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1.
Chemical and mineralogical analyses of a well-controlled suite of ferromanganese encrustations from the Line Islands Archipelago (Central Pacific) suggest that they represent purely hydrogenous deposits—i.e. they have formed through the slow accumulation of trace metal-enriched oxides directly from the water-column. Mineralogically they consist predominantly of δMnO2 and amorphous FeOOHxH2O. Compositionally, they are similar to δMnO2 nodules from adjoining basinal areas but are enriched in both Mn (mean = 20.4%, max = 29.3%) and Co (mean = 0.55%, max = 1.57%). δMnO2 is the most important trace metal bearing phase; strong associations are noted between it and Co, Mo, Ni, Zn, and Cd, whilst only Be is associated specifically with FeOOH. V, Sr and Pb are partitioned between the authigenic oxide phases, whilst Ti most probably occurs as TiO2xH2O. Cu is contained in both aluminosilicate contaminant phases and Fe oxide phases. These relations are considered to reflect the differing scavenging behaviour of Mn and Fe oxides in the water column.Crusts from ~1–2 km are enriched in Mn and the Mn-related elements and exhibit higher MnFe ratios than deeper crusts, which are compositionally constant. The higher MnFe ratios may result from a supply of Mn from continental borderland sediments at these depths, which is transported horizontally by advective-diffusive processes. Since manganophile elements are enriched relative to Mn in the 1–2 km crusts, it is considered that the supply of Mn is scavenged by existing oxides, is oxidised and effectively occludes them. A higher proportion of oxide particles thus exhibit Mn oxide scavenging properties in the 1–2 km depth zone. The increased vertical flux of Mn resulting from the supply at ~1–2 km is not reflected by higher MnFe ratios in deeper crusts, so that the vertical flux of oxides is not simply related to the standing crop. The MnFe ratios of the crusts thus reflect the composition of suspended oxides at similar depths.  相似文献   

2.
The extent of oxygen isotopic exchange between detrital clay minerals and sea water was investigated by analyzing O18O16 ratios of separated fine-grained size fractions of deep-sea sediments from three North Pacific ocean cores. Isotopic results were interpreted according to models based on the assumption that the extent of isotopic exchange should increase with decreasing particle size and increasing time of exchange between the sediment and sea water. The data indicate that information concerning the provenance and mode of formation of detrital clay minerals can be obtained from the O18O16 ratios of the coarser-than-0.1 μm fraction of deep-sea sediments younger than several million years and the finer-than-0.1 μm fraction of deep-sea sediments younger than several tens of thousands of years. Furthermore, if the extent of chemical reaction between detrital clays and sea water is similar to the extent of oxygen isotopic exchange, such reaction may be important in regulating the chemistry of sea water.  相似文献   

3.
Diogenites contain equilibrated orthopyroxene-olivine assemblages. Mn is very regularly partitioned between olivine and orthopyroxene in pallasites, diogenites and synthetic eucrite melts, with an FeOMnO partition ratio for olivine versus orthopyroxene of 1.6 by weight over a very wide range of FeO contents. In contrast to diogenites, Fe and Mn are not regularly partitioned between the olivine and orthopyroxene of mesosiderites and these minerals were not in equilibrium. Mesosiderite olivine differs from diogenite olivine in FeMn and CaMn ratios. Lack of olivine-orthopyroxene equilibrium suggests that olivine in mesosiderites was derived not from a pyroxenite component analogous to diogenites but from dunites.  相似文献   

4.
Chemical and Sr isotopic analyses have been made of waters from 16 geothermal sites in Iceland with particular reference to the systems at Reykjanes and Svartsengi for which compositions of geothermal sea water and fresh and hydrothermally-altered rocks have been compared. The alkalies display mixing relationships indicating a hydrothermal input of Rb and K to local meteoric and sea waters as do results for Sr and Ca involving high-temperature fluids. 87Sr86Sr ratios of the geothermal waters of meteoric origin parallel those of associated rocks but are higher. Ratios for geothermal sea waters are 0.7042 (Reykjanes) and 0.7040 (Svartsengi), lower than for normal sea water (0.7092) because of leaching of Sr from rocks followed by partial removal into alteration minerals, of which epidote and chlorite may be most important. Consequently, associated hydrothermally-altered rocks have been subject to significant Sr isotopic contamination by sea water Sr raising 87Sr86Sr ratios from 0.7032 for fresh rock to 0.7038–0.7042 (Reykjanes) and to 0.7039–0.7041 (Svartsengi). Altered basalt is only ~50% equilibrated isotopically with geothermal sea water, at a water/rock ratio of ~2, but is internally equilibrated whereas palagonitized rocks (water/rock ratio of 3 to 4) are close to Sr isotopic equilibrium with associated sea water but show significant internal Sr disequilibrium. Hydrothermal input is unlikely to be important in the oceanic mass balance of Sr but is likely to be highly significant in controlling the strontium isotopic composition of sea water.  相似文献   

