31 resultados para Al-MCM-41. Thermogravimetry. Model free kinetics. Apparent activation energy

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Today the deep western boundary current (DWBC) east of New Zealand is the most important route for deep water entering the Pacific Ocean. Large-scale changes in deep water circulation patterns are thought to have been associated with the development of the East Antarctic Ice Sheet (EAIS) close to the main source of bottom water for the DWBC. Here we reconstruct the changing speed of the southwest Pacific DWBC during the middle Miocene from ~15.5-12.5 Ma, a period of significant global ice accumulation associated with EAIS growth. Sortable silt mean grain sizes from Ocean Drilling Program Site 1123 reveal variability in the speed of the Pacific inflow on the timescale of the 41 kyr orbital obliquity cycle. Similar orbital period flow changes have recently been demonstrated for the Pleistocene epoch. Collectively, these observations suggest that a strong coupling between changes in the speed of the deep Pacific inflow and high-latitude climate forcing may have been a persistent feature of the global thermohaline circulation system for at least the past 15 Myr. Furthermore, long-term changes in flow speed suggest an intensification of the DWBC under an inferred increase in Southern Component Water production. This occurred at the same time as decreasing Tethyan outflow and major EAIS growth between ~15.5 and 13.5 Ma. These results provide evidence that a major component of the deep thermohaline circulation was associated with the middle Miocene growth of the EAIS and support the view that this time interval represents an important step in the development of the Neogene icehouse climate.

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The climate during the Cenozoic era changed in several steps from ice-free poles and warm conditions to ice-covered poles and cold conditions. Since the 1950s, a body of information on ice volume and temperature changes has been built up predominantly on the basis of measurements of the oxygen isotopic composition of shells of benthic foraminifera collected from marine sediment cores. The statistical methodology of time series analysis has also evolved, allowing more information to be extracted from these records. Here we provide a comprehensive view of Cenozoic climate evolution by means of a coherent and systematic application of time series analytical tools to each record from a compilation spanning the interval from 4 to 61 Myr ago. We quantitatively describe several prominent features of the oxygen isotope record, taking into account the various sources of uncertainty (including measurement, proxy noise, and dating errors). The estimated transition times and amplitudes allow us to assess causal climatological-tectonic influences on the following known features of the Cenozoic oxygen isotopic record: Paleocene-Eocene Thermal Maximum, Eocene-Oligocene Transition, Oligocene-Miocene Boundary, and the Middle Miocene Climate Optimum. We further describe and causally interpret the following features: Paleocene-Eocene warming trend, the two-step, long-term Eocene cooling, and the changes within the most recent interval (Miocene-Pliocene). We review the scope and methods of constructing Cenozoic stacks of benthic oxygen isotope records and present two new latitudinal stacks, which capture besides global ice volume also bottom water temperatures at low (less than 30°) and high latitudes. This review concludes with an identification of future directions for data collection, statistical method development, and climate modeling.

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Downhole temperature and thermal conductivity measurements in core samples recovered during Legs 127 and 128 in the Japan Sea resulted in five accurate determinations of heat flow through the seafloor and accurate estimates of temperature vs. depth over the drilled sections. The heat flows measured at these sites are in excellent agreement with nearby seafloor measurements. Drilling sampled basaltic rocks that form the acoustic basement in the Yamato and Japan basins and provided biostratigraphic and isotopic estimates of the age of these basins. The preliminary age estimates are compared with predicted heat flow values for two different thermal models of the lithosphere. A heat flow determination from the crest of the Okushiri Ridge yielded an anomalously high heat flow of 156 mW/m**2. This excessive heat flow value may have resulted from frictional heating on an active reverse fault that bounds the eastern side of the Ridge. Accurate estimates of sedimentation rates and temperatures in the sedimentary section combined with models of basin formation provide an opportunity to test thermochemical models of silica diagenesis. The current location of the opal-A/opal CT transition in the sedimentary section is determined primarily by the thermal history of the layer in which the transition is now found. Comparison of the ages and temperatures of the layer where the opal-A/opal-CT is found today is compatible with an activation energy of 14 to 17 kcal/mole.

