首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献，搜索用时 31 毫秒
1.
We have determined the Nd3+ diffusion kinetics in natural enstatite crystals as a function of temperature, f(O2) and crystallographic direction at 1 bar pressure and applied these data to several terrestrial and planetary problems. The diffusion is found to be anisotropic with the diffusion parallel to the c-axial direction being significantly greater than that parallel to a- and b-axis. Also, D(//a) is likely to be somewhat greater than D(//b). Diffusion experiments parallel to the b-axial direction as a function of f(O2) do not show a significant dependence of D(Nd3+) on f(O2) within the range defined by the IW buffer and 1.5 log unit above the WM buffer. The observed diffusion anisotropy and weak f(O2) effect on D(Nd3+) may be understood by considering the crystal structure of enstatite and the likely diffusion pathways. Using the experimental data for D(Nd3+), we calculated the closure temperature of the Sm-Nd geochronological system in enstatite during cooling as a function of cooling rate, grain size and geometry, initial (peak) temperature and diffusion direction. We have also evaluated the approximate domain of validity of closure temperatures calculated on the basis of an infinite plane sheet model for finite plane sheets showing anisotropic diffusion. These results provide a quantitative framework for the interpretation of Sm-Nd mineral ages of orthopyroxene in planetary samples. We discuss the implications of our experimental data to the problems of melting and subsolidus cooling of mantle rocks, and the resetting of Sm-Nd mineral ages in mesosiderites. It is found that a cooling model proposed earlier [Ganguly J., Yang H., Ghose S., 1994. Thermal history of mesosiderites: Quantitative constraints from compositional zoning and Fe-Mg ordering in orthopyroxene. Geochim. Cosmochim. Acta 58, 2711-2723] could lead to the observed ∼90 Ma difference between the U-Pb age and Sm-Nd mineral age for mesosiderites, thus obviating the need for a model of resetting of the Sm-Nd mineral age by an “impulsive disturbance” [Prinzhoffer A, Papanastassiou D.A, Wasserburg G.J., 1992. Samarium-neodymium evolution of meteorites. Geochim. Cosmochim. Acta 56, 797-815].  相似文献   

2.
Thermochronology has revolutionized our understanding of the establishment and evolution of lithospheric thermal structure. However, many potential benefits provided by the application of diffusion theory to thermochronology have yet to be fully exploited. This study uses apatite (Tc = 450-550 °C) and titanite (Tc = 550-650 °C) U-Pb ID-TIMS thermochronology at the single- to sub-grain scale to separate the variable effects of volume diffusion of Pb from metamorphic (over)growth above and below the Tc of a mineral. Data are presented from two ca. 3227 Ma tonalite samples from north and south of the Barberton Greenstone Belt (BGB), southern Africa. Two distinct populations of apatite from a sample north of the BGB record fast cooling followed by metamorphic growth ∼10 Myr later. Both apatite and titanite dates from south of the BGB show a strong correlation with the grain size and record 100 Myr of post-emplacement cooling. Complex core-rim zoning observed in cathodoluminescence images of apatite is interpreted to reflect metamorphic overgrowth above the Tc. The age and topology of grain size versus date curves from titanite and apatite are used in combination with a finite-difference numerical model to show that slow, non-linear, cooling and not thermal resetting is responsible for the observed distribution. The thermal histories from either side of the BGB are very different and provide unique insight into the BGB’s tectonic evolution: a ∼70 Myr period of apparent stability after ca. 3.2 Ga terrane assembly was followed by fast exhumation south of the BGB that led to lower-crustal melting and intrusion of granitic batholiths ca. 3.14-3.10 Ga.  相似文献   

