a comparative study using coeval bubbly ice from Berkner Island and ice from the bubble-clathrate transformation zone (BCTZ) of EPICA Dome C (EDC). In the EDC samples the gas is partitioned into clathrates and remaining bubbles as shown by erroneously low and scattered CO2 concentration values, presenting a worst-case test for d13CO2 reconstructions. Even so, the reconstructed atmospheric d13CO2 values show only slightly larger scatter. The difference to data from coeval bubbly ice is statistically significant. However, the 0.16 per mil magnitude of the offset is small for practical purposes, especially in light of uncertainty from non-uniform corrections for diffusion related fractionation that could contribute to the discrepancy. Our results are promising for palaeo-atmospheric studies of d13CO2 using a ball mill dry extraction technique below the BCTZ of ice cores, where gas is not subject to fractionation into microfractures and between clathrate and bubble reservoirs.

Stable oxygen isotope data and geophysical measurements from Red Sea of core M174/Kl11

To settle debate on the timing of sea level fluctuations during marine isotope stage (MIS) 3, we present records of d18O ruber (sea level proxy) and magnetic susceptibility from the same samples within the single sediment archive (i.e., "coregistered") of central Red Sea core GeoTü-KL11. Core-scanning X-ray fluorescence and environmental magnetic data establish the suitability of magnetic susceptibility as a proxy for eolian dust content in Red Sea sediments. The eolian dust data record similar variability as Greenland d18O ice during early to middle MIS 3, in agreement with previous observations that regional Arabian Sea climate fluctuated with a timing similar to that of Greenland climate variations. In contrast, the sea level record fluctuates with a timing similar to that of Antarctic-style climate variations. The coregistered nature of the two records in core KL11 unambiguously reveals a distinct offset in the phase relationship between sea level and eolian dust fluctuations. The results confirm that sea level rises, indicated by shifts in Red Sea d18O ruber to lighter values, occurred during cold episodes in Greenland during early to middle MIS 3. This indicates that the amplitudes of the reconstructed MIS 3 sea level fluctuations would not be reduced by inclusion of regional climate fluctuations in the Red Sea sea level method. Our analysis comprehensively supports our earlier conclusions of large-amplitude sea level variations during MIS 3 with a timing that is strongly similar to Antarctic-style climate variations.

(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.

THE MICROSTRUCTURES OF ZR-EXCEL ALLOY: EFFECTS OF HEAVY ION IRRADIATION, PLASTIC DEFORMATION, THERMAL TREATMENT AND IN-SITU HEATING

Zr-Excel alloy (Zr-3.5Sn-0.8Nb-0.8Mo) is a dual phase (α + β) alloy in the as-received pressure tube condition. It has been proposed to be the pressure tube candidate material for the Generation-IV CANDU-Supercritical Water Reactor (CANDU-SCWR). In this dissertation, the effects of heavy ion irradiation, deformation and heat treatment on the microstructures of the alloy were investigated to enable us to have a better understanding of the potential in-reactor performance of this alloy. In-situ heavy ion (1 MeV) irradiation was performed to study the nucleation and evolution of dislocation loops in both α- and β-Zr. Small and dense type dislocation loops form under irradiation between 80 and 450 °C. The number density tends to saturate at ~ 0.1 dpa. Compared with the α-Zr, the defect yield is much lower in β-Zr. The stabilities of the metastable phases (β-Zr and ω-Zr) and the thermal-dynamically equilibrium phase, fcc Zr(Mo, Nb)2, under irradiation were also studied at different temperatures. Chemi-STEM elemental mapping was carried out to study the elemental redistribution caused by irradiation. The stability of these phases and the elemental redistribution are strongly dependent on irradiation temperature. In-situ time-of-flight neutron diffraction tensile and compressive tests were carried out at different temperatures to monitor lattice strain evolutions of individual grain families during these tests. The β-Zr is the strengthening phase in this alloy in the as-received plate material. Load is transferred to the β-Zr after yielding of the α-Zr grains. The temperature dependence of static strain aging and the yielding sequence of the individual grain families were discussed. Strong tensile/compressive asymmetry was observed in the {0002} grain family at room temperature. The microstructures of the sample deformed at 400 °C and the samples only subjected to heat treatment at the same temperature were characterized with TEM. Concentration of β phase stabilizers in the β grain and the morphology of β grain have significant effect on the stability of β- and ω-Zr under thermal treatment. Applied stress/strain enhances the decomposition of isothermal ω phase but suppresses α precipitation inside the β grains at high temperature. An α → ω/ZrO phase transformation was observed in the thin foils of Zr-Excel alloy and pure Zr during in-situ heating at 700 °C in TEM.