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Here we present an improved astronomical timescale since 5 Ma as recorded in the ODP Site 1143 in the southern South China Sea, using a recently published Asian summer monsoon record (hematite to goethite content ratio, Hm/Gt) and a parallel benthic d18O record. Correlation of the benthic d18O record to the stack of 57 globally distributed benthic d18O records (LR04 stack) and the Hm/Gt curve to the 65°N summer insolation curve is a particularly useful approach to obtain refined timescales. Hence, it constitutes the basis for our effort. Our proposed modifications result in a more accurate and robust chronology than the existing astronomical timescale for the ODP Site 1143. This updated timescale further enables a detailed study of the orbital variability of low-latitude Asian summer monsoon throughout the Plio-Pleistocene. Comparison of the Hm/Gt record with the d18O record from the same core reveals that the oscillations of low-latitude Asian summer monsoon over orbital scales differed considerably from the glacial-interglacial climate cycles. The popular view that summer monsoon intensifies during interglacial stages and weakens during glacial stages appears to be too simplistic for low-latitude Asia. In low-latitude Asia, some strong summer monsoon intervals appear to have also occurred during glacial stages in addition to their increased occurrence during interglacial stages. Vice versa, some notably weak summer monsoon intervals have also occurred during interglacial stages next to their anticipated occurrence during glacial stages. The well-known mid-Pleistocene transition (MPT) is only identified in the benthic d18O record but not in the Hm/Gt record from the same core. This suggests that the MPT may be a feature of high- and middle-latitude climates, possibly determined by high-latitude ice sheet dynamics. For low-latitude monsoonal climate, its orbital-scale variations respond more directly to insolation and are little influenced by high-latitude processes, thus the MPT is likely not recorded. In addition, the Hm/Gt record suggests that low-latitude Asian summer monsoon intensity has a long-term decreasing trend since 2.8 Ma with increased oscillation amplitude. This long-term variability is presumably linked to the Northern Hemisphere glaciation since then.

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Global cooling and the development of continental-scale Antarctic glaciation occurred in the late middle Eocene to early Oligocene (~38 to 28 million years ago), accompanied by deep-ocean reorganization attributed to gradual Antarctic Circumpolar Current (ACC) development. Our benthic foraminiferal stable isotope comparisons show that a large d13C offset developed between mid-depth (~600 meters) and deep (>1000 meters) western North Atlantic waters in the early Oligocene, indicating the development of intermediate-depth d13C and O2 minima closely linked in the modern ocean to northward incursion of Antarctic Intermediate Water. At the same time, the ocean's coldest waters became restricted to south of the ACC, probably forming a bottom-ocean layer, as in the modern ocean. We show that the modern four-layer ocean structure (surface, intermediate, deep, and bottom waters) developed during the early Oligocene as a consequence of the ACC.

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A long-standing question in Paleogene climate concerns the frequency and mechanism of transient greenhouse gas-driven climate shifts (hyperthermals). The discovery of the greenhouse gas-driven Paleocene-Eocene Thermal Maximum (PETM; ~55 Ma) has spawned a search for analogous events in other parts of the Paleogene record. On the basis of high-resolution bulk sediment and foraminiferal stable isotope analyses performed on three lower Danian sections of the Atlantic Ocean, we report the discovery of a possible greenhouse gas-driven climatic event in the earliest Paleogene. This event - that we term the Dan-C2 event - is characterized by a conspicuous double negative excursion in delta13C and delta18O, associated with a double spike in increased clay content and decreased carbonate content. This suggests a double period of transient greenhouse gas-driven warming and dissolution of carbonates on the seafloor analogous to the PETMin the early Paleocene at ~65.2 Ma. However, the shape of the two negative carbon isotope excursions that make up the Dan-C2 event is different from the PETM carbon isotope profile. In the Dan-C2 event, these excursions are fairly symmetrical and each persisted for about ~40 ky and are separated by a short plateau that brings the combined duration to ~100 ky, suggesting a possible orbital control on the event. Because of the absence of a long recovery phase, we interpret the Dan-C2 event to have been associated with a redistribution of carbon that was already in the biosphere. The Dan-C2 event and other early Paleogene hyperthermals such as the short-lived early Eocene ELMO eventmay reflect amplification of a regular cycle in the size and productivity of the marine biosphere and the balance between burial of organic and carbonate carbon.

