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1.
The equilibrium hydrogen isotope fractionation factor (α) between kaolinite and water in the temperature range 330 to 0°C is 1000 In αkaol-water = −2.2 × 106T−2 − 7.7. This monotonic expression is based on a combination of experimental data with >75% of exchange and empirical calibrations. The previously proposed and widely accepted complex fractionation expression is considered to reflect the role of surface and intersite fractionation effects in the low percent of exchange experiments(Liu and Epstein, 1984), and incorrect δD water values for the empirical values (Lambert and Epstein, 1980). There is no measurable fractionation between dickite and kaolinite. The temperature dependence of the kaolinite-water hydrogen isotope fractionation factor can probably be used as a model for other phyllosilicate-water systems below 350°C.  相似文献   

2.
The extent of hydrogen and oxygen isotope exchange between clay minerals and water has been measured in the temperature range 100–350° for bomb runs of up to almost 2 years. Hydrogen isotope exchange between water and the clays was demonstrable at 100°. Exchange rates were 3–5 times greater for montmorillonite than for kaolinite or illite and this is attributed to the presence of interlayer water in the montmorillonite structure.Negligible oxygen isotope exchange occurred at these low temperatures. The great disparity in D and O18 exchange rates observed in every experiment demonstrates that hydrogen isotope exchange occurred by a mechanism of proton exchange independent of the slower process of O18 exchange.At 350° kaolinite reacted to form pyrophyllite and diaspore. This was accompanied by essentially complete D exchange but minor O18 exchange and implies that intact structural units in the pyrophyllite were inherited from the kaolinite precursor.  相似文献   

3.
Isotopic fractionation factors for oxygen, hydrogen and silicon have been calculated using first-principles methods for the kaolinite, quartz, water (ice and gas water) system. Good agreement between theory and experiment is obtained for mineral-water oxygen isotope fractionation. This approach gives reliable results on isotopic fractionation factors as a function of temperature, within a relative precision of typically 5%. These calculations provide independent quantitative constraints on the internal fractionation of oxygen in kaolinite, the fractionation of silicon isotopes at equilibrium, or hydrogen fractionation between kaolinite and water. Calculated fractionation factors at 300 K are 12.5‰ for the kaolinite internal-fractionation of oxygen, and 1.6‰ for silicon fractionation between quartz and kaolinite.  相似文献   

4.
Hydrogen isotope fractionation factors between hydroxyl-bearing minerals and water were determined at temperatures ranging between 400 and 850°C. The hydrogen isotope exchange rates for the mineral-water pairs examined were very slow. In most cases it was necessary to use an interpolation method for the determination of the hydrogen isotope equilibrium fractionation factor, αe.For the temperature range of 450–850°C the hydrogen isotope fractionation factors for the mica-water and amphibole-water systems are simply expressed as a function of temperature and the molar fractions of the six-fold coordinated cations in the crystal, regardless of mineral species, as follows: 103 In αe(mineral-water) = ? 22.4 (106T?2) + 28.2 + (2XAl ? 4XMg ? 68XFe), where X is the molar fraction of the cations. As the equation indicates, for any specific composition of the OH-bearing minerals, the change of αe with temperature, over the temperature range investigated, is the same for all minerals studied. Thus for any specified values of XAl, XMg, and XFe for these minerals, the relationship between αe and T is 103 In αe = αT?2 + k. Consequently, hydrogen isotope fractionation among coexisting minerals is temperature independent and cannot be used as a hydrogen isotope geothermometer.Some exceptions to the above general observations exist for minerals such as boehmite and kaolinite. In these minerals hydrogen bonding modifies the equilibrium hydrogen isotopic fractionation between mineral and water.  相似文献   

5.
Hydrogen fractionation laws between selected hydrous minerals (brucite, kaolinite, lizardite, and gibbsite) and perfect water gas have been computed from first-principles quantum-mechanical calculations. The β-factor of each phase was calculated using the harmonic phonon dispersion curves obtained within density functional theory. All the fractionation laws show the same shape, with a minimum between 200 °C (brucite) and 500 °C (gibbsite). At low temperatures, the mineral/liquid water fractionation laws have been obtained using the experimental gas/liquid water fractionation laws. The resulting fractionation laws systematically overestimate measurements by 15‰ at low temperatures to 8‰ at ≈400 °C. Based on this general agreement, all calculated laws were empirically corrected with reference to brucite/water data. These considerations suggest that the experimental or natural calibrations by Xu and Zheng (1999) and Horita et al. (2002) (brucite/water), Gilg and Sheppard (1996) (kaolinite/water), Wenner and Taylor (1973) (lizardite/water), and in some extents Vitali et al. (2001) (gibbsite/water) are representative of equilibrium fractionations. Besides, internal isotopic fractionation of hydrogen between inner-surface and inner hydroxyl groups has been computed for kaolinite and lizardite. The obtained fractionation is large, of opposite sign for the two systems (respectively, −23‰ and +63‰ at 25 °C) and is linear in T-2. Internal fractionation of hydrogen in TO phyllosilicates might thus be used in geothermometry.  相似文献   

6.
Hydrogen and oxygen