978 resultados para Spectrophotometry, Atomic Absorption


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The variations in major elements and isotope composition (87Sr/86Sr, delta18O, deltaD) of interstitial waters in Leg 104 sediments is most probably caused by the alteration of volcanic matter. A reaction scheme where volcanic glass reacts with pore-water magnesium and potassium to form trioctahedral smectite, phillipsite, and chert is proposed. Model calculations demonstrate that the pore waters may evolve their negative 6180 signatures without recourse to unreasonably large amounts of volcanic detritus or external sources.

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The differential solubility of ferromanganese oxides can lead to stratigraphic separation of iron and manganese. Results of chemical analysis of a sequence of ferromanganese nodules overlying iron-rich crusts in northern Green Bay show that selec¬tive ion transport is important in concentrating manganese and associated trace elements near the oxygenated water-sediment interface. Manganese carbonate, which cements ferromanganese nodules, occurs in dark-gray silty sands that are located adjacent to the organic-rich muds of southern Green Bay. These muds contain an average of approximately 3.5 ppm (6x10-5M) interstitial Mn with 2.8 meq/l carbonate alkalinity. Thermodynamic calculation shows that interstitial water approaches equilibrium with MnCO3 in the upper 10 cm of sediment. This carbonate has a composition (Mn73Ca22Fe5)CO3 and has been identified as rhodochrosite.

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Atomic-absorption spectrophotometry and instrumental neutron activation analysis were used to determine concentrations of SiO2, Al2O3, FeOt, MgO, CaO, Na2O, K2O, MnO, La, Ce, Sm, Eu, Tb, Yb, Lu, Sc, Co, Cr, Th, Hf, and Ta for 14 basalt samples from the lower portion of Hole 462A in the Nauru Basin. The basalts are similar to normal midocean ridge basalt (MORB) for the elements analyzed, and light rare-earth elements (LREE) are depleted relative to heavy rare-earth elements (HREE). Two samples are extensively altered to smectites and show significant reductions in Al2O3, CaO, MnO, Na2O, REE, Sc, Co, and Hf and gains in MgO and FeOt relative to unaltered samples. The increase in MgO and decrease in CaO indicate that alteration was caused by hydrothermal solutions.

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Clay mineralogic and inorganic geochemical investigations of Cretaceous and Cenozoic sediments of the western Gulf of Mexico lead to the following main conclusions. (1) Transition of lowermost Cretaceous continental to marine sedimentation is marked by a clay evaporitic stage, north of the Campeche Escarpment. (2) Existence of combined mineralogic and geochemical stratigraphy allows us to propose correlations between Sites 535 and 540, especially for the Albian. (3) Predominance of detrital clay assemblages is indicative of hot and variably humid continental climate until the early late Cenozoic. (4) Tectonic destabilization of the margins of Gulf of Mexico occurred at different periods, especially until the middle Cretaceous, with a mixed erosion of rocks and soils and temporary oxidized conditions of deposition. (5) Successive developments of confined perimarine basins occurred from the earliest Cretaceous until the Miocene, chiefly in the Florida area. The sources of inorganic materials were chiefly situated on the east of the studied area until the late Tertiary and after that in the Mississippi River basin. (6) Occasionally, volcanic activity influenced the clay mineralogy and mainly the geochemistry, and possibly contributed to the rather strong magnesian character of the deposition until the late Paleogene. (7) The argillaceous diagenesis is weak; variability of the carbonate diagenesis is marked by the relation Sr = f(CaO) and chiefly depends on the depth of burial, the clay content, the porosity, and the geologic age.

