965 resultados para chlorine substituent


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Recent sediments with distinct signs of hydrothermal alteration sampled in the Hess Deep(Galapagos Ridge, East Pacific Rise) contained a piece of ash-gray rock, which differed from other rock fragments by degree of consolidation, conchoidal fracture, and had properties of asbestos. Our studies found that the sample represented mixture of asbestos-like pyroxene of diopside-hedenbergite composition, amphibole of tremolite composition and a new mineral, which basic structure consisted of bands of triple pyroxene chains with the radical [Si6O16]. The latter can be regarded as intermediate between amphiboles and layered silicates. Also in some parts of the sample presence of trioctahedral vermiculite-chlorite was indicated. Genesis of the studied asbestos rock is considered from the standpoint of high-temperature hydrothermal-metasomatic alteration of sediment by post-magmatic mineralized halide solutions.

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Data on concentrations of the major ions (Cl, SO4, Alk, Na, K, Ca, Mg, NH4) in interstitial waters from sediments of three brine-bearing deeps of the Red Sea rift zone are reported. Interstitial waters of the Atlantis-II Deep have the highest salinity (310.1 g/l), of the Discovery Deep - slightly lower (298.8 g/l), and of the Suakin Deep - the lowest (159.9 g/l). Interstitial waters of all three deeps are characterized by low, compared with sea water, absolute and relative concentrations of Mg and SO4 ions and have extremely low alkaline reserve (0.15-0.64 meq/l). Concentrations of K, Ca and especially Na and Cl ions, as compared with sea water, are highly increased. Interstitial waters from the deeps in study have high, compared with sea water, concentrations of NH4 (12-62 mg/l).

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Fifty m of basement rocks underlying 185 m of Neogene and Mesozoic sediments were drilled seaward of the Mazagan Slope about 100 km west of Casablanca during Leg 79. These rocks are metagranites with mylonitic textures consisting dominantly of quartz, plagioclase, and potassium feldspar. Chemically, they are strongly peraluminous. This along with the absence of hornblende suggest that these rocks are similar to the S-type granites. Petrographic and chemical data suggest the possible existence of a former weathering surface on top of the Mazagan metagranite.

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Samples of chert, porcellanite, and chalk/limestone from Cretaceous chert-bearing sections recovered during Leg 198 were studied to elucidate the nature and origin of chert color zonations with depth/age. Sedimentary structures, trace fossils, compactional features, sediment composition, texture, geochemistry, and diagenetic history were compared among lithologies. Trends in major and minor element composition were determined. Whereas geochemical analyses demonstrate systematic elemental differences among the different lithologies, there are less distinct patterns in composition for the colored cherts. The color of the chert appears to be related primarily to the amount of silica and secondarily to the proportion of other components. Red cherts are almost pure silica with only minor impurities. This may allow pigmentation from fine Fe oxides to dominate the color. These red cherts are from places where geophysical logs indicate that chert is the dominant rock type of the section. These red chert intervals cannot be unequivocally distinguished from surrounding chert-bearing lithologies in terms of sedimentary structures.