3.
Recent work [Shuster D. L., Flowers R. M. and Farley K. A. (2006) The influence of natural radiation damage on helium diffusion kinetics in apatite. Earth Planet. Sci. Lett.249(3-4), 148-161] revealing a correlation between radiogenic 4He concentration and He diffusivity in natural apatites suggests that helium migration is retarded by radiation-induced damage to the crystal structure. If so, the He diffusion kinetics of an apatite is an evolving function of time and the effective uranium concentration in a cooling sample, a fact which must be considered when interpreting apatite (U-Th)/He ages. Here we report the results of experiments designed to investigate and quantify this phenomenon by determining He diffusivities in apatites after systematically adding or removing radiation damage.Radiation damage was added to a suite of synthetic and natural apatites by exposure to between 1 and 100 h of neutron irradiation in a nuclear reactor. The samples were then irradiated with a 220 MeV proton beam and the resulting spallogenic 3He used as a diffusant in step-heating diffusion experiments. In every sample, irradiation increased the activation energy (Ea) and the frequency factor (Do/a2) of diffusion and yielded a higher He closure temperature (Tc) than the starting material. For example, 100 h in the reactor caused the He closure temperature to increase by as much as 36 °C. For a given neutron fluence the magnitude of increase in closure temperature scales negatively with the initial closure temperature. This is consistent with a logarithmic response in which the neutron damage is additive to the initial damage present. In detail, the irradiations introduce correlated increases in Ea and ln(Do/a2) that lie on the same array as found in natural apatites. This strongly suggests that neutron-induced damage mimics the damage produced by U and Th decay in natural apatites.To investigate the potential consequences of annealing of radiation damage, samples of Durango apatite were heated in vacuum to temperatures up to 550 °C for between 1 and 350 h. After this treatment the samples were step-heated using the remaining natural 4He as the diffusant. At temperatures above 290 °C a systematic change in Tc was observed, with values becoming lower with increasing temperature and time. For example, reduction of Tc from the starting value of 71 to ∼52 °C occurred in 1 h at 375 °C or 10 h at 330 °C. The observed variations in Tc are strongly correlated with the fission track length reduction predicted from the initial holding time and temperature. Furthermore, like the neutron irradiated apatites, these samples plot on the same Ea − ln(Do/a2) array as natural samples, suggesting that damage annealing is simply undoing the consequences of damage accumulation in terms of He diffusivity.Taken together these data provide unequivocal evidence that at these levels, radiation damage acts to retard He diffusion in apatite, and that thermal annealing reverses the process. The data provide support for the previously described radiation damage trapping kinetic model of Shuster et al. (2006) and can be used to define a model which fully accommodates damage production and annealing.  相似文献   

4.
Rapid Pb-Pb dating of natural rutile crystals by laser ablation multiple-collector inductively coupled plasma mass spectrometry (LA-MC-ICPMS) is investigated as a tool for constraining geological temperature-time histories. LA-MC-ICPMS was used to analyse Pb isotopes in rutile from granulite-facies rocks from the Reynolds Range, Northern Territory, Australia. The resultant ages were compared with previous U-Pb zircon and monazite age determinations and new mica (muscovite, phlogopite, and biotite) Rb-Sr ages from the same metamorphic terrane. Rutile crystals ranging in size from 3.5 to 0.05 mm with ?20 ppm Pb were ablated with a 300-25 μm diameter laser beam. Crystals larger than 0.5 mm yielded sufficiently precise 206Pb/204Pb and 207Pb/204Pb ratios to correct for the presence of common Pb, and individual rutile crystals often exhibited sufficient Pb isotopic heterogeneity to allow isochron calculations to be performed on replicate analyses of a single crystal. The mean of 12 isochron ages is 1544 ± 8 Ma (2 SD), with isochron ages for single crystals having uncertainties as low as ±1.3 Myr (2 SD). The 207Pb-206Pb ages calculated without correction for common Pb are typically <0.5% higher than the common-Pb-corrected isochron ages reflecting the very minor amounts of common Pb present in the rutile. The LA-MC-ICPMS method described samples only the outer 0.1-0.2 mm of the rutile crystals, resulting in a grain size-independent apparent closure temperature (Tc) for Pb diffusion in rutile that is less than the Tc of monazite ?0.1 mm in diameter, but significantly higher than the Rb-Sr system in muscovite (550 °C), phlogopite (435 °C) and biotite (400 °C). Even small rutile crystals are extremely resistant to isotopic resetting. For the established slow cooling rate of ca. 3 °C/Myr, the Tc for Pb diffusion in the analysed rutile is ca. 630 °C. This is in excellent agreement with recent experimental results that indicate that rutile has a higher Tc than previously thought (ca. 600-640 °C for rutile 0.1-0.2 mm diameter cooled at 3 °C/Myr; near 600 °C [Cherniak D.J., 2000. Pb diffusion in rutile. Contrib. Mineral. Petrol. 139, 198-207], versus 400 °C [Mezger, K., Hanson G.N., Bohlen S.R., 1989a. High precision U-Pb ages of metamorphic rutile: applications to the cooling history of high-grade terranes. Earth Planet. Sci. Lett. 96, 106-118.] for 1 °C/Myr), and with current Tc estimates for monazite and other high temperature geochronometers, which have been revised upwards in recent years. The new rutile ages, together with the other geochronological data from the region, support the interpretation that the Reynolds Range underwent prolonged slow cooling on a conductive geotherm, under nearly steady-state conditions. Slow cooling at ca. 3 °C/Myr persisted for at least 40 Myr followed the peak of high-T/low-P metamorphism to granulite-facies conditions, and probably continued at ca. 2-3 °C/Myr for ca. 200 Myr overall.  相似文献   