Stable water isotope composition of precipitation from O'Higgins Station, Antarctica, 2008-2009

In order to investigate the climate variability in the northern Antarctic Peninsula region, this paper focuses on the relationship between stable isotope content of precipitation and firn, and main meteorological variables (air temperature, relative humidity, sea surface temperature, and sea ice extent). Between 2008 and 2010, we collected precipitation samples and retrieved firn cores from several key sites in this region. We conclude that the deuterium excess oscillation represents a robust indicator of the meteorological variability on a seasonal to sub-seasonal scale. Low absolute deuterium excess values and the synchronous variation of both deuterium excess and air temperature imply that the evaporation of moisture occurs in the adjacent Southern Ocean. The d18O-air temperature relationship is complicated and significant only at a (multi)seasonal scale. Backward trajectory calculations show that air-parcels arriving at the region during precipitation events predominantly originate at the South Pacific Ocean and Bellingshausen Sea. These investigations will be used as a calibration for ongoing and future research in the area, suggesting that appropriate locations for future ice core research are located above 600 m a.s.l. We selected the Plateau Laclavere, Antarctic Peninsula as the most promising site for a deeper drilling campaign.

Stable carbon isotope ratios and accumulation rates of organic carbon and nutrients of DSDP Hole 79-545 (Appendix A)

Future warming is predicted to shift the Earth system into a mode with progressive increase and vigour of extreme climate events possibly stimulating other mechanisms that invigorate global warming. This study provides new data and modelling investigating climatic consequences and biogeochemical feedbacks that happened in a warmer world ~112 Myr ago. Our study focuses on the Cretaceous Oceanic Anoxic Event (OAE) 1b and explores how the Earth system responded to a moderate ~25,000 yr lasting climate perturbation that is modelled to be less than 1 °C in global average temperature. Using a new chronological model for OAE 1b we present high-resolution elemental and bulk carbon isotope records from DSDP Site 545 from Mazagan Plateau off NW Africa and combine this information with a coupled atmosphere-land-ocean model. The simulations suggest that a perturbation at the onset of OAE 1b caused almost instantaneous warming of the atmosphere on the order of 0.3 °C followed by a longer (~45,000 yr) period of ~0.8 °C cooling. The marine records from DSDP Site 545 support that these moderate swings in global climate had immediate consequences for African continental supply of mineral matter and nutrients (phosphorous), subsequent oxygen availability, and organic carbon burial in the eastern subtropical Atlantic, however, without turning the ocean anoxic. The match between modelling results and stratigraphic isotopic data support previous studies [summarized in Jenkyns 2003, doi:10.1098/rsta.2003.1240] in that methane emission from marine hydrates, albeit moderate in dimension, may have been the trigger for OAE 1b, though we can not finally rule out alternative mechanisms. Following the hydrate mechanism a total of 1.15 * 10**18 g methane carbon (delta13C=-60 ?), equivalent to about 10% to the total modern gas hydrate inventory, generated the delta13Ccarb profile recorded in the section. Modelling suggests a combination of moderate-scale methane pulses supplemented by continuous methane emission at elevated levels over ~25,000 yr. The proposed mechanism, though difficult to finally confirm in the geological past, is arguably more likely to occur in a warmer world and apparently perturbs global climate and ocean chemistry almost instantaneously. This study shows that, once set-off, this mechanism can maintain Earth's climate in a perturbed mode over geological time leading to pronounced changes in regional climate.

In situ characterization of porous VPO catalysts with fibrous structure: Identifying the redox behavior and the stability of active sites