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Surface and deep water circulation patterns in the eastern Indian Ocean during the Paleocene Epoch are inferred based on an integrated magnetobiostratigraphic and stable isotope investigation of Ocean Drilling Program Hole 761B, drilled on the Wombat Plateau. A combination of magnetostratigraphy, biostratigraphy and isotope stratigraphy demonstrates that numerous deep sea sites that have been considered to show continuous, or nearly continuous sedimentation through the Paleocene are punctuated by a series of hiatuses, some of which exceeding a duration of 1 Myr. Therefore, our study is based on a detailed temporal interpretation of the stratigraphic successions we used for paleoceanographic reconstructions. We compare detailed planktonic and benthic foraminiferal carbon and oxygen isotope records from Hole 761B with several temporally correlative records published from different oceanic provinces in order to distinguish between local and global patterns within the eastern Indian Ocean. Although Site 761 was situated at low latitudes during the Paleocene, its surface waters were predominantly influenced by circulation originating from the Southern Ocean as indicated by inferred cool sea surface temperatures and reduced surface to deep water temperature gradients. We suggest that deep waters in the eastern Indian Ocean were not directly fed by the Southern or Tethys Oceans. Rather, the more negative delta13C composition of the bottom waters recorded by benthic foraminifera implies the presence and/or active contribution of aged deep waters from the Pacific during this time, at least prior to ~60.2 Ma and subsequent to ~59.0 Ma. The Indian continent, Ninetyeast Ridge, Kerguelen Plateau and Broken Ridge may have played a significant role as submarine barriers to deep water circulation during the Paleocene.

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Detailed biostratigraphy in Site 1006 based on planktonic foraminifers and nannofossils shows large-scale sedimentation rate variability in the Florida Strait west of the Great Bahama Bank. A 'floating' cyclostratigraphy based mainly on resistivity logs and magnetic susceptibility data has been fixed to the biostratigraphy in the absence of magnetostratigraphy. The strongest orbital cycle present is the precessional beat, which is present in the borehole logs throughout the record. Counting the cycles resulted in an accurate time scale and thus a sedimentation rate time series. Spectral analysis of the sedimentation rate time series shows that the short-term cycle of eccentricity (~125 k.y.) and the long term cycle of eccentricity (~400 k.y.) are pervasive throughout the Miocene record, together with the long-term ~2-m.y. eccentricity cycle. The Great Bahama Bank produced pulses of shallow carbonate input once every precessional (sea level) cycle during the Miocene and perhaps two pulses per cycle in the early Pliocene. The amount of sediment exported in these pulses appears to be controlled by eccentricity modulation of the precessional amplitude and therefore the amplitude of the sea-level rise. Finally, an increase in sedimentation rate just after the Miocene/Pliocene boundary is attributed to a change in the location and strength of sediment drift currents in the Florida Strait due to reorganization of the currents following the closure of the Panama Isthmus.

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Total sediment oxygen consumption rates (TSOC or Jtot), measured during sediment-water incubations, and sediment oxygen microdistributions were studied at 16 stations in the Arctic Ocean (Svalbard area). The oxygen consumption rates ranged between 1.85 and 11.2 mmol m**-2 d**-1, and oxygen penetrated from 5.0 to >59 mm into the investigated sediments. Measured TSOC exceeded the calculated diffusive oxygen fluxes (Jdiff) by 1.1-4.8 times. Diffusive fluxes across the sediment-water interface were calculated using the whole measured microprofiles, rather than the linear oxygen gradient in the top sediment layer. The lack of a significant correlation between found abundances of bioirrigating meiofauna and high Jtot/Jdiff ratios as well as minor discrepancies in measured TSOC between replicate sediment cores, suggest molecular diffusion, not bioirrigation, to be the most important transport mechanism for oxygen across the sediment-water interface and within these sediments. The high ratios of Jtot/Jdiff obtained for some stations were therefore suggested to be caused by topographic factors, i.e. underestimation of the actual sediment surface area when one-dimensional diffusive fluxes were calculated, or sampling artifacts during core recovery from great water depths. Measured TSOC correlated to water depth raised to the -0.4 to -0.5 power (TSOC = water depth**-0.4 to -0.5) for all investigated stations, but they could be divided into two groups representing different geographical areas with different sediment oxygen consumption characteristics. The differences in TSOC between the two areas were suggested to reflect hydrographic factors (such as ice coverage and import/production of reactive particulate organic material) related to the dominating water mass (Atlantic or polar) in each of the two areas. The good correlation between TSOC and water depth**-0.4 to -0.5 rules out any of the stations investigated to be topographic depressions with pronounced enhanced sediment oxygen consumption.