5.
Hydrothermal treatment of closely sized muscovite aggregates in a piston-cylinder apparatus induced 40Ar∗ loss that is revealed in 40Ar/39Ar step heating spectra. Age spectra and Arrhenius data, however, differ from that expected from a single diffusion length scale. A numerical model of episodic loss assuming the presence of multiple diffusion domains yields excellent fits between synthetic and actual degassing spectra. We used this model to isolate 40Ar∗ loss from the grains that remained intact during hydrothermal treatment at 10 kbar permitting calculation of diffusion coefficients in the temperature range 730-600 °C. Diffusion data generated in this manner yield an activation energy (E) of 63 ± 7 kcal/mol and frequency factor (Do) of 2.3  cm2/s. Experiments at 20 kbar yield diffusivities lower by about an order of magnitude and correspond to an activation volume of ∼14 cm3/mol. Together, these parameters predict substantially greater retentivity of Ar in muscovite than previously assumed and correspond to a closure temperature (Tc) of 425 °C for a 100 μm radius grain cooling at 10 °C/Ma at 10 kbar (Tc = 405 °C at 5 kbar. Age and log (r/ro) spectra for the run products show strong correlations indicating that muscovites can retain Ar diffusion boundaries and mechanisms that define their natural retentivity during vacuum step heating. This may permit the application of high resolution, continuous 40Ar/39Ar thermochronology to low grade, regionally metamorphosed terranes.  相似文献   

6.
In order to investigate the incorporation of Sr, Mg, and U into coral skeletons and its temperature dependency, we performed a culture experiment in which specimens of the branching coral (Porites cylindrica) were grown for 1 month at three seawater temperatures (22, 26, and 30 °C). The results of this study showed that the linear extension rate of P. cylindrica has little effect on the skeletal Sr/Ca, Mg/Ca, and U/Ca ratios. The following temperature equations were derived: Sr/Ca (mmol/mol) = 10.214(±0.229) − 0.0642(±0.00897) × T (°C) (r2 = 0.59, p < 0.05); Mg/Ca (mmol/mol) = 1.973(±0.302) + 0.1002(±0.0118) × T (°C) (r2 = 0.67, p < 0.05); and U/Ca (μmol/mol) = 1.488(±0.0484) − 0.0212(±0.00189) × T (°C) (r2 = 0.78, p < 0.05). We calculated the distribution coefficient (D) of Sr, Mg, and U relative to seawater temperature and compared the results with previous data from massive Porites corals. The seawater temperature proxies based on D calibrations of P. cylindrica established in this study are generally similar to those for massive Porites corals, despite a difference in the slope of DU calibration. The calibration sensitivity of DSr, DMg, and DU to seawater temperature change during the experiment was 0.64%/°C, 1.93%/°C, and 1.97%/°C, respectively. These results suggest that the skeletal Sr/Ca ratio (and possibly the Mg/Ca and/or U/Ca ratio) of the branching coral P. cylindrica can be used as a potential paleothermometer.  相似文献   

7.
Laser depth profiling studies of helium diffusion in Durango fluorapatite   总被引：1，自引：0，他引：1  
Ultraviolet lasers coupled with sensitive mass spectrometers provide a useful way to measure laboratory-induced noble gas diffusion profiles in minerals, thus enabling the calculation of diffusion parameters. We illustrate this laser ablation depth profiling (LADP) technique for a previously well-studied mineral-isotopic system: 4He in Durango fluorapatite. LADP studies were conducted on oriented, polished slabs from a single crystal that were heated under vacuum to a variety of temperatures between 300 and 450 °C for variable times. The resolved 4He profiles exhibited error-function loss as predicted by previous bulk 4He diffusion studies. All of the slabs, regardless of crystallographic orientation, yielded modeled diffusivities that are statistically co-linear on an Arrhenius diagram, suggesting no diffusional anisotropy of 4He in this material. The data indicate an activation energy of 142.2 ± 5.0 (2σ) kJ/mol and diffusivity at infinite temperature - reported as ln(D0) - of −4.71 ± 0.94 (2σ) m2/s. These values imply a bulk closure temperature for 4He in Durango fluorapatite of 74 °C for a 50 μm radius grain, infinite cylinder geometry, and a cooling rate of 10 °C/Myr.  相似文献   