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Petrography and isotope geochemical characteristics of H, O, S, Sr, and Nd have been described for basalts recovered from Hole 504B during Leg 111 of the Ocean Drilling Program. The petrographic and chemical features of the recovered basalts are similar to those obtained previously (DSDP Legs 69, 70, and 83); they can be divided into phyric (plagioclase-rich) and aphyric (Plagioclase- and clinopyroxene-rich) basalts and show low abundances of TiO2, Na2O, K2O, and Sr. This indicates that the basalts belong to Group D, comprising the majority of the upper section of the Hole 504B. The diopside-rich nature of the clinopyroxene phenocrysts and Ca-rich nature of the Plagioclase phenocrysts are also consistent with the preceding statement. The Sr and Nd isotope systematics (average 87Sr/86Sr = 0.70267 ± 0.00007 and average 143Nd/144Nd = 0.513157 ± 0.000041) indicate that the magma sources are isotopically heterogeneous, although the analyzed samples represent only the lowermost 200-m section of Hole 504B. The rocks were subjected to moderate hydrothermal alteration throughout the section recovered during Leg 111. Alteration is limited to interstices, microfractures, and grain boundaries of the primary minerals, forming chlorite, actinolite, talc, smectite, quartz, sphene, and pyrite. In harmony with the moderate alteration, the following alteration-sensitive parameters show rather limited ranges of variation: H2O = 1.1 ±0.2 wt%, dD = - 38 per mil ± 4 per mil, d180 = 5.4 per mil ± 0.3 per mil, total S = 562 ± 181 ppm, and d34S = 0.8 per mil ± 0.3 per mil. Based on these data, it was estimated that the hydrothermal fluids had dD and d180 values only slightly higher than those of seawater, the water/rock ratios were as low as 0.02-0.2, and the temperature of alteration was 300°-400°C. Sulfur exists predominantly as pyrite and in minor quantities as chalcopyrite. No primary monosulfide was detected. This and the d34S values of pyrite (d34S = 0.8 per mil) suggest that primary pyrrhotite was almost completely oxidized to pyrite by reaction with hydrothermal fluids containing very little sulfate.

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Analyses by atomic absorption spectrophotometry and spark-source mass spectrography of 25 basal metalliferous sediment units from widely spaced locations on the western flank of the East Pacific Rise show that the deposits are enriched relative to normal pelagic sediment in Fe, Mn, Ni, Cu, Pb, Zn, and many trace elements. The elements are partitioned differently between the various mineralogic constituents of the sediment, with Fe and Mn largely in separate phases and many of the remaining elements primarily associated with reducible ferromanganese oxide minerals but also with iron minerals and other phases. Most of the iron in the deposits is probably of volcanic origin, and much of the manganese and minor elements is derived from sea water. The bulk composition of the deposits varies with age; this is thought to be due to variations in the incidence of volcanic activity at the East Pacific Rise crest where the deposits were formed.

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A preliminary report on the manganese nodule field southwest of Western Australia published in this Journal recently (Frakes, Exon and Granath, 1977) quoted chemical analyses which were carried out on air-dried material. Significantly higher metal values have been recorded in some later analyses done on nodules dried at 105°C. Tests have shown that the ground, air-dried material retains considerable moisture, which accounts for the higher metal values of the later analyses. The average water content (after drying at 105°C) has been determined at 16 percent. The relevant chemical data now available on this material are summarised in the accompanying table: in this table metal values (by atomic absorption spectrophotometry) have been recalculated assuming a moisture content of 16 percent.

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In the collective monograph results of geological and geophysical studies in the Tadjura Rift carried out by conventional outboard instruments and from deep/sea manned submersibles "Pisces" in winter 1983-1984 are reported. Main features of rift tectonics, geology, petrology, and geochemistry of basalts from the rift are under consideration. An emphasis is made on lithology, stratigraphy, and geochemistry of bottom sediments. Roles of terrigenous, edafogenic, biogenic, and hydrothermal components in formation of bottom sediments from the rift zone are shown.