5.
Attempts have been made to study the entire growth history of a manganese nodule from the northern part of Peru Basin in the Pacific using radiochemical profiles of 230Th232Th, 227Th230Th, and 10Be9Be. Combined with the observations on Fe-Mn contents and textural variation, the radiochemical data indicate that the nodule grew more or less concentrically throughout most of its existence since it formed 1.5 my ago, receiving Mn from both bottom water and pore water. This condition appeared to have changed about 180 ky ago when the growth became asymmetric in that the top and bottom sides became fixed in their relative positions on the sea floor. Since then, the bottom side accreted with a fast rate of close to 200 mm/my, apparently fueled by the supply of diagenetically remobilized Mn in pore water from the sediment substrate. In the meantime, the top side accumulated at about 6 mm/my, a value which is in the normal range for deep-sea nodules having their Mn supplied from the hydrogenous source.  相似文献   

6.
Two-to threefold inward increase of 10Be, 9Be, Cu and Ni have been found in surface layers of marine ferromanganese deposits. We interpret this phenomenon as reflecting the manner in which the Be isotopes and probably other trace metals (e.g. Cu and Ni) are incorporated. On reaching the sea floor exchangeable Be is released from its carrier phase to the pore water of the ferromanganese deposits, diffuses inward and gets fixed into the deposits. The fixation process may be related to the mineralogical reorganizations suggested by previous studies. We have modeled this concept and applied it to a Mn crust on which detailed analyses of Cu, Ni and natural decay-series nuclides, as well as Be isotopes are made. Post-depositional fixation of Th isotopes may also occur. The redistributions of Be and Th isotopes are confined to regions very close to the surface of the deposits. For all practical purposes, they will not affect growth rate determinations conventionally done using these isotopes. The “linearly” extrapolated 10Be9Be ratio to the surface from deep layers of a Mn deposit does not necessarily represent that ratio in sea water.  相似文献   

7.
Below the zone where manganese is remobilized as Mn2+(aq), reductively cleaned foraminifera in deep sea sediments have much higher MnCa than those in core tops and sediment traps. MnCa ranges from less than 20 × 10?6 in and above the MnO2 maximum to as high as 700 × 10?6 in reducing Panama Basin sediments. The most plausible explanation for this enrichment is that the tests are coated with Mn carbonate overgrowths. These coatings can account for a significant proportion of the Mn in reduced deep-sea sediments. Uptake of manganous ion by carbonate may explain the absence of Mn nodules in areas of high carbonate accumulation. Extreme degrees of overgrowth can alter foram trace element values, but this artifact can be avoided by avoiding foraminifera with high Mn/Ca.  相似文献   

8.
A new condensation sequence appears if the CO ratio in a gas of otherwise solar composition is increased by less than a factor of two. As the ratio increases from the solar value of 0.6 to ? 1 the gas becomes extremely reduced, the condensation temperatures of silicates and oxides are depressed markedly ~ 400 K and a new suite of refractory minerals appears: AIN, CaS, MgS, SiC, TiN, graphite, Si2N2O and probably metastable (Fe,Ni)3C. Many of these minerals are unique to enstatite chondrites and may be analogues of the refractory silicates and oxides found in more oxidized meteorites such as Allende.The change in chemistry is related to the stability of CO, the most stable C or O compound at high T. Since the elements occur in a 1:1 ratio in CO, only the element which is in excess is free to form other compounds. But as T decreases CO reacts with H2 to form graphite, CH4 or other hydrocarbons thereby freeing O to form H2O. If equilibrium is maintained oxides and silicates form at about 1000 K (CO > 1, Pτ = 10?4atm) as products of reactions among the carbides, nitrides, sulfides and the gas. The possibility that equilibrium was not maintained among the C-bearing species was also investigated. If either graphite or CH4 does not form as predicted the stability fields of the reduced minerals expands to lower temperatures. If neither graphite nor CH4 form as predicted, CO remains stable and the nebular gas is highly reduced at all temperatures.Enstatite chondrites appear to have originated in a region of the nebula where the CO ratio was somewhat higher than the solar value. Various fractionation mechanisms are considered. An interesting possibility is that graphite, which is quite refractory under a wide range of conditions, survived the collapse of the solar nebula.  相似文献   