8.
Helium diffusivity was measured in synthetic rare-earth-element orthophosphates with systematically varying properties to evaluate potential controls on He transport in minerals. In the zircon structure phosphates (in this study, the phosphates of Tb, Dy, Ho, Er, Tm, Yb, and Lu as well as synthetic xenotime, YPO4), He diffusion is strongly anisotropic. Transport apparently proceeds preferentially through channels aligned with the c-axis. The activation energy for diffusion is almost the same (122 ± 6 kJ/mol) in all members of this family, but there is a monotonic decrease in Do with atomic number from TbPO4 (∼105 cm2/s) to LuPO4 (∼10 cm2/s). The c-parallel channels become increasingly constricted in the same sequence, likely accounting for the systematically decreasing diffusivity. The He closure temperature (r = 1 cm, dT/dt = 10 °C/Myr) increases with atomic number from 44 °C for TbPO4 to 88 °C for LuPO4. Diffusion of radiogenic helium from natural zircon and xenotime is much slower than these synthetic analogs predict, suggesting that coupled substitution of REE and P for Zr and Si and/or radiation damage profoundly modify the energetics of interstitial He diffusion. In particular, α-recoil may play a key role by damaging the continuity and integrity of the channels.Monazite structure phosphates (here La, Ce, Pr, Nd, Sm, and Gd phosphate) are far more He retentive than those of the zircon structure. Activation energies increase smoothly with atomic number from LaPO4 (183 kJ/mol) to NdPO4 (224 kJ/mol) then decrease again to GdPO4 (198 kJ/mol). Do values mimic this pattern, spanning a range from ∼10−1 cm2/s (GdPO4) to 104 cm2/s (NdPO4). Nevertheless, He closure temperatures increase monotonically with atomic number, from 300 °C in LaPO4 to 410 °C in GdPO4. No evidence was obtained bearing on diffusion anisotropy, but the monazite structure lacks through-going channels so it is not expected. Diffusion parameters for radiogenic helium in natural monazite are similar to those obtained on the synthetic analogs.Ionic porosity is not the primary control on He diffusion in the orthophosphates. Within a given structure and with limited elemental substitution, ionic porosity and He closure temperature are negatively correlated, as predicted. However, differences between crystal structures are far more important than ion packing density: at comparable ionic porosity the monazite structure phosphates have He closure temperatures ∼300 °C higher than the xenotime structure phosphates. Modifications to the structures by radiation damage likely play a similarly significant role in controlling He diffusion.  相似文献   

9.
Diffusive isotopic fractionation factors are important in order to understand natural processes and have practical application in radioactive waste storage and carbon dioxide sequestration. We determined the isotope fractionation factors and the effective diffusion coefficients of chloride and bromide ions during aqueous diffusion in polyacrylamide gel. Diffusion was determined as functions of temperature, time and concentration. The effect of temperature is relatively large on the diffusion coefficient (D) but only small on isotope fractionation. For chlorine, the ratio, D35Cl/D37Cl varied from 1.00128 ± 0.00017 (1σ) at 2 °C to 1.00192 ± 0.00015 at 80 °C. For bromine, D79Br/D81Br varied from 1.00098 ± 0.00009 at 2 °C to 1.0064 ± 0.00013 at 21 °C and 1.00078 ± 0.00018 (1σ) at 80 °C. There were no significant effects on the isotope fractionation due to concentration. The lack of sensitivity of the diffusive isotope fractionation to anything at the most common temperatures (0 to 30 °C) makes it particularly valuable for application to understanding processes in geological environments and an important natural tracer in order to understand fluid transport processes.  相似文献   