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During the International Indian Ocean Expedition (1964/65) sediment cores were taken on six profiles off the western coast of the Indian Subcontinent. These profiles run approximately perpendicular to the coast, from the deep-sea over the continental slope to the continental shelf. Additional samples and cores were taken in a dense pattern in front of the delta of the Indus River. This pattern of sampling covered not only marine sediments, but also river and beach sediments in Pakistan. The marine samples were obtained with piston, gravity and box corers and by a Van Veen grab sampler. The longest piston core is about 5 meters long. 1. Distribution of the elements on the sediment surface The area of maximal carbonate values (aprox. 80-100% CaCO3) essentially coincides with the continental shelf. The highest Sr values were observed largely within this area, but only in the vicinity of the Gulf of Cambay. Mainly the aragonitic coprolites are responsible for those high Sr contents. The Mg contents of the carbonates are comparatively low; surprisingly enough the highest Mg concentrations were also measured in the coprolites. The maximum contents of organic matter (Core) were found along the upper part of the continental slope. They coincide with the highest porosity and water content of the sediments. Frequently the decomposition of organic matter by oxydation is responsible for the measured Corg contents. On the other side the quantity of originally deposited organic material is less important in most cases. The enrichment of the "bauxitophile" elements Fe, Ti, Cr and V in the carbonate- and quartz-free portions of the sediments is essentially due to the influence of coarse terrigenous detritus. For the elements Mn, Ni and Cu (in per cent of the carbonateand quartz-free sediment) a strong enrichment was observed in the deep-sea realm. The strong increase in Mn toward the deep-sea is explained by authigenesis of Mn-Fe-concretions. Mn-nodules form only under oxydizing conditions which obviously are possible only at very low rates of deposition. The Mg, B and, probably also Mn contents in the clay minerals increase with increasing distance from the continent. This can be explained by the higher adsorption of those elements from sea water because of increasing duration of the clay mineral transport. The comparison of median contents of some elements in our deep-sea samples with deep-sea sediments described by TUREKIAN & WEDEPOHL (1961) shows that clear differences in concentration exist only in the case of "bauxitophile" elements Cr and Be. The Cr and Be contents show a clear increase in the Indian Ocean deep-sea samples compared to those described by TUREKIAn & WEDEPOHL (1961) which can obviously be attributed to the enrichment in the lateritic and bauxitic parent rocks. The different behaviour of the elements Fe, Ti and Mn during decomposition of the source rocks, transport to the sea and during oxydizing and reducing conditions in the marine environment can be illustrated by Ti02/Fe and MnO/Fe ratios. The different compositions of the sediments off the Indus Delta and those of the remaining part of the area investigated are characterized by a different distribution of the elements Mn and Ti. 2. Chemical inhomogenities in the sediments Most longer cores show 3 intervals defined by chemical and sedimentological differences. The top-most interval is coarse-grained, the intermedial interval is fine grained and the lower one again somewhat coarser. At the same time it is possible to observe differences from interval to interval in the organogenic and detrital constituents. During the formation of the middle interval different conditions of sedimentation from those active during the previous and subsequent periods have obviously prevailed. Looking more closely at the organogenic constituents it is remarkable that during the formation of the finer interval conditions of a more intensive oxydation have prevailed that was the case before and after: Core decreases, whereas P shows a relative increase. This may be explained by slower sedimentation rate or by a vertical migration of the oxygen rich zone of the sea-water. The modifications of the elements from minerals in detrital portion of the sediments support an explanation ascribing this fact to modifications of the conditions of denudation and transportation which can come about through a climatic change or through tectonic causes. The paleontological investigations have shown (ZOBEL, in press) that in some of the cores the middle stratum of fine sedimentation represents optimal conditions for organic life. This fact suggests also oxydizing conditions during the sedimentation of this interval. In addition to the depositional stratification an oxydation zone characterized by Mn-enrichment can be recognized. The thickness of the oxidation zone decreases towards the coast and thins out along the middle part of the continental slope. At those places, where the oxydation zone is extremely thin, enrichment of Mn has its maximum. This phenomenon can probably be attributed to the migration of Mn taking place in its dissociated form within the sediment under reducing conditions. On the other side this Mn-migration in the sediment does not take place in the deep-sea, where oxydizing conditions prevail. 3. Interstitial waters in the sediments Already at very small core depths, the interstitial waters have undergone a distinct modification compared with the overlying sea water. This distinct modification applies both to total salinity and to the individual ions. As to the beginning of diagenesis the following conclusions can be drawn: a) A strong K-increase occurs already at an early stage. It may be attributable to a diffusion barrier or to an exchange of Mg-ions on the clays. Part of this increase may also originate from the decomposition of K-containing silicates (mica and feldspars). A K-decrease owing to the formation of illite (WEAVER 1967), however, occurs only at much greater sediment depth. b) Because of an organic protective coating, the dissolution of carbonate is delayed in recent organogenic carbonates. At the same time some Ca is probably being adsorbed on clay minerals. Consequently the Ca-content of the interstitial water drops below the Ca-content of the sea water. c) Already at an early stage the Mg adsorption on the clays is completed. The adsorbed Mg is later available for diagenetic mineral formations and transformations.

