41 resultados para cation exchange capacity


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Observations of hummock and string-like microrelief features were made in High Arctic hydric meadows. Thermal shearing of thick bryophyte mats, and subsequent roll back during spring flooding appears to be one way in which this topography is formed. Hummocky and non-hummocky (flat) meadows show distinct floristic differences which may in part be due to observed differences in temperature, nutrient concentrations and moisture relations.

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Cation exchange experiments (ammonium acetate and cation resin) on celadonite-smectite vein minerals from three DSDP holes demonstrate selective removal of common Sr relative to Rb and radiogenic Sr. This technique increases the Rb/Sr ratio by factors of 2.3 to 22 without significantly altering the age of the minerals, allowing easier and more precise dating of such vein minerals. The ages determined by this technique (Site 261 - 121.4+/-1.6 m.y.; Site 462A - 105.1+/-2.8 m.y.; Site 516F - 69.9+/-2.4 m.y.) are 34, 54 and 18 m.y. younger, respectively, than the age of crust formation at the site; in the case of site 462A, the young age is clearly related to off-ridge emplacement of a massive sill/flow complex. At the other sites, either the hydrothermal circulation systems persisted longer than for normal crust (10-15 m.y.), or were reactivated by off-ridge igneous activity. Celadonites show U and Pb contents and Pb isotopic compositions little changed from their basalt precursors, while Th contents are significantly lower. Celadonites thus have unusually high alkali/U,Th ratios and low Th/U ratios. If this celadonite alteration signature is significantly imprinted on oceanic crust as a whole, it will lead to very distinctive Pb isotope signatures for any hot spot magmas which contain a component of aged subducted recycled oceanic crust. Initial Sr isotope ratios of ocean crust vein minerals (smectite, celadonite, zeolite, calcite) are intermediate between primary basalt values and contemporary sea water values and indicate formation under seawaterdominated systems with effective water/rock ratios of 20-200.

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A new technique for the precise and accurate determination of Ge stable isotope compositions has been developed and applied to silicate rocks and biogenic opal. The analyses were performed using a continuous flow hydride generation system coupled to a MC-ICP-MS. Samples have been purified through anion- and cation-exchange resins to separate Ge from matrix elements and eliminate potential isobaric interferences. Variations of 74Ge/70Ge ratios are expressed as d74Ge values relative to our internal standard and the long-term external reproducibility of the data is better than 0.2? for sample size as low as 15 ng of Ge. Data are presented for igneous and sedimentary rocks, and the overall variation is 2.4? in d74Ge, representing 12 times the uncertainty of the measurements and demonstrating that the terrestrial isotopic composition of Ge is not unique. Co-variations of 74Ge/70Ge, 73Ge/70Ge and 72Ge/70Ge ratios follow a mass-dependent behaviour and imply natural isotopic fractionation of Ge by physicochemical processes. The range of d74Ge in igneous rocks is only 0.25? without systematic differences among continental crust, oceanic crust or mantle material. On this basis, a Bulk Silicate Earth reservoir with a d74Ge of 1.3+/-0.2? can be defined. In contrast, modern biogenic opal such as marine sponges and authigenic glauconite displayed higher d74Ge values between 2.0? and 3.0?. This suggests that biogenic opal may be significantly enriched in light isotopes with respect to seawater and places a lower bound on the d74Ge of the seawater to +3.0?.This suggests that seawater is isotopically heavy relative to Bulk Silicate Earth and that biogenic opal may be significantly fractionated with respect to seawater. Deep-sea sediments are within the range of the Bulk Silicate Earth while Mesozoic deep-sea cherts (opal and quartz) have d74Ge values ranging from 0.7? to 2.0?. The variable values of the cherts cannot be explained by binary mixing between a biogenic component and a detrital component and are suggestive of enrichment in the light isotope of diagenetic quartz. Further work is now required to determine Ge isotope fractionation by siliceous organisms and to investigate the effect of diagenetic processes during chert lithification.