10.
Plagioclase is not only the most abundant mineral in the Earth’s crust, but is present in almost all terrestrial tectonic settings and is widespread in most extraterrestrial material. Applying the K-Ar system to this common mineral would provide a powerful tool for quantifying thermal histories in a wide variety of settings. Nonetheless, plagioclase has rarely been used for thermochronometry, largely due to difficulties in simultaneously acquiring precise geochronologic data and quantifying argon diffusion kinetics from a mineral with low-K concentration. Here we describe an analytical technique that generates high-precision 40Ar/39Ar data and quantifies Ar diffusion kinetics of low-K minerals. We present results of five diffusion experiments conducted on single crystals of plagioclase from the Bushveld Complex, South Africa. The observed diffusion kinetics yield internally consistent thermochronological constraints, indicating that plagioclase is a reliable thermochronometer. Individual grains have activation energies of 155-178 kJ/mol and ln(D0/a2) varies between 3.5 and 6.5. These diffusion parameters correspond to closure temperatures of 225-300 °C, for a 10 °C/Ma cooling rate. Age spectra generally conform to single-domain diffusive loss profiles, suggesting that grain-scale diffusion dominates argon transport in this fairly simple plagioclase. Conjointly examining several single-grain analyses enables us to distinguish episodic reheating from slow cooling and indicates that the Bushveld Complex cooled rapidly and monotonically from magmatic temperature to <300 °C over 3 Ma, followed by protracted cooling to ambient crustal temperatures of 150-200 °C over ∼600 Ma.  相似文献   

11.
Self-diffusion of sulfur in pyrite (FeS2) was characterized over the temperature range ∼500-725 °C (∼1 bar pressure) by immersing natural specimens in a bath of molten elemental 34S and characterizing the resulting diffusive-exchange profiles by Rutherford backscattering spectroscopy (RBS). The temperature dependence of the sulfur diffusivity (DS) conforms to DS = Do exp(−Ea/RT), where the pre-exponential constant (Do) and the activation energy (Ea) are constrained as follows:
  相似文献   

12.
In the last decade the zircon (U-Th)/He (ZHe) thermochronometer has been applied to a variety of geologic problems. Although bulk diffusion coefficients for He in zircon are available from laboratory step-heating experiments, little is known about the diffusion mechanism(s) and their dependence on the crystallographic structure of zircon. Here, we investigate the diffusion of He in perfectly crystalline zircon using atomistic simulation methods that provide insights into the structural pathways of He migration in zircon. Empirical force fields and quantum-mechanical calculations reveal that the energy barriers for He diffusion are strongly dependent on structure. The most favorable pathway for He diffusion is the [0 0 1] direction through the open channels parallel to the c-axis (, activation energy for tracer diffusion of a He atom along [0 0 1]). In contrast, energy barriers are higher in other directions where narrower channels for He diffusion are identified, such as [1 0 0], [1 0 1], and [1 1 0] (ΔE∗ of 44.8, 101.7, and 421.3 kJ mol−1, respectively). Molecular dynamics simulations are in agreement with these results and provide additional insight in the diffusion mechanisms along different crystallographic directions, as well as the temperature dependence. Below the closure temperature of He in zircon [Tc ∼ 180 °C, Reiners P. W., Spell T. L., Nicolescu S., and Zanetti K. A. (2004) Zircon (U-Th)/He thermochronometry: He diffusion and comparisons with Ar-40/Ar-39 dating. Geochim. Cosmochim. Acta68, 1857-1887], diffusion is anisotropic as He moves preferentially along the [0 0 1] direction, and calculated tracer diffusivities along the two most favorable directions differ by approximately five orders of magnitude (D[001]/D[100] ∼ 105, at T = 25 °C). Above this temperature, He atoms start to hop between adjacent [0 0 1] channels, along [1 0 0] and [0 1 0] directions (perpendicular to the c-axis). The diffusion along [1 0 0] and [0 1 0] is thermally activated, such that at higher temperatures, He diffusion in zircon becomes nearly isotropic (D[001]/D[100] ∼ 10, at T = 580 °C). These results suggest that the anisotropic nature of He diffusion at temperatures near the closure temperature should be considered in future diffusivity experiments. Furthermore, care should be taken when making geologic interpretations (e.g., exhumation rates, timing of cooling, etc.) from this thermochronometer until the effects of anisotropic diffusion on bulk ages and closure temperature estimates are better quantified.  相似文献   