9.
Marine sediments and ferromanganese nodules from the Pacific Ocean have been analyzed for the OMn ratio of solid manganese. We tested six chemical methods and concluded that the iodometric and oxalate methods were equivalent and were the best choice in terms of accuracy and precision on natural samples. We choose the iodometric method for most of our analyses because the oxalate procedure is a method of differences.The ferromanganese nodules that we analyzed were all from MANOP site H and had MnFe ratios that ranged from 5.6 to 70. These nodules were invariably highly oxidized with OMn values ranging from 1.90 to 2.00. Our most precise analyses suggest that less than 1% of the total manganese is present as Mn(II).We also analyzed red clay and hemipelagic sediments from the eastern tropical Pacific (Baja borderland and MANOP site H) and carbonate ooze samples from the equatorial Pacific. These sediments are also highly oxidized (OMn= 1.90 to 2.00) except when Mn(II) appears in the interstitial water. As dissolved Mn(II) increases the value of the OMn ratio in the solid phase decreases. The OMn ratio decreases to values as low as 1.40. This decrease appears to be due to a decrease in oxidized manganese by reduction, however, an increase in reduced manganese in the solid sediments by adsorption or MnCO3 formation can not be ruled out in all cases.  相似文献   

10.
Drillcores and waters from Wairakei and Broadlands geothermal areas New Zealand have been analyzed for Li, Rb, Cs, Na, K, Mg, Ca, Al, Ti, Mn, and Be. The drillcores were altered to various degrees at temperatures below 300°C in slightly alkaline chloride water, probably derived from rock-water interaction in untapped horizons at higher temperature. It changes its composition as it leaches Ca and Na from the rock and adds K, Rb, Cs and Li. Evaluation of these changes in relation to the dimensions of the altered zone under observation suggests that a high mass ratio of water to rock (e.g., 100) and a period of up to 1 million years are responsible for the present stage of alteration.Increase of K and Rb in the altered rocks is a result of the formation of abundant adularia in addition to illite. The KRb ratio of the rock decreases during alteration but remains higher than that of the fluid. Only clay materials and zeolites that preferentially absorb Rb give slightly lower KRb ratios than the fluid.The mineral phases responsible for the uptake of lithium during alteration are chlorite (300 ppm Li) and quartz (up to 430 ppm Li). Li uptake in quartz is considered to be the mechanism by which Al-rich quartz crystallises from alumino-silicates. LiAl atomic ratios of 0.3–0.57 and Al concentrations up to 3000 ppm have been observed.Relatively small concentrations of Cs are found in potassic minerals (e.g. 10 ppm Cs in adularia, 44 ppm Cs in illite). However, 240 ppm Cs are found in wairakite from Wairakei equilibrated at 235°C. Lower equilibration temperatures may lead to higher cesium concentrations. This effect, in conjunction with a more concentrated hydrothermal fluid, could explain a content of 4500 ppm Cs in wairakite extracted from a drillcore taken in the El-Tatio geothermal field in Chile.  相似文献   

11.
A computer programme has been developed to calculate the composition and aqueous speciation of geothermal reservoir waters including pH, redox potential and gas partial pressures. The programme is specifically suited to handle geochemical data from wet-steam wells, hot-water wells and boiling hot springs, but it may also be used for non-thermal waters. Solubility data for selected geothermal minerals are incorporated to facilitate the study of solutionmineral equilibria. The programme may also be used to study chemical changes in water chemistry accompanying boiling, variable degassing and cooling, and how these changes disturb solutionmineral equilibria.  相似文献   