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Late Holocene laminated sediments from a core transect centred in the oxygen minimum zone (OMZ) impinging at the continental slope off Pakistan indicate stable oxygen minimum conditions for the past 7000 calendar years. High SW-monsoon-controlled biological productivity and enhanced organic matter preservation during this period is reflected in high contents of total organic carbon (TOC) and redox-sensitive elements (Ni, V), as well as by a low-diversity, high-abundance benthic foraminiferal Buliminacea association and high abundance of the planktonic species Globigerina bulloides indicative of upwelling conditions. Surface-water productivity was strongest during SW monsoon maxima. Stable OMZ conditions (reflected by laminated sediments) were found also during warm interstadial events (Preboreal, Bølling-Allerød, and Dansgaard-Oeschger events), as well as during peak glacial times (17-22.5 ka, all ages in calendar years). Sediment mass accumulation rates were at a maximum during the Preboreal and Younger Dryas periods due to strong riverine input and mobilisation of fine-grained sediment coinciding with rapid deglacial sea-level rise, whereas eolian input generally decreased from glacial to interglacial times. In contrast, the occurrence of bioturbated intervals from 7 to 10.5 ka (early Holocene), in the Younger Dryas (11.7-13 ka), from 15 to 17 ka (Heinrich event 1) and from 22.5 to 25 ka (Heinrich event 2) suggests completely different conditions of oxygen-rich bottom waters, extremely low mass and organic carbon accumulation rates, a high-diversity benthic fauna, all indicating lowered surface-water productivity. During these intervals the OMZ was very poorly developed or absent and a sharp fall of the aragonite compensation depth favoured the preservation of pteropods. The abundance of lithogenic proxies suggests aridity and wind transport by northwesterly or northeasterly winds during these periods coinciding with the North Atlantic Heinrich events and dust peaks in the Tibetan Loess records. The correlation of the monsoon-driven OMZ variability in the Arabian Sea with the rapid climatic fluctuations in the high northern latitudes suggests a close coupling between the climates of the high and low latitudes at a global scale.

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Very significant enhancements of the element iridium have been observed in association with the Cretaceous/ Tertiary boundary in marine sediments laid down 65 m.y. ago and subsequently uplifted above the ocean's surface. If our hypothesis for the origin of the iridium and the cause of the Cretaceous/Tertiary life extinctions (the asteroid-impact theory) (Alvarez et al., 1980) is correct, the Ir anomaly should be associated with the Cretaceous/ Tertiary boundary region wherever it is intact. The present work was undertaken to search for the Ir anomaly in a deep-sea-drilling core, in order to check this aspect of the asteroid-impact theory.

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On the basis of the radiocarbon (14C) plateau-tuning method a new age model for Timor Sea Core MD01-2378 was established. It revealed a precise centennial-scale phasing of climate events in the ocean, cryo-, and atmosphere during the last deglacial and provides important new insights into causal linkages controlling events of global climate change. At Site MD01-2378 reservoir ages of surface waters dropped from 1600 yr prior to 20 cal ka to 250-500 yr after 18.8 cal ka. This evidence was crucial for generating a high-resolution age model for deglacial events in the Indo-Pacific Warm Pool. Sea-surface temperatures (SST) started to change near 18.8 cal ka, that is ~500 yr after the start of, presumably northern hemispheric, deglacial melt and sea level rise as shown by the benthic foraminiferal oxygen isotope ratio (d18O). However, the SST rise occurred 500-1000 yr prior to the onset of deglacial Antarctic warming and the first major rise in atmospheric carbon dioxide at about 18 ka. The increase in SST may partly reflect reduced seasonal upwelling of cold subsurface waters along the eastern margin of the Indian Ocean, which is reflected by a doubling of the thermal gradient between the sea surface and the thermocline, a halving of chlorin productivity from 19 to 18.5 cal ka, and in particular, by the strong decrease in surface water reservoir ages. Two significant increases in deglacial Timor Sea surface salinities from 19-18.5 and 15.5-14.5 cal ka, may partly reflect the deglacial increase in the distance of local river mouths, partly an inter-hemispheric millennial-scale see-saw in tropical monsoon intensity, possibly linked to a deglacial increase in the dominance of Pacific El Niño regimes over Heinrich stadial 1.