13.
The sulfur concentration at pyrrhotite- and anhydrite-saturation in primitive hydrous basaltic melt of the 2001-2002 eruption of Mt. Etna was determined at 200 MPa, T = 1050-1250 °C and at log fO2 from FMQ to FMQ+2.2 (FMQ is Fayalite-Magnetite-Quartz oxygen buffer). At 1050 °C Au sample containers were used. A double-capsule technique, using a single crystal olivine sample container closed with an olivine piston, embedded in a sealed Au80Pd20 capsule, was developed to perform experiments in S-bearing hydrous basaltic systems at T > 1050 °C. Pyrrhotite is found to be a stable phase coexisting with melt at FMQ-FMQ+0.3, whereas anhydrite is stable at FMQ+1.4-FMQ+2.2. The S concentration in the melt increases almost linearly from 0.12 ± 0.01 to 0.39 ± 0.02 wt.% S at FeS-saturation and from 0.74 ± 0.01 to 1.08 ± 0.04 wt.% S at anhydrite-saturation with T ranging from 1050-1250 °C. The relationships between S concentration at pyrrhotite and/or anhydrite saturation, MgO content of the olivine-saturated melt, T, and log fO2 observed in this study and from previous data are used to develop an empirical model for estimating the magmatic T and fO2 from the S and MgO concentrations of H2O-bearing olivine-saturated basaltic melts. The model can also be used to determine maximum S concentrations, if fO2 and MgO content of the melt are known. The application of the model to compositions of melt inclusions in olivines from Mt. Etna indicates that the most primitive magmas trapped in inclusions might have been stored at log fO2 slightly higher than FMQ+1 and at T = 1100-1150 °C, whereas more evolved melts could have been trapped at T ? 1100 °C. These values are in a good agreement with the estimates obtained by other independent methods reported in the literature.  相似文献   

14.
We have studied the formation conditions of Al-rich chondrules by doing isothermal and dynamic crystallization experiments at one atmosphere on four different chondrule analogue compositions within the pure CaO-MgO-Al2O3-SiO2 system. For the dynamic crystallization experiments, we cooled from both liquidus and subliquidus peak temperatures (Tmax), at cooling rates from 5-1000 °C/h. The starting compositions include two with anorthite and two with forsterite as the dominant liquidus phases, all at or near spinel-saturation. One of each pair evolves towards diopside crystallization, and the others cordierite or enstatite crystallization, giving a total of four completely different crystallization sequences analogous to the four basic varieties of Al-rich chondrule recently proposed. Bulk composition is the main controlling factor, both in terms of mineralogy and texture. The textures of the anorthite-rich compositions are more sensitive to Tmax than they are to cooling rate, whereas the textures of the forsterite-rich compositions are more sensitive to cooling rate. Comparisons of natural Al-rich chondrules having similar compositions to our synthetic analogues indicate that the natural objects reflect a range of peak heating temperatures, ∼1400-1500 °C, and cooling rates of 10-500 °C/h for porphyritic chondrules and possibly higher (1000 °C/h) for barred chondrules. These conditions are consistent with the conditions inferred for ferromagnesian chondrules but differ from those inferred for some calcium-aluminum-rich inclusions.  相似文献   

15.
Petrological and geochemical study of volatile bearing phases (fluid inclusions, amphibole, and nominally anhydrous minerals) in a spinel lherzolite xenolith suite from Quaternary lavas at Injibara (Lake Tana region, Ethiopian plateau) shows compelling evidence for metasomatism in the lithospheric mantle in a region of mantle upwelling and continental flood basalts. The xenolith suite consists of deformed (i.e., protogranular to porphyroclastic texture) Cl-rich pargasite lherzolites, metasomatized (LILE and Pb enrichment in clinopyroxene and amphibole) at T ? 1000 °C. Lherzolites contain chlorine-rich H2O-CO2 fluid inclusions, but no melt inclusions. Fluid inclusions are preserved only in orthopyroxene, while in olivine, they underwent extensive interaction with the host mineral. The metasomatic fluid composition is estimated: XCO2 = 0.64, XH2O = 0.33, XNa = 0.006, XMg = 0.006, XCl = 0.018, (salinity = 14-10 NaCl eq. wt.%, aH2O = 0.2, Cl = 4-5 mol.%). Fluid isochores correspond to trapping pressures of 1.4-1.5 GPa or 50-54 km depth (at T = 950 °C). Synchrotron sourced micro-infrared mapping (ELECTRA, Trieste) shows gradients for H2O-distribution in nominally anhydrous minerals, with considerable enrichment at grain boundaries, along intragranular microfractures, and around fluid inclusions. Total water amounts in lherzolites are variable from about 150 up to 400 ppm. Calculated trace-element pattern of metasomatic fluid phases, combined with distribution and amount of H2O in nominally anhydrous minerals, delineate a metasomatic Cl- and LILE-rich fluid phase heterogeneously distributed in the continental lithosphere. Present data suggest that Cl-rich aqueous fluids were important metasomatic agents beneath the Ethiopian plateau, locally forming a source of high water content in the peridotite, which may be easily melted. High Cl, LILE, and Pb in metasomatic fluid phases suggest the contribution of recycled altered oceanic lithosphere component in their source.  相似文献   

