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1.
The isotopic ratios 18O16O and 13C12C show an annual periodicity in the coral Montastrea annularis from Bermuda, Jamaica and Barbados. The abundances of 18O and 13C are positively correlated in the Jamaica and Barbados samples, but inversely related in the Bermuda sample. Annual high density growth bands are formed during the season of warmest water temperature at all 3 sites and are enriched in 16O. M. Annularis has a constant displacement from oxygen isotopic equilibrium and accurately records seasonal temperature variations via the temperature-dependent aragonite-water fractionation factor. Light intensity, through the activity of the coral's endosymbiotic algae, regulates the depth-dependent and seasonal variations in the skeletal carbon isotopic composition.  相似文献   

2.
Aragonite mineralization was observed in serpentinized peridotites from the Romanche and Vema Fracture Zones in the Atlantic and the Owen Fracture Zone in the Indian Ocean, either in veins or as radial aggregates in cavities within the serpentinites. Evidence of incipient dissolution of the aragonite crystals was observed in one case. The aragonites tend to have lower Mg content (< 0.03%) and higher Sr content (> 0.95%) relative to other marine aragonites. Their 18O16O, 13C12C and 87Sr86Sr isotopic ratios suggest the aragonite was deposited at ocean floor temperatures from solutions derived from sea water circulating in fissures and fractures within the ultramafic rocks. The 18O16O ratios of the serpentines indicate serpentinization occurred at higher temperatures, probably deeper in the crust. Low-T reactions between circulating seawater and Mg-silicates (primarily serpentine and pyroxenes) caused high pH and enrichment of Mg and Ca in the solution, conditions favoring carbonate precipitation. Aragonite was formed rather than calcite presumably because the high Mg2+ concentration in the solution inhibited calcite precipitation. The high Sr content of the aragonites is probably related, at least in part, to their low temperature of formation. Opaque mineral grains containing over 8% NiO and over 40% MnO were observed concentrated along the margins of some of the aragonite veins, suggesting that Ni is one of the elements mobilized during reactions between ultramafic rocks and circulating seawater.  相似文献   

3.
The solubility of rutile has been determined in a series of compositions in the K2O-Al2O3-SiO2 system (K1 = K2O(K2O + Al2O3) = 0.38–0.90), and the CaO-Al2O3-SiO2 system (C1 = CaO(CaO + Al2O3) = 0.47–0.59). Isothermal results in the KAS system at 1325°C, 1400°C, and 1475°C show rutile solubility to be a strong function of the K1 ratio. For example, at 1475°C the amount of TiO2 required for rutile saturation varies from 9.5 wt% (K1 = 0.38) to 11.5 wt% (K1 = 0.48) to 41.2 wt% (K1 = 0.90). In the CAS system at 1475°C, rutile solubility is not a strong function of C1. The amount of TiO2 required for saturation varies from 14 wt% (C1 = 0.48) to 16.2 wt% (C1 = 0.59).The solubility changes in KAS melts are interpreted to be due to the formation of strong complexes between Ti and K+ in excess of that needed to charge balance Al3+. The suggested stoichiometry of this complex is K2Ti2O5 or K2Ti3O7. In CAS melts, the data suggest that Ca2+ in excess of A13+ is not as effective at complexing with Ti as is K+. The greater solubility of rutile in CAS melts when C1 is less than 0.54 compared to KAS melts of equal K1 ratio results primarily from competition between Ti and Al for complexing cations (Ca vs. K).TiKβ x-ray emission spectra of KAS glasses (K1 = 0.43–0.60) with 7 mole% added TiO2, rutile, and Ba2TiO4, demonstrate that the average Ti-O bond length in these glasses is equal to that of rutile rather than Ba2TiO4, implying that Ti in these compositions is 6-fold rather than 4-fold coordinated. Re-examination of published spectroscopic data in light of these results and the solubility data, suggests that the 6-fold coordination polyhedron of Ti is highly distorted, with at least one Ti-O bond grossly undersatisfied in terms of Pauling's rules.  相似文献   

4.
18O16O, 13C12C and 87Sr86Sr ratios have been measured on the same samples for carbonatite complexes. The results show that besides the ‘carbonatite box’ of Tayloret al. (1967) there exist higher δ18O and δ13C values than can be explained by late magmatic or deuteric processes. These processes correspond to high concentrations of CO2 and lead to big enrichments in 18O and 13C as well as in some ‘volatile’ elements. Strontium results are consistent with a model of selective contamination of deep-seated material by highly radiogenic strontium. The whole study leads to the opinion that parent magmas of carbonatites differentiated in a crustal environment with or without significant contamination.  相似文献   