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New geochemical data from the Cocos Plate constrain the composition of the input into the Central American subduction zone and demonstrate the extent of influence of the Galápagos Hotspot on the Cocos Plate. Samples include sediments and basalts from Ocean Drilling Program (ODP) Site 1256 outboard of Nicaragua, gabbroic sills from ODP Sites 1039 and 1040, tholeiitic glasses from the Fisher Ridge off northwest Costa Rica, and basalts from the Galápagos Hotspot Track outboard of Central Costa Rica. Site 1256 basalts range from normal to enriched MORB in incompatible elements and have Pb and Nd isotopic compositions within the East Pacific Rise MORB field. The sediments have similar 206Pb/204Pb and only slightly more radiogenic 207Pb/204Pb and 208Pb/204Pb isotope ratios than the basalts. Altered samples from the subducting Galápagos Hotspot Track have similar Nd and Pb isotopic compositions to fresh Galápagos samples but have significantly higher Sr isotopic composition, indicating that the subduction input will have a distinct geochemical signature from Galápagos-type mantle material that may be present in the wedge beneath Costa Rica. Gabbroic sills from Sites 1039 and 1040 in East Pacific Rise (EPR) crust show evidence for influence of the Galápagos Hotspot ?100 km beyond the morphological hotspot track.

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A ridge of strongly serpentinized, plagioclase-bearing peridotite crops out at the boundary between the Atlantic oceanic crust and the Galicia continental margin (western Spain). These peridotites, cored at Hole 637A (ODP Leg 103) have been mylonitized at high-temperature, low-pressure conditions and under large deviatoric stress during their uplift (Girardeau et al., 1988, doi:10.2973/odp.proc.sr.103.135.1988). After this main ductile deformation event, the peridotite underwent a polyphase metamorphic static episode in the presence of water, with the crystallization of Ti- and Cr-rich pargasites at high-temperature (800°-900°C) interaction with a metasomatic fluid or alkaline magma. Introduction of water produced destabilization of the pyroxenes and the subsequent development of hornblendes and tremolite at temperatures decreasing from 750° to 350°C. The main serpentinization of the peridotite occurred at a temperature below 300°C, and possibly around 50°C, as a consequence of the introduction of a large amount of seawater, which is suggested by stable isotope (d18O and SD) data. Finally, calcite derived from seawater precipitated in late-formed fractures or locally pervasively impregnated the peridotite at low temperature (~10°C).

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The normal boiling point is a fundamental thermo-physical property, which is important in describing the transition between the vapor and liquid phases. Reliable method which can predict it is of great importance, especially for compounds where there are no experimental data available. In this work, an improved group contribution method, which is second order method, for determination of the normal boiling point of organic compounds based on the Joback functional first order groups with some changes and added some other functional groups was developed by using experimental data for 632 organic components. It could distinguish most of structural isomerism and stereoisomerism, which including the structural, cis- and trans- isomers of organic compounds. First and second order contributions for hydrocarbons and hydrocarbon derivatives containing carbon, hydrogen, oxygen, nitrogen, sulfur, fluorine, chlorine and bromine atoms, are given. The fminsearch mathematical approach from MATLAB software is used in this study to select an optimal collection of functional groups (65 functional groups) and subsequently to develop the model. This is a direct search method that uses the simplex search method of Lagarias et al. The results of the new method are compared to the several currently used methods and are shown to be far more accurate and reliable. The average absolute deviation of normal boiling point predictions for 632 organic compounds is 4.4350 K; and the average absolute relative deviation is 1.1047 %, which is of adequate accuracy for many practical applications.