16.
Considerable advances in our understanding of physicochemical properties of geological fluids and their roles in many geological processes have been achieved by the use of synthetic fluid inclusions. We have developed a new method to synthesize fluid inclusions containing organic and inorganic material in fused silica capillary tubing. We have used both round (0.3 mm OD and 0.05 or 0.1 mm ID) and square cross-section tubing (0.3 × 0.3 mm with 0.05 × 0.05 mm or 0.1 × 0.1 mm cavities). For microthermometric measurements in a USGS-type heating-cooling stage, sample capsules must be less than 25 mm in length. The square-sectioned capsules have the advantage of providing images without optical distortion. However, the maximum internal pressure (P; about 100 MPa at 22 °C) and temperature (T; about 500 °C) maintained by the square-sectioned capsules are less than those held by the round-sectioned capsules (about 300 MPa at room T, and T up to 650 °C).The fused silica capsules can be applied to a wide range of problems of interest in fluid inclusion and hydrothermal research, such as creating standards for the calibration of thermocouples in heating-cooling stages and frequency shifts in Raman spectrometers. The fused silica capsules can also be used as containers for hydrothermal reactions, especially for organic samples, including individual hydrocarbons, crude oils, and gases, such as cracking of C18H38 between 350 and 400 °C, isotopic exchanges between C18H38 and D2O and between C19D40 and H2O at similar temperatures. Results of these types of studies provide information on the kinetics of oil cracking and the changes of oil composition under thermal stress.When compared with synthesis of fluid inclusions formed by healing fractures in quartz or other minerals or by overgrowth of quartz at elevated P-T conditions, the new fused-silica method has the following advantages: (1) it is simple; (2) fluid inclusions without the presence of water can be formed; (3) synthesized inclusions are large and uniform, and they are able to tolerate high internal P; (4) it is suitable for the study of organic material; and (5) redox control is possible due to high permeability of the fused silica to hydrogen.  相似文献   

17.
Published data on the distribution of Fe and Mg between the two distinct octahedral sites (M1 and M2) in orthopyroxenes show that the equilibrium Fe-Mg distribution coefficient (KD) is roughly constant at intermediate ferrosilite content (XFs of 0.2 to 0.6) but at low XFs (<0.2) is either anomalously high (Mössbauer data) or low (XRD data) compared to KD at intermediate XFs. We report an experimental study on the equilibrium KD values for two natural single crystals of orthopyroxene (with XFs of 0.011 and 0.160) using a high-sensitivity Mössbauer spectrometer. The KD values were determined at 1 bar and temperatures between 600 and 1000°C, and reversed at 600 to 900°C. The values are found to be independent of orthopyroxene composition at a given temperature within analytical uncertainties, and in agreement with KD values at intermediate XFs. A least-squares fit to the KD data yields: lnKD = 0.391(±0.131) − 2205(±141)/T, where T is temperature in K, and uncertainties are at the 2σ level. This equation is valid for XFs values up to at least 0.6. We suggest that previous Mössbauer and XRD data at low XFs were compromised by analytical difficulties. The new result that KD is roughly independent of XFs greatly simplifies treatment of equilibrium and speedometry based on Fe-Mg order-disorder in orthopyroxene.  相似文献   

