953 resultados para N-15-nmr Chemical-shifts


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This paper reports results of geological studies carried out during two marine expeditions of R/VAkademik M.A. Lavrent'ev (Cruises 37 and 41) in 2005 and 2006 at the underwater Vityaz Ridge. Dredging has yielded various rocks from the basement and sedimentary cover of the ridge within three polygons. On the basis of radioisotope age determinations, petrochemical, and paleontological data all the rocks have been subdivided into the following complexes: volcanic rock of Paleocene, Eocene, Late Oligocene, Middle Miocene, and Pliocene-Pleistocene; volcanogenic-sedimentary rocks of Late Cretaceous - Early Paleocene, Paleogene (undifferentiated), Oligocene - Early Miocene, and Pliocene-Pleistocene. Determinations of age and chemical composition of the rocks have enabled to specify formation conditions of the complexes and to trace geological evolution of the Vityaz Ridge. Presence of young Pliocene-Pleistocene volcanites allows to conclude about the modern tectono-magmatic activity of the central part of the Pacific slope of the Kuril Islands.

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Bottom-simulating reflectors were observed beneath the southeastern slope of the Dongsha Islands in the South China Sea, raising the potential for the presence of gas hydrate in the area. We have analyzed the chemical and isotopic compositions of interstitial water, headspace gas, and authigenic siderite concretions from Site 1146. Geochemical anomalies, including a slight decrease of chlorine concentration in interstitial water, substantial increase of methane concentration in headspace gas, and 18O enrichment in the authigenic siderite concretion below 400 meters below seafloor are probably caused by the decomposition of gas hydrate. The low-chlorine pore fluids contain higher molecular-weight hydrocarbons and probably migrate to Site 1146 along faults or bedded planes.

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A blue-green smectite (iron-rich saponite) and green mica (celadonite) are the dominant sheet silicates in veins within the 10.5 m of basalt cored during DSDP Leg 34, Site 32l, in the Nazca plate. Oxygen isotopic analyses of these clays, and associated calcite, indicate a formation temperature of <25°C. Celadonite contains appreciable Fe2O3, K2O and SiO2, intermediate MgO, and very little Al2O3. Celadonite is commonly associated with goethite and hematite, which suggests that this phase formed by precipitation within a dominantly oxygenated environment of components leached from basalt and provided by seawater. A mass balance estimate indicates that celadonite formation can remove no more than 15% of the K annually transported to the oceans by rivers. In contrast, iron-rich saponite containing significant Al2O3 appears to have precipitated from a nonoxidizing, distinctly alkaline fluid containing a high Na/K ratio relative to unmodified seawater. Seawater-basalt interaction at low temperatures, resulting in the formation of celadonite and smectite may explain chemical gradients observed in interstitial waters of sediments overlying basalts.

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The Astoria submarine fan, located off the coast of Washington and Oregon, has grown throughout the Pleistocene from continental input delivered by the Columbia River drainage system. Enormous floods from the sudden release of glacial lake water occurred periodically during the Pleistocene, carrying vast amounts of sediment to the Pacific Ocean. DSDP site 174, located on the southern distal edge of the Astoria Fan, is composed of 879 m of terrigenous sediments. The section is divided into two major units separated by a distinct seismic discontinuity: an upper, turbidite fan unit (Unit I), and an underlying finer-grained unit (Unit II). Both units have overlapping ranges of Nd and Hf isotope compositions, with the majority of samples having e-Nd values of -7.1 to -15.2 and eHf values -6.2 to -20.0; the most notable exception is the uppermost sample in the section, which is identical to modern Columbia River sediment. Nd depleted mantle model ages for the site range from 2.0 to 1.2 Ga and are consistent with derivation from cratonic Proterozoic source regions, rather than Cenozoic and Mesozoic terranes proximal to the Washington-Oregon coast. The Astoria Fan sediments have significantly less radiogenic Nd (and Hf) isotopic compositions than present day Columbia River sediment (e-Nd=-3 to -4; [Goldstein, S.J., Jacobsen, S.B., 1987. Nd and Sr isotopic systematics of river water suspended material: implications for crustal evolution. Earth. Planet. Sci. Lett. 87, 249-265; doi:10.1016/0012-821X(88)90013-1]), and suggest that outburst flooding, tapping Proterozoic source regions, was the dominant sediment transport mechanism in the genesis and construction of the Astoria Fan. Pb isotopes form a highly linear 207Pb/204Pb - 206Pb/204Pb array, and indicate the sediments are a binary mixture of two disparate sources with isotopic compositions similar to Proterozoic Belt Supergroup metasediments and Columbia River Basalts. The combined major, trace and isotopic data argue that outburst flooding was responsible for depositing the majority (top 630 m) of the sediment in the Astoria Fan.