Two VPO materials with fibrillar morphology have been prepared by the aid of electrospinning technique. One is a VPO carbon-supported material (VCF200) with fibrous morphology and very high surface area that is stable under oxidizing conditions up to 350C. The other material is a bulk mixed VPO oxide (VPO500) with fibrous structure obtained after optimizing the calcination of the carbon support in VCF200. Despite it is a bulk oxide material, this material exhibits a high surface area (> 60 m2/g). The redox behavior of both samples was monitored by in situ Raman spectroscopy under oxidation/reduction cycles. For the dehydrated supported sample (VCF200), the pyrophosphate phase (VO)2P2O7 (Raman ~930 cm-1) is detected, which has been described as the active phase (see Figure (a) below). This phase is quite stable since it does not disappear upon subsequent oxidation/reduction cycles. Under reduction conditions at 125C, in consecutive cycles, additional Raman bands appear at ~1090 cm-1 that are characteristic of the αII-VOPO4 phase. On the other hand, the bulk phases show a reversible behavior under redox cycles (Figure (b)). Under reducing conditions, a Raman band appears at ~980 cm-1 (β-VPO phase), whereas under oxidation conditions some segregation to VOx oxides occurs. Nevertheless, this segregation is reversible and the β-VPO phase forms again under reducing conditions. Thus, these results demonstrate that the active VPO phases of these fibrous catalysts are quite stable, and that their structure is reversible under several redox cycles, which make them suitable as oxidation catalysts.

Estudo do processo de combustão in-situ em reservatórios maduros de óleos médios e leves (high pressure air injection)

Nearly 3 x 1011 m3 of medium and light oils will remain in reservoirs worldwide after conventional recovery methods have been exhausted and much of this volume would be recovered by Enhanced Oil Recovery (EOR) methods. The in-situ combustion (ISC) is an EOR method in which an oxygen-containing gas is injected into a reservoir where it reacts with the crude oil to create a high-temperature combustion front that is propagated through the reservoir. The High Pressure Air Injection (HPAI) method is a particular denomination of the air injection process applied in light oil reservoirs, for which the combustion reactions are dominant between 150 and 300°C and the generation of flue gas is the main factor to the oil displacement. A simulation model of a homogeneous reservoir was built to study, which was initially undergone to primary production, for 3 years, next by a waterflooding process for 21 more years. At this point, with the mature condition established into the reservoir, three variations of this model were selected, according to the recovery factors (RF) reached, for study the in-situ combustion (HPAI) technique. Next to this, a sensitivity analysis on the RF of characteristic operational parameters of the method was carried out: air injection rate per well, oxygen concentration into the injected gas, patterns of air injection and wells perforations configuration. This analysis, for 10 more years of production time, was performed with assistance of the central composite design. The reservoir behavior and the impacts of chemical reactions parameters and of reservoir particularities on the RF were also evaluated. An economic analysis and a study to maximize the RF of the process were also carried out. The simulation runs were performed in the simulator of thermal processes in reservoirs STARS (Steam, Thermal, and Advanced Processes Reservoir Simulator) from CMG (Computer Modelling Group). The results showed the incremental RF were small and the net present value (NPV) is affected by high initial investments to compress the air. It was noticed that the adoption of high oxygen concentration into the injected gas and of the five spot pattern tends to improve the RF, and the wells perforations configuration has more influence with the increase of the oil thickness. Simulated cases relating to the reservoir particularities showed that smaller residual oil saturations to gas lead to greater RF and the presence of heterogeneities results in important variations on the RF and on the production curves

Can gut microbiota analysis be beneficial for ex-situ and in-situ conservation of threatened animal species?

Ex-situ conservation and the in-situ conservation of natural habitats are the tools to conserve biodiversity. Habitats and ecosystems have been becoming altered by human activities and a growing number of species requires form of management to ensure their survival. Conservation queries become more complex and urgent. Developing scientifically based and innovative approaches to ex-situ conservation is necessary. Recent studies underline importance of gut microbiome in animal health with implications for animal conservation and management. Animal and human studies have demonstrated that environmental factors can impact gut microbiome composition. Within this scenario, the present work focused on species belonging to different taxa, reptiles and mammals: Aldabrachelys gigantea, the giant tortoise of the Seychelles islands and Indri indri, the greatest leaving lemur of Madagascar. The Seychelles giant tortoise is vulnerable species with declining population, whereas the indri is a critically endangered species that could reach the extinction within 25 years. Both need research to help them to survive. Tortoises live for very long time and to observe how they can afford the environmental changes is very difficult. Indris, instead, are able to survive only in a small area of the Madagascar forest, with a very strong link between the species’ survival and the environment. The obtained results underline importance of environmental factors, both in-situ and ex-situ, for species conservation. Microbiome could help the organisms to respond on a short timescale and cope with, environmental changes. However, species with long generation time might not be able to adapt to fast changes but bacteria with a short generation time can adapt on a shorter timescale allowing the host to cope with fluctuating environment. Gut microbiome plays an important role in an animal’s health and has the potential to improve the management of individuals under human care for conservation purposes.