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Major and rare earth element (REE) data for basalts from Holes 483, 483B, and 485A of DSDP Leg 65, East Pacific Rise, mouth of the Gulf of California, support a simple fractional crystallization model for the genesis of rocks from this suite. The petrography and mineral chemistry (presented in detail elsewhere) provide no evidence for magma mixing, but rather a simple multistage cooling process. Based on its lowest TiO2 content (0.88%), FeO*/MgO ratio (0.95 with total Fe as FeO), and Mg# (100 Mg/Mg + Fe" = 70), sample 483-17-2-(78-83) has been selected as the most primitive primary magma of the samples analyzed. This is supported by the REE data which show this sample has the lowest total REE content, a La/Sm_cn (chondrite-normalized) = 0.36, and Eu/Sm_cn = 1.05. Because other samples analyzed have higher SiO2, lower Mg#, and a negative Eu anomaly (Eu/Sm_cn as low as 0.89), they are most likely derivative magmas. Wright-Doherty and trace element modelling support fractional crystallization of 14.1% plagioclase (An88), 6.7% olivine (Fo86), and 4.7% clinopyroxene (Wo41En49Fs10) from 483-17-2-(78-83) to form the least differentiated sample with Mg# = 63. The La/Sm_cn of this derivative magma is almost identical to the parent magma (0.35 to 0.36), but the other samples have higher La/Sm_cn (0.45 to 0.51), more total REE, and lower Mg# (60 to 56). Both Wright-Doherty and trace element modelling indicate that the primary magma chosen cannot produce these more evolved samples. For the major elements, the TiO2 and P2O5 are too low in the calculated versus the observed (1.38 to 1.90; 0.11 to 0.17, respectively, for example). Rayleigh fractionation calculates a lower La/Sm_cn and requires about 60% crystal removal versus 40% for the Wright-Doherty. These more evolved samples must be derived from a parent magma different from the one selected here and, unfortunately, not sampled in this study. A magma formed by a smaller degree of partial melting with slightly more residual clinopyroxene left in the mantle than for sample 483-17-2-(78-83) is required.

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Concentrations and compositions of rare earth elements (REE) in three micronodule fractions (50-250, 250-500, and >500 ?m), coexisting macronodules, and host sediments were studied. Samples were collected at three sites (Guatemala Basin, Peru Basin, and northern equatorial Pacific) located in elevated bioproductivity zones of surface waters. Influence of micronodule size is dominant for REE compositions and subordinate for REE concentrations. For example, Ce concentration inversely correlates with micronodule size and drops to the lowest value in macronodules and host sediments. Decrease of Ce concentration is generally accompanied by Mn/Fe increase in micro- and macronodules. Hence, the role of diagenetic source of material directly correlates with micronodule sizes. Contribution of the diagenetic source is maximal for macronodules. REE composition distinctions for micronodules and macronodules can be attributed to variations of hydrogenic iron oxyhydroxides and diagenetic (hydrothermal) iron hydroxophosphates that are the major REE carriers in ferromanganese ore deposits. Relationship and general trend in chemistry of coexisting macronodules suggest that they can represent products of the initial stage of nodule formation.

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Basalt underlying early Campanian chalk at Deep Sea Drilling Project (DSDP) Site 163 is divided into seven extrusive cooling units bounded by glassy margins. The margins have dips of 15° to 70°, suggestive of pillow flows rather than tabular flows. The margins are fresh sideromelane (glass) grading inward to opaque and reddish-brown globules containing microcrystalline material with radial, undulose extinction. Relative to adjacent sideromelane, the reddish-brown globules are enriched in sodium and calcium, whereas the opaque globules are depleted in these elements and enriched in iron and magnesium. It appears that basalt just inside the pillow margins has differentiated in place into globules of two distinct compositions. This globule zone grades inward to less rapidly cooled pyroxene varioles and intergrowths of plagioclase and opaque minerals. In the center of the thicker cooling units, the texture is diabasic. Alteration and calcite vein abundance are greatest at pillow margins and decrease inward; the interior of the thickest cooling unit is only slightly altered, and calcite veins are absent. Chemical analysis of whole rock by atomic absorption spectrophotometry, and of sideromelane by electron microprobe, indicates that the rock is a slightly weathered tholeiite. The atomic absorption analyses, except the one nearest the top of the basalt, are relatively uniform and similar to the sideromelane microprobe analyses, including those near the top of the basalt. This suggests that deep penetration is not necessary to get through the severely altered layer at the basalt surface, and that within this altered layer, analyses of sideromelane may be more representative of crustal composition than analyses of whole rock.