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We report an optimized method for extracting neodymium (Nd) from fossil fish teeth with a single-stage column (125 µl stem volume; LN Resin, Eichrom Industries, Darien Illinois) for isotopic analysis by multi-collector inductively coupled mass spectrometry (MC-ICMPS). Three reference materials (basalt: BCR-2, BHVO-2; phosphate: fossil bone composite) and splits of fossil fish teeth samples previously processed with existing two-stage column methods were processed using the single-stage column method. 143Nd/144Nd values of reference materials agree within error with published values, and the values for fish teeth correspond with sample splits processed with two-stage columns. Precision to ± ~0.23 epsilon-Nd was achieved for 30 ng Nd samples of reference materials, and Nd isotope measurements of fossil fish tooth sample replicates as small as 7 ng Nd were reproducible within long term instrumental uncertainty. We demonstrate the utility of the new method with the first high resolution Nd isotope record spanning the ~40.0 Ma middle Eocene Climatic Optimum, which shows an excursion of 0.65 epsilon-Nd during the peak warming at the study site (Ocean Drilling Program Leg 119, Site 738; 30 kyr sample spacing from 40.3 to 39.6 Ma). LN Resin is already used in standard methods for separating Nd, and Nd isotopes are routinely measured by MC-ICPMS with high efficiency inlet systems. Our innovation is a single, small volume LN Resin column for Nd separation. The streamlined approach results in a 10X increase in sample throughput.

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By means of spectrographic analysis 96 samples of marine sediments were analyzed quantitatively for V, Ti, Zr, Co, Ni, Sc, Cr, and La, and semi-quantitatively for Ba and Sr. Ca has been estimated by visual comparison of spectrographic plates, and several Fe values have also been determined in the same way. Geographically 40 of these samples are from the Pacific Ocean basin, one of which is a manganese nodule, 21 from the Gulf of Mexico, 11 from Atchafalaya Bay, 8 from American Devonian to Miocene sedimentary rocks, 4 from the Mississippi Delta, 3 from the San Diego trough, 3 from off Grand Isle, 3 from Lake Pontchartrain, from Bay Rambour, 1 from Laguna Madre off the Texas coast, and 1 from the Guadalupe River, Texas. The afore-mentioned elements were sought using PdCl2 as an internal standard, after the method developed by Ahrens (1950) and his co-workers. Samples were run in duplicate, and standard deviations varied from 5 to 14 percent. Working curves, from which final values were obtained, were constructed with the use of standard granite, G1, and the standard diabase, W1, as standards. See Fairbairn and others (1951). An experiment was carried out to determine the effect of matrix change, involving CaCO3, on the spectral line intensities of the quantitatively analyzed elements. The distribution of each of the elements is discussed separately, and particular emphasis is given to oceanic "red clay", in which many elements are enriched. A general discussion is given to mineralogy of the sediments, cation exchange in its bearing on this thesis, and a brief recount of the two hypotheses of origin of oceanic "red clay". An application of the findings of this thesis to aid in the choice of the more likely hypothesis is made.

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We have analysed the concentrations of Li, K, Rb, Cs, and B, and the isotopic ratios of Li and B of a suite of pore fluids recovered from ODP Sites 1037 (Leg 169; Escanaba Trough) and 1034 (Leg 169S; Saanich Inlet). In addition, we have analysed dissolved K, Rb, and Cs concentrations for estuarine mixing of the Ganges-Brahmaputra river system. Together, these data sets have been used to assess the role of sediments in the marine geochemical cycles of the alkali elements and boron. Uptake onto clay minerals during estuarine mixing removes 20-30% of the riverine input of dissolved Cs and Rb to the oceans. Prior to this study, the only other recognised sink of Rb and Cs was uptake during low-temperature alteration of the oceanic crust. Even with this additional sink there is an excess of inputs over outputs in their modern oceanic mass balance. Pore fluid data show that Li and Rb are transferred into marine sediments during early diagenesis. However, modeling of the Li isotope systematics of the pore fluids from Site 1037 shows that seawater Li taken up during marine sedimentation can be readily returned to solution in the presence of less hydrated cations, such as NH4+. This process also appears to result in high concentrations of pore fluid Cs (relative to local seawater) due to expulsion of adsorbed Cs from cation exchange sites. Flux calculations based on pore fluid data for a series of ODP sites indicate that early diagenesis of clay sediments removes around 8% of the modern riverine input of dissolved Li. Although NH4+-rich fluids do result in a flux of Cs to the oceans, on the global scale this input only augments the modern riverine Cs flux by ~3%. Nevertheless, this may have implications for the fate of radioactive Cs in the natural environment and waste repositories.