12.
The isotopic composition of Sr has been measured in brine samples from the Upper Jurassic Smackover Formation in southern Arkansas; 87Sr86Sr ratios range from 0.7071 to 0.7101. With one exception, the 32 Smackover brines contain Sr which is significantly more radiogenic than the Sr in Late Jurassic sea water, indicating sizable Sr contributions from detrital sources. Isotopic analyses of core samples from rock units associated with the brines and regional stratigraphic relationships suggest that the radiogenic Sr was released from detrital minerals in Bossier shale to interstitial fluids expelled from the underlying Louann Salt in the North Louisiana salt basin. These fluids migrated through the Bossier Formation updip to the South Arkansas shelf, where they entered the upper Smackover carbonate grainstone. The radiogenic fluids mixed with Sr-rich interstitial marine waters that had the isotopic composition of Late Jurassic sea water; mixing in variable proportions resulted in the random distribution pattern of variable 87Sr86Sr ratios that is observed in Smackover brines within the 5000 km2 study area. Isotopic analyses of nonskeletal carbonate grains and coexisting coarse calcspar cement from the upper Smackover grainstone imply that the grains were diagenetically stabilized in the presence of interstitial marine waters, whereas the calcspar cement is a relatively late diagenetic phase precipitated after the arrival of radiogenic fluids.  相似文献   

13.
The condensation temperatures of refractory silicates and oxides in a gas of cosmic composition are strongly dependent on the CO ratio. As the ratio increases from 0.4 to 0.9 (solar ~ cosmic ~ 0.6), condensation temperatures of compounds such as A12O3, Ca2Al2SiO7, MgAl2O4, Mg2SiO4 and MgSiO3 decrease by 50–100°. As CO increases from 0.9 to 1.0, these temperatures drop an additional 300–400°. Other chemical differences result when CO$?0.9 include: a new suite of high temperature minerals appears (graphite, CaS, Fe3C, SiC and TiN); the reaction CO + 3H2 → CH4 + H2O proceeds to the right at higher temperatures; and iron, whose condensation temperature is unaffected, condenses at higher temperatures than any silicate or oxide.  相似文献   

14.
HD Fractionation factors between epidote minerals and water, and between the AlO(OH) dimorphs boehmite and diaspore and water, have been determined between 150 and 650°C. Small water mineral ratios were used to minimise the effect of incongruent dissolution of epidote minerals. Waters were extracted and analysed directly by puncturing capsules under vacuum. Hydrogen diffusion effects were eliminated by using thick-walled capsules.HD Exchange rates are very fast between epidote and water (and between boehmite and water), complete exchange taking only minutes above 450°C but several months at 250°C. Exchange between zoisite and water (and between diaspore and water) is very much slower, and an interpolation method was necessary to determine fractionation factors at 450 and below.For the temperature range 300–650°C, the HD equilibrium fractionation factor (αe) between epidote and water is independent of temperature and Fe content of the epidote, and is given by 1000 In αepidote-H2Oe = ?35.9 ± 2.5, while below 300°C 1000 In αepidote-H2Oe = 29.2(106T2) ? 138.8, with a ‘cross-over’ estimated to occur at around 185°C. By contrast, zoisite-water fractionations fit the relationship 1000 In αzoisite-H2Oe = ? 15.07 (106T2) ? 27.73.All studied minerals have hydrogen bonding. Fractionations are consistent with the general relationship: the shorter the O-H -- O bridge, the more depleted is the mineral in D.On account of rapid exchange rates, natural epidotes probably acquired their H-isotope compositions at or below 200°C, where fractionations are near or above 0%.; this is in accord with the observation that natural epidotes tend to concentrate D relative to other coexisting hydrous minerals.  相似文献   

15.
For the northern half of the Chesapeake Bay. Maryland, an evaluation has been made of the relative importance of various human and natural sources of Cr, Mn, Fe, Co, Ni, Cu, Cd, Zn, and Pb. For rive of these (Mn, Fe, Co, Ni, and Zn) river discharge, shore erosion and salt water advection from the oceans account for more than half of the total input. On the other hand, the principal source for Cr and Cu is direct industrial discharge, for Cd is municipal wastewater, and for Pb is atmospheric dust and rain. In the subestuary of Baltimore Harbor, industry is the major contributor of all the elements except Cd and Pb, which again come mostly from wastewater and the atmosphere, respectively. Estimates of the removal of these elements by sedimentation suggest that less than 13 of the annual input of each metal is removed, except in the case of Cr and Fe where more than 23 is removed. These results suggest that human enhancement of normal input rates for these elements has the potential to produce a regional rather than merely a local biologic impact. It is of interest that for most of the elements, the percentage of the total input that is retained in the sediments is similar for heavily stressed Baltimore Harbor as it is for the northern Bay system as a whole.  相似文献   