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We present the data used to construct the Cenozoic and Cretaceous portion of the Phanerozoic curve of seawater 87Sr/86Sr that had been given in summary form by W.H. Burke co-workers. All Cenozoic samples (128) and 22 Cretaceous samples are foram-nannofossil oozes and limestones from DSDP cores distributed among 13 sites in the Atlantic, Pacific and Indian Oceans, and the Caribbean Sea. Non-DSDP Cretaceous samples (126) include limestone, anhydrite and phosphate samples from North America, Europe and Asia. Determination of the 87Sr/86Sr value of seawater at particular times in the past is based on comparison of ratios derived from coeval marine samples from widely separated geographic areas. These samples are characterized by a wide variety of diagenetic and burial histories. The large size and cosmopolitan nature of the data set decreases the likelihood that, among coeval data, systematic error has been introduced by a similar pattern of diagenetic alteration of the ratios. There is good clustering of data points throughout the Cenozoic and Cretaceous curve. The consistency of data is illustrated by Cenozoic and Cretaceous data plots that include a separate symbol for each DSDP site and non-DSDP sample location. More than 98% of the data points are enclosed by upper and lower lines that define a narrow band. For any given time, the correct seawater ratio probably lies within this band. A line drawn within the band represents our estimate of the actual seawater ratio as a function of time. The general configuration of the Cenozoic and Cretaceous curve appears to be strongly influenced by the history of plate interactions and sea-floor spreading. Specific rises and falls in the 87Sr/86Sr of seawater, however, may be caused by a variety of factors such as variation in lithologic composition of the crust exposed to weathering, configuration and topographic relief of continents, volcanic activity, rate of sea-floor spreading, extent of continental inundation by epeiric seas, and variations in both climate and paleooceanographic conditions. Many or all of these factors are probably related to global tectonic processes, yet their combined effect on the temporal variation of seawater 87Sr/86Sr can complicate a direct platetectonic interpretation for portions of the seawater curve.

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The 87Sr/86Sr ratios and Sr concentrations in sediment and pore fluids are used to evaluate the rates of calcite recrystallization at ODP Site 807A on the Ontong Java Plateau, an 800-meter thick section of carbonate ooze and chalk. A numerical model is used to evaluate the pore fluid chemistry and Sr isotopes in an accumulating section. The deduced calcite recrystallization rate is 2% per million years (%/Myr) near the top of the section and decreases systematically in older parts of the section such that the rate is close to 0.1/age (in years). The deduced recrystallization rates have important implications for the interpretation of Ca and Mg concentration profiles in the pore fluids. The effect of calcite recrystallization on pore fluid chemistry is described by the reaction length, L, which varies by element, and depends on the concentration in pore fluid and solid. When L is small compared to the thickness of the sedimentary section, the pore fluid concentration is controlled by equilibrium or steady-state exchange with the solid phase, except within a distance L of the sediment-water interface. When L is large relative to the thickness of sediment, the pore fluid concentration is mostly controlled by the boundary conditions and diffusion. The values of L for Ca, Sr, and Mg are of order 15, 150, and 1500 meters, respectively. L_Sr is derived from isotopic data and modeling, and allows us to infer the values of L_Ca and L_Mg. The small value for L_Ca indicates that pore fluid Ca concentrations, which gradually increase down section, must be equilibrium values that are maintained by solution-precipitation exchange with calcite and do not reflect Ca sources within or below the sediment column. The pore fluid Ca measurements and measured alkalinity allow us to calculate the in situ pH in the pore fluids, which decreases from 7.6 near the sediment-water interface to 7.1+/-0.1 at 400-800 mbsf. While the calculated pH values are in agreement with some of the values measured during ODP Leg 130, most of the measurements are artifacts. The large value for L_Mg indicates that the pore fluid Mg concentrations at 807A are not controlled by calcite-fluid equilibrium but instead are determined by the changing Mg concentration of seawater during deposition, modified by aqueous diffusion in the pore fluids. We use the pore fluid Mg concentration profile at Site 807A to retrieve a global record for seawater Mg over the past 35 Myr, which shows that seawater Mg has increased rapidly over the past 10 Myr, rather than gradually over the past 60 Myr. This observation suggests that the Cenozoic rise in seawater Mg is controlled by continental weathering inputs rather than by exchange with oceanic crust. The relationship determined between reaction rate and age in silicates and carbonates is strikingly similar, which suggests that reaction affinity is not the primary determinant of silicate dissolution rates in nature.