5.
Measurements of the C12C13 ratio on two generations of calcite and the matrix from a single specimen are given and discussed. This ratio has also been determined for four examples of graphite and limestone occurring together. The formation of the graphite is briefly discussed in relation to the C12C13 ratios.  相似文献   

6.
The sequence of vegetation phases in the late Glacial was studied in a sediment section from the bog Tourbière de Chirens by means of pollen analysis. 18O16O ratios of samples of lacustrine marl, obtained from the same profile, reflect variations of 18O16O in precipitation and thus provide an additional, independent paleoclimatic record. The observed 18O16O variations agree well with the climatic history as deduced from pollen analysis. The climatic transition from the Oldest Dryas to the Bølling period sensu lato, as well as the beginning and end of the Younger Dryas cold phase, is marked by abrupt changes in the 18O16O ratio which were observed also in other regions of the Alps. These drastic climatic changes probably took place simultaneously over large areas of Central Europe and occurred within short time spans.  相似文献   

7.
DH, 18O16O and 13C12C analyses were made of 14 whole rock and 28 mineral samples of rodingites associated dominantly with lizardite-chrysotile serpentinites from the West Coast of the U.S.A., New Zealand, and the Northern Appalachian Mtns. The δD values of the rodingite minerals are in three groupings: 5 monomineralic veins of pectolite, ?281 to ?429; 8 monomineralic veins of xonotlite, ?112 to ?135; all other minerals, including hydrogarnet, idocrase, prehnite, actinolite, nephrite, and chlorite, ?34 to ?80. Most calcites in rodingites have δ18O (+9.3 to +14.4) and (δ13C (?6.7 to +0.9) values similar to calcites in other Franciscan rocks, but distinct from the very low temperature calcite veins in serpentinites. The DH data, combined with δ18O values of xonotlite (+5.7 to +10.9) and pectolite (+8.9 to +12.4) suggest formation from meteoric-type waters at low temperatures; the DH depletion of pectolite, however, is anomalous. Rodingite whole rock values range from δ18O = +4.1 to +11.5 and δD = ?50 to ?86; one sample containing minor amounts of lizardite-chrysotile serpentinite has δD = ?92, outside this range. However, most rodingites of basaltic or gabbroic parentage are more restricted in δ18O (+4.1 to +8.6). Such a wide range in δ18O is consistent with the idea that most rodingites form over a relatively broad range of hydrothermal temperatures. Hydrogen isotopic data for most rodingite minerals (except xonotlite and pectolite) and for whole rocks are suggestive of non-meteoric waters. These DH data overlap those observed for veins of hydrous minerals found in Franciscan igneous rocks studied by Margaritz and Taylor (1976, Geochim. Cosmochim. Acta40, 215–234), possibly suggesting evolved D-enriched, connate type metamorphic waters generated during high P, low T Franciscan-type metamorphism at temperatures (250–500°C) comparable to estimates based on mineral stabilities. Such an interpretation is supported by the 18O16O and 13C12C data for calcite in rodingites.The isotope data appear to contradict some of the conclusions derived from geologic and petrologic studies that indicate concomitant metasomatism and serpentinization of their presently observed host rock. These data appear most consistent with the interpretation that most rodingite minerals, with the exception of late-stage veins of xonotlite and possibly pectolite, may involve metasomatism in association with antigorite serpentinization of ultramafic rock. Subsequent upward tectonic transport in many instances may result in incorporation of the rodingites into their presently observed lizarditechrysotile host rock during or subsequent to pervasive shallow level serpentinization by meteoric waters.  相似文献   

8.
Eggwaters from the chambered cephalopod Nautilus are depleted in both 18O and deuterium relative to ambient seawater. Eggwaters from six other species, including the related chambered cephalopod Sepia, do not show such depletion. These observations indicate that the previously observed step towards more positive δ18O values in calcium carbonate laid down after Nautilus hatches, relative to carbonate precipitated prior to hatching, can be explained by equilibration of the carbonate with water in the egg before hatching and with seawater after hatching. The presence of an oxygen isotope difference between eggwater and seawater for Nautilus and its absence for Sepia suggest that hatching will be recorded in the δ18O values of shell carbonates for some but not all extinct and extant chambered cephalopods.The δ13C values of the organic fraction of the siphuncle in Nautilus do not show any consistent pattern with regard to the time of formation before or after hatching. This observation suggests that the minimum in δ13C values previously observed for calcium carbonate precipitated after Nautilus hatches is not caused by a change in food sources once the animal becomes free-swimming, as has been suggested.  相似文献   