16.
Twenty-six new high precision 87Sr86Srratio determinations and existing analyses are used to discuss the strontium isotopic composition of the Upper Cretaceous ophiolitic rocks of the Troodos Massif, Cyprus. Relative to initial magmatic 87Sr86Sr ratios (0.70338 ± 0.00010 to 0.70365 ± 0.00005), the hydrothermally metamorphosed pillow lavas and dyke complex have been contaminated by isotopically heavier strontium.This observation confirms the hypothesis that hydrothermal metamorphism was a consequence of sea water-rock interaction, since sea water was the only readily accessible reservoir of isotopically heavier strontium. The fact that metagabbros and altered trondhjemites were also Sr isotopically contaminated shows that sea water penetrated approximately 2 km into the oceanic crust represented by the ophiolitic sequence.The amount of Sr isotopic contamination requires that the bulk sea water: rock ratio was at least ~15:1 and shows that water-rock interaction occurred in a flow system. The degree of oxidation decreases with increasing depth. This shows that the vertical component of fluid flow was downward. The absolute bulk water/rock ratio (for water at S.T.P.), as estimated from the oxidation profile, may have been as large as ~3 × 103:1 —a large figure which independently confirms that rocks showing strong δ18O shifts have interacted with large volumes of water.The sites of discharge of the hot fluid, which must have come out of the system, are identified as the cupriferous pyrite ore deposits. This process of mass transfer corresponds to hydrothermal convection in a permeable medium with an open upper boundary surface.  相似文献   

17.
Sixty-nine analyses are given for NH4 in minerals of metamorphic and granitic rocks mostly from the Ryoke belt, Japan. The distribution of NH4 in coexisting minerals is quite systematic, suggesting that NH4 is one of the stable geochemical components in high temperature processes.Biotite has the highest content of NH4, followed by muscovite, K-feldspar and plagioclase. Pure quartz is almost free from NH4. Calcic plagioclase contains less NH4 than does sodic plagioclase. The partition coefficients DPlBi, DKfBi and DKfBi are, on the average, 0.11, 0.38 and 0.43 respectively. The fractionation of NH4 in these minerals is quite similar to that of Rb but much smaller than that of Cs.Distribution of NH4 as well as those of Rb and Cs appears to be explained by its ionic radius and the shortest cation-O distances in alkali positions of minerals.  相似文献   

18.
The 87Sr86Sr ratio of interstitial waters squeezed from recent sediments of the Pacific Ocean increases from 0.70920 ± 0.00017 (2σ) to 0.70960 ± 0.0023 and 0.70984 ± 0.00040 at 1.50 and 1.60 m depth—reference value for sea water: 0.70910 ± 0.00035. This variation underlines the likely existence of exchanges between the clays and the interstitial environment. The isotopic homogenization of strontium between the clays and their environment, result of these changes, becomes thus a credible phenomenon. This is a new argument for the dating of clays by the RbSr method.  相似文献   

19.
The 87Sr86Sr ratio in sea water has varied over geologic time due to the addition of strontium to the sea from rocks with a variety of 87Sr86Sr ratios. The measurements by Petermanet al. (Geochim. Cosmochim. Acta34, 105–120, 1970) of the value of the marine 87Sr86Sr ratio have been confirmed by several other workers and by some new measurements on JOIDES samples. They form the basis of a model calculation of the relative proportions of ‘basaltic’ (87Sr86Sr = 0.704) and ‘granitic’ (87Sr86Sr = 0.718) strontium being supplied to the sea. For the last 200 million years, the proportions of these two sources appear to reflect the history of global tectonics; ‘basaltic’ during rifting and increasingly ‘granitic’ during the present episodes of uplift and continental collision  相似文献   

20.
Solubility product determinations suggest that the hydrous phosphates of the rare earths, REPO4 · xH2O, are important in controlling the sea water REE concentrations. Two of these solids, rhabdophane, (P6222) and “hydrous xenotime”, (141/amd), have been synthesized at 100°C via the acid hydrolysis of the respective REE pyrophosphate. The solubility products at infinite dilution were determined to be pK0 = 24.5, (La at 25°C); 26.0, (Pr at 100°C); 25.7, (Nd at 100°C): and 25.5, (Er at 100°C). On the basis of calculations involving the reaction of RE3+ with apatite to form the hydrous phosphate, the lanthanum concentration in sea water is predicted to be about 140 pmol/L. Laboratory experiments support the hypothesis that apatite is a substrate for reactions with dissolved REE.  相似文献   

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