18.
The δ18O of ground water (−13.54 ± 0.05 ‰) and inorganically precipitated Holocene vein calcite (+14.56 ± 0.03 ‰) from Devils Hole cave #2 in southcentral Nevada yield an oxygen isotopic fractionation factor between calcite and water at 33.7 °C of 1.02849 ± 0.00013 (1000 ln αcalcite-water = 28.09 ± 0.13). Using the commonly accepted value of ∂(αcalcite-water)/∂T of −0.00020 K−1, this corresponds to a 1000 ln αcalcite-water value at 25 °C of 29.80, which differs substantially from the current accepted value of 28.3. Use of previously published oxygen isotopic fractionation factors would yield a calcite precipitation temperature in Devils Hole that is 8 °C lower than the measured ground water temperature. Alternatively, previously published fractionation factors would yield a δ18O of water, from which the calcite precipitated, that is too negative by 1.5 ‰ using a temperature of 33.7 °C. Several lines of evidence indicate that the geochemical environment of Devils Hole has been remarkably constant for at least 10 ka. Accordingly, a re-evaluation of calcite-water oxygen isotopic fractionation factor may be in order.Assuming the Devils Hole oxygen isotopic value of αcalcite-water represents thermodynamic equilibrium, many marine carbonates are precipitated with a δ18O value that is too low, apparently due to a kinetic isotopic fractionation that preferentially enriches 16O in the solid carbonate over 18O, feigning oxygen isotopic equilibrium.  相似文献   

19.
Low temperature vent fluids (<91 °C) issuing from the ultramafic-hosted hydrothermal system at Lost City, 30°N Mid-Atlantic Ridge, are enriched in dissolved volatiles (H2,CH4) while attaining elevated pH values, indicative of the serpentization processes that govern water/rock interactions deep in the oceanic crust. Here, we present a series of theoretical models to evaluate the extent of hydrothermal alteration and assess the effect of cooling on the systematics of pH-controlled B aqueous species. Peridotite-seawater equilibria calculations indicate that the mineral assemblage composed of diopside, brucite and chrysotile likely dictates fluid pH at moderate temperature serpentinization processes (<300 °C), by imposing constraints on the aCa++/a2H+ ratios and the activity of dissolved SiO2. Based on Sr abundances and the 87Sr/86Sr isotope ratios of vent fluids reported from Lost City, estimated water/rock mass ratios (w/r = 2-4) are consistent with published models involving dissolved CO2 and alkane concentrations. Combining the reported δ18O values of vent fluids (0.7‰) with such w/r mass ratios, allows us to bracket subseafloor reaction temperatures in the vicinity of 250 °C. These estimates are in agreement with previous theoretical studies supporting extensive conductive heat loss within the upflow zones. Experimental studies on peridotite-seawater alteration suggest that fluid pH increases during cooling which then rapidly enhances boron removal from solution and incorporation into secondary phases, providing an explanation for the highly depleted dissolved boron concentrations measured in the low temperature but alkaline Lost City vent fluids. Finally, to account for the depleted 11B composition (δ11B ∼25-30‰) of vent fluids relative to seawater, isotopic fractionation between tetrahedrally coordinated aqueous boron species with BO3-bearing mineral sites (e.g. in calcite, brucite) is proposed.  相似文献   

20.
Two strains of moderately halophilic bacteria were grown in aerobic culture experiments containing gel medium to determine the Sr partition coefficient between dolomite and the medium from which it precipitates at 15 to 45 °C. The results demonstrate that Sr incorporation in dolomite does occur not by the substitution of Ca, but rather by Mg. They also suggest that Sr partitioning between the culture medium and the minerals is better described by the Nernst equation (DSrdol = Srdol/Srbmi), instead of the Henderson and Kracek equation (DSrdol = (Sr/Ca)dol/(Sr/Ca)solution. The maximum value for DSrdol occurs at 15 °C in cultures with and without sulfate, while the minimum values occur at 35 °C, where the bacteria exhibit optimal growth. For experiments at 25, 35 and 45 °C, we observed that DSrdol values are greater in cultures with sulfate than in cultures without sulfate, whereas DSrdol values are smaller in cultures with sulfate than in cultures without sulfate at 15 °C.Together, our observations suggest that DSrdol is apparently related to microbial activity, temperature and sulfate concentration, regardless of the convention used to assess the DSrdol. These results have implications for the interpretation of depositional environments of ancient dolomite. The results of our culture experiments show that higher Sr concentrations in ancient dolomite could reflect microbial mediated primary precipitation. In contrast, previous interpretations concluded that high Sr concentrations in ancient dolomites are an indication of secondary replacement of aragonite, which incorporates high Sr concentrations in its crystal lattice, reflecting a diagenetic process.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号