9.
We describe the analytical techniques developed for the precise measurement of the titanium isotope abundances using a TiO+ ion beam. Terrestrial, lunar, and bulk meteorite samples yield identical results. Using a normalization to 46Ti48Ti for mass dependent isotope fractionation, we obtain the normal Ti composition: 46Ti48Ti = 0.108548; 47Ti48Ti = 0.099315 ± 0.000005; 49Ti48Ti = 0.074463 ± 0.000004; 50Ti48Ti = 0.072418 ± 0.000004 (2σ grand mean), taking 18O16O = 0.002045 and 17O16O = 0.00037. Measurements on thirteen coarse-grained and fine-grained Ca-Al-Ti-rich inclusions from the Allende and Leoville meteorites show the presence of widespread, significant, nonlinear isotope anomalies in the Ti isotopes which were not used for normalization. The data require the addition of at least three exotic components. The distinct correlation of non-linear effects for the most neutron-rich isotopes of Ca and Ti and the absence of substantial effects at 46Ca in the FUN samples EK-1-4-1 and C-1 indicate that the effects reflect neutron-rich equilibrium or quasi-equilibrium nucleosynthetic processes in the outer layers of a supernova core. The results on Ca and Ti in conjunction with the isotopic effects on other elements (Mg, Sr, Ba, Nd, Sm) show that the samples represent mixtures of different nucleosynthetic components from distinctive processes (‘e’, ‘r’, ‘p’) which do not appear to be related to processes in the same stellar sites.  相似文献   

10.
The DH and 13C12C ratios of the cellulose nitrate and saponifiable lipid fractions prepared from eleven annual growth rings of a California redwood were determined. The DH ratios of the two fractions are related to one another for the annual rings in the sapwood portion of the tree, but not for those in the heartwood or in the wood undergoing the transition from sapwood to heartwood. No relationship was observed between the 13C12 ratios of the two fractions. These results suggest that analysis of the hydrogen isotopic composition of the saponifiable lipid fractions in plants will provide information useful for climatic reconstruction provided the initial isotopic record has not been changed by subsequent physiological or diagenetic processes.  相似文献   

11.
An isotopic type-curve has been defined based on the 13C12C ratios of the saturated, aromatic, heterocomponent (NOSs), and asphaltene fractions of crude oils. These fractions show 13C enrichments with increasing polarity or polarizability. This systematic pattern can be used to estimate the 13C12C ratio of the kerogen from which the oil had been generated. Genetically associated source rock oil pairs have been used to show that the difference between the measured and the estimated δ-values of kerogen is about ?0.5%., and between the δ-values of the kerogen and the asphaltene fraction is approximately +0.6%.  相似文献   

12.
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   

13.
The geochemical history of Lake Lisan, the Pleistocene precursor of the Dead Sea, has been studied by geological, chemical and isotopic methods.Aragonite laminae from the Lisan Formation yielded (equivalent) Sr/Ca ratios in the range 0.5 × 10?2?1 × 10?2, Na/Ca ratios from 3.6 × 10?3 to 9.2 × 10?3, δ18OPDB values between 1.5 and 7%. and δ13CPDB from ?7.7 to 3.4%..The distribution coefficient of Na+ between aragonite and aqueous solutions, λANa, is experimentally shown to be very sensitive to salinity and nearly temperature independent. Thus, Na/Ca in aragonite serves as a paleosalinity indicator.Sr/Ca ratios and δ18O values in aragonite provide good long-term monitors of a lake's evolution. They show Lake Lisan to be well mixed, highly evaporated and saline. Except for a diluted surface layer, the salinity of the lake was half that of the present Dead Sea (15 vs 31%).Lake Lisan evolved from a small, yet deep, hypersaline Dead Sea-like, water body. This initial lake was rapidly filled-up to its highest stand by fresh waters and existed for about 40,000 yr before shrinking back to the present Dead Sea. The chemistry of Lake Lisan at its stable stand represented a material balance between a Jordan-like input, an original large mass of salts and a chemical removal of aragonite. The weighted average depth of Lake Lisan is calculated, on a geochemical basis, to have been at least 400, preferably 600 m.The oxygen isotopic composition of Lake Lisan water, which was higher by at least 3%. than that of the Dead Sea, was probably dictated by a higher rate of evaporation.Na/Ca ratios in aragonite, which correlate well with δ13C values, but change frequently in time, reflect the existence of a short lived upper water layer of varying salinity in Lake Lisan.  相似文献   