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Cores from Sites 1129, 1131, and 1132 (Ocean Drilling Program (ODP) Leg 182) on the uppermost slope at the edge of the continental shelf in the Great Australian Bight reveal the existence of upper Pleistocene bryozoan reef mounds, previously only detected on seismic lines. Benthic foraminiferal oxygen isotope data for the last 450,000 years indicate that bryozoan reef mounds predominantly accumulated during periods of lower sea level and colder climate since stage 8 at Sites 1129 and 1132 and since stage 4 at the deeper Site 1131. During glacials and interstadials (stages 2-8) the combination of lowered sea level, increased upwelling, and absence of the Leeuwin Current probably led to an enhanced carbon flux at the seafloor that favored prolific bryozoan growth and mound formation at Site 1132. At Site 1129, higher temperatures and downwelling appear to have inhibited the full development of bryozoan mounds during stages 2-4. During that time, favorable hydrographic conditions for the growth of bryozoan mounds shifted downslope from Site 1129 to Site 1131. Superimposed on these glacial-interglacial fluctuations is a distinct long-term paleoceanographic change. Prior to stage 8, benthic foraminiferal assemblages indicate low carbon flux to the seafloor, and bryozoan mounds, although present closer inshore, did not accumulate significantly at Sites 1129 and 1132, even during glacials. Our results show that the interplay of sea level change (eustatic and local, linked to platform progradation), glacial-interglacial carbon flux fluctuations (linked to local hydrographic variations), and possibly long-term climatic change strongly influenced the evolution of the Great Australian Bight carbonate margin during the late Pleistocene.

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The Ocean Drilling Program Leg 175 recovered a unique series of stratigraphically continuous sedimentary sections along the SW African margin, an area which is presently affected by active coastal upwelling. The accumulation rates of organic and inorganic carbon are a major component of this record. Four Leg 175 sites (1082, 1084, 1085, 1087) are chosen as part of a latitudinal transect from the present northern to southern boundaries of the Benguela Current upwelling system, to decipher the Pliocene-Pleistocene history of biogenic production and its relationship with global and local changes in oceanic circulation and climate. The pattern of CaCO3 and Corg mass accumulation rates (MARs) over 0.25-Myr intervals indicates that the evolution of carbon burial is highly variable between the northern and the southern Benguela regions, as well as between sites that have similar hydrological conditions. This, as well as the presence over most locations of high-amplitude, rapid changes of carbon burial, reflect the partitioning of biogenic production and patterns of sedimentation into local compartments over the Benguela margin. The combined mapping of CaCO3 and Corg MARs at the study locations suggests four distinct evolutionary periods, which are essentially linked with major steps in global climate change: the early Pliocene, the mid-Pliocene warm event, a late Pliocene intensification of northern hemisphere glaciation and the Pleistocene. The early Pliocene spatially heterogeneous patterns of carbon burial are thought to reflect the occurrence of mass-gravitational movements over the Benguela slope which resulted in disruption of the recorded biogenic production. This was followed (3.5-3 Ma) by an episode of peak carbonate accumulation over the whole margin and, subsequently, by the onset of Benguela provincialism into a northern and a southern sedimentary regime near 2 Ma. This mid and late Pliocene evolution is interpreted as a direct response to changes in the ventilation of bottom and intermediate waters, as well as to dynamics of the subtropical gyral circulation and associated wind stress.

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