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The origin and modes of transportation and deposition of inorganic sedimentary material of the Black Sea were studied in approximately 60 piston, gravity, and Kasten cores. The investigation showed that the sediment derived from the north and northwest (especially from the Danube) has a low calcite-dolomite ratio and a high quartz-feldspar ratio. Rock fragments are generally not abundant; garnet is the principal heavy mineral and illite is the predominant clay mineral. This sedimentary material differs markedly from that carried by Anatolian rivers, which is characterized by a high calcite-dolomite ratio and a low quartz-feldspar ratio. Rock fragments are abundant; pyroxene is the principal heavy mineral and montmorillonite is the predominant clay mineral. In generel, the clay fraction is large in all sediments (27.6-86.9 percent), and the lateral distributian indicates an increase in clay consent from the coasts toward two centers in the western and eastern Black Sea basin. Illite is the most common clay mineral in the Black Sea sediments. The lateral changes in composition of the clay mineral can easily be traced to the petrologic character of northern (rich in illite) and southern (rich in montmorillonite) source areas. In almost all cores, a rhythmic change of the montmorillonite-illite ratio with depth was observed. These changes may be related to the changing influence of the two provinces during the Holocene and late Pleistocene. Higher montmorillonite content seems to indicate climctic changes, probably stages of glaciation end permafrost in the northern area, at which time the illite supply was diminished to a large extent. The composition of the sand fraction is relatad to the different petrologic and morphologic characteristics of two major source provimces: (1) a northern province (rich in quartz, feldspars, and garnet) characterized by a low elevation, comprising the Danube basin area and the rivers draining the Russian platform; and (2) a southern province (rich in pyroxene and volcanic and metamorphic rocks) in the mountainous region of Anatolia and the Caucasus, characterized by small but extremely erosive rivers. The textural properties (graded bedding) of the deep-sea send layers clearly suggest deposition from turbidity currents. The carbonate content of the contemporary sediments ranges from 5 to 65 percent. It increases from the coast to a maximum in two centers in the western and eastern basin. This pattern reflects the distribution of the <2-µm fraction. The contemporary mud sedimentation is governed by two important factors: (1) the deposition of terrigenous allochthonous material of low carbonate content originating from the surrounding hinterland (northern and southern source areas), and (2) the autochthonous production of large quantities of biogenic calcite by coccolithophores during the last period of about 3,000-4,000 years.

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Amino acid-based geochronological analyses were carried out on fossil mollusc shell and foraminifera from Unit 3.1, Cape Roberts Project core CRP-1. Ratios of D-alloIsoleucine to L-Isoleucine (D/L) were measured from 19 fossil samples using cation exchange High Performance Liquid Chromatography (HPLC) methods. Preliminary interpretation of these results suggest that Unit 3.1 contains carbonate fossils having multiple ages. The interpreted ages have a bimodal distribution between ~220 Ka (Quaternary) and ~2.4 Ma (Pliocene). However, these results lack a comprehensive regional and taxonomic context for amino acid studies in Antarctica and therefore should be regarded as preliminary age estimates of fossil shell ages.

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The increase in atmospheric CO2 due to anthropogenic activity results in an acidification of the surface waters of the oceans. The impact of these chemical changes depends on the considered organisms. In particular, it depends on the ability of the organism to control the pH of its inner fluids. Among echinoderms, this ability seems to differ significantly according to species or taxa. In the present paper, we investigated the buffer capacity of the coelomic fluid in different echinoderm taxa as well as factors modifying this capacity. Euechinoidea (sea urchins except Cidaroidea) present a very high buffer capacity of the coelomic fluid (from 0.8 to 1.8 mmol/kg SW above that of seawater), while Cidaroidea (other sea urchins), starfish and holothurians have a significantly lower one (from -0.1 to 0.4 mmol/kg SW compared to seawater). We hypothesize that this is linked to the more efficient gas exchange structures present in the three last taxa, whereas Euechinoidea evolved specific buffer systems to compensate lower gas exchange abilities. The constituents of the buffer capacity and the factors influencing it were investigated in the sea urchin Paracentrotus lividus and the starfish Asterias rubens. Buffer capacity is primarily due to the bicarbonate buffer system of seawater (representing about 63% for sea urchins and 92% for starfish). It is also partly due to coelomocytes present in the coelomic fluid (around 8% for both) and, in P. lividus only, a compound of an apparent size larger than 3 kDa is involved (about 15%). Feeding increased the buffer capacity in P. lividus (to a difference with seawater of about 2.3 mmol/kg SW compared to unfed ones who showed a difference of about 0.5 mmol/kg SW) but not in A. rubens (difference with seawater of about 0.2 for both conditions). In P. lividus, decreased seawater pH induced an increase of the buffer capacity of individuals maintained at pH 7.7 to about twice that of the control individuals and, for those at pH 7.4, about three times. This allowed a partial compensation of the coelomic fluid pH for individuals maintained at pH 7.7 but not for those at pH 7.4.