14.
The stability of the amphibole pargasite [NaCa2Mg4Al(Al2Si6))O22(OH)2] in the melting range has been determined at total pressures (P) of 1.2 to 8 kbar. The activity of H2O was controlled independently of P by using mixtures of H2O + CO2 in the fluid phase. The mole fraction of H2O in the fluid (XH2O1fl) ranged from 1.0 to 0.2.At P < 4 kbar the stability temperature (T) of pargasite decreases with decreasing XH2O1fl at constant P. Above P ? 4 kbar stability T increases as XH2O1fl is decreased below one, passes through a T maximum and then decreases with a further decrease in XH2O1fl. This behavior is due to a decrease in the H2O content of the silicate liquid as XH2O1fl decreases. The magnitude of the T maximum increases from about 10°C (relative to the stability T for XH2O1fl= 1) at P = 5 kbar to about 30°C at P = 8 kbar, and the position of the maximum shifts from XH2O1fl ? 0.6 at P = 5 kbar to XH2O1fl? 0.4 at P = 8 kbar.The H2O content of liquid coexisting with pargasite has been estimated as a function of XH2O1fl at 5 and 8 kbar P, and can be used to estimate the H2O content of magmas. Because pargasite is stable at low values of XH2O1fl at high P and T, hornblende can be an important phase in igneous processes even at relatively low H2O fugacities.  相似文献   

15.
Diopside-melt and forsterite-melt rare earth (REE) and Ni partition coefficients have been determined as a function of bulk compositions of the melt. Available Raman spectroscopic data have been used to determine the structures of the melts coexisting with diopside and forsterite. The compositional dependence of the partition coefficients is then related to the structural changes of the melt.The melts in all experiments have a ratio of nonbridging oxygens to tetrahedral cations (NBOT) between 1 and 0. The quenched melts consist of structural units that have, on the average, 2 (chain), 1 (sheet) and 0 (three-dimensional network) nonbridging oxygens per tetrahedral cation. The proportions of these structural units in the melts, as well as the overall NBOT, change as a function of the bulk composition of the melt.It has been found that Ce, Sm, Tm and Ni crystal-liquid partition coefficients (Kcrystal?liqi = CcrystaliCliqi) decrease linearly with increasing NBOT. The values of the individual REE crystal-liquid trace element partition coefficients have different functional relations to NBOT, so that the degree of light REE enrichment of the melts would depend on their NBOT.The solution mechanisms of minor oxides such as CO2, H2O, TiO2, P2O5 and Fe2O3 in silicate melts are known. These data have been recast as changes of NBOT of the melts with regard to the type of oxide and its concentration in the melt. From such data the dependence of crystal-liquid partition coefficients on concentration and type of minor oxide in melt solution has been calculated.  相似文献   

16.
Numerical modeling of the terrestrial oxygen budget based on the revised δ13Ccarb record by Veizeret al. (1980) has shown that total photosynthetic oxygen has varied between ±7% and ±10% of its average reservoir size (~3.2 × 1022 g) during the last 800 myr as a result of oscillations of the sedimentary reservoir of organic carbon. Calculated curves of oxygen evolution display a distinct minimum in the Early Paleozoic framed by two maxima in the Latest Proterozoic and the Mesozoic. The sympathetic relationship observed between the curves of total oxygen evolution and respective functions for the partial reservoir of sulfate-bound oxygen suggests that the O2 required for an additional conversion of sulfide to sulfate was most probably provided by excess burial of organic carbon, the results of the modeling thus adding credence to current interpretations proposed for the negative correlation between the secular 13C12C and 34S32S trends.  相似文献   

17.
Equations are developed for calculating the density of aluminosilicate liquids as a function of composition and temperature. The mean molar volume at reference temperature Tr, is given by Vr = ∑XiV?oi + XAV?oA, where the summation is taken over all oxide components except A12O3, X stands for mole fraction, V?oi terms are constants derived independently from an analysis of volume-composition relations in alumina-free silicate liquids, and V?oA is the composition-dependent apparent partial molar volume of Al2O3. The thermal expansion coefficient of aluminosilicate liquids is given by α = ∑Xi\?gaio + XA\?gaAo, where \?gaio terms are constants independent of temperature and composition, and \?gaoA is a composition-dependent term representing the effect of Al2O3 on the thermal expansion. Parameters necessary to calculate the volume of silicate liquids at any temperature T according to V(T) = Vrexp[α(T-Tr)], where Tr = 1400°C have been evaluated by least-square analysis of selected density measurements in aluminosilicate melts. Mean molar volumes of aluminosilicate liquids calculated according to the model equation conform to experimentally measured volumes with a root mean square difference of 0.28 ccmole and an average absolute difference of 0.90% for 248 experimental observations. The compositional dependence of V?oA is discussed in terms of several possible interpretations of the structural role of Al3+ in aluminosilicate melts.  相似文献   

18.
A parameter ΔO2?, defined as the difference between the Gibbs energy of formation of a given oxide and its aqueous cation, was used to obtain linear relationships among Gibbs energies of formation from the elements of hydroxides, oxides and aqueous metallic ions (Tardy and Garrels, 1976). Use of this parameter has now been extended to meta- and orthosilicates for which the Gibbs energies of formation of silicates from their oxides are shown to be linear functions of the ΔO2? values of their constituent cations. The function obtained for metasilicates is:
ΔGo?silicate ? ∑ΔGo?oxides = ? 23(ΔO2?cation ? ΔO2?silicon
and that for orthosilicates is:
ΔGo?silicate ? ∑ΔGo?oxides = ? 44(ΔO2?cation ? ΔO2?silicon
in which Δo? silicate is the Gibbs energy of formation from the elements of a silicate of a given cation and ∑ΔGo? oxides is the sum of the Gibbs energies of formation from the elements of the constituent oxides of the silicate considered.These functions can be used to test for consistency within and between various sources of thermodynamic data and to estimate free energy of formation values for previously unstudied species.  相似文献   

19.
Light hydrocarbon (C1-C3) concentrations in the water from four Red Sea brine basins (Atlantis II, Suakin, Nereus and Valdivia Deeps) and in sediment pore waters from two of these areas (Atlantis II and Suakin Deeps) are reported. The hydrocarbon gases in the Suakin Deep brine (T = ~ 25°C, Cl? = ~ 85‰, CH4 =~ 711) are apparently of biogenic origin as evidenced by C1(C2 + C3) ratios of ~ 1000. Methane concentrations (6–8 μl/l) in Suakin Deep sediments are nearly equal to those in the brine, suggesting sedimentary interstitial waters may be the source of the brine and associated methane.The Atlantis II Deep has two brine layers with significantly different light hydrocarbon concentrations indicating separate sources. The upper brine (T = ~ 50°C, Cl? = ~ 73‰, CH4 = ~ 155 μl/l) gas seems to be of biogenic origin [C1(C2 + C3) = ~1100], whereas the lower brine (T = ~ 61°C, Cl? = ~ 155‰, CH4 = ~ 120μl/l) gas is apparently of thermogenic origin [C1(C2 + C3) = ~ 50]. The thermogenic gas resulting from thermal cracking of organic matter in the sedimentary column apparently migrates into the basin with the brine, whereas the biogenic gas is produced in situ or at the seawater-brine interface. Methane concentrations in Atlantis II interstitial waters underlying the lower brine are about one half brine concentrations; this difference possibly reflects the known temporal variations of hydrothermal activity in the basin.  相似文献   

20.
Radiocarbon and 230Th-234U dates of calcic horizons from calciorthid soil profiles in the Mojave Desert were used to calculate the rate of deposition of pedogenic CaCO3. A major period of CaCO3 deposition appears to have occurred about 20000 yBP forming calcic horizons below 100-cm depth during a climatic regime with greater effective rainfall than in the present. The overall rate of deposition has been 1.0 to 3.5 g CaCO3/m2/yr during soil formation. This rate is consistent with present-day rates, assuming that the atmospheric deposition of Ca limits the process. Stable isotope ratios in calcic horizons indicate that CaCO3 precipitated from a soil environment with CO2 of ? 15.5%. 13C12C (vs. PDB) and H2O of + 2.0%. 18O16O (vs. SMOW). These values suggest that CaCO3 precipitates when seasonal drought simultaneously lowers soil pore pCO2 and enriches soil water 18O by evaporation. The role of soil calcic horizons in the global geochemical cycle of carbon is discussed.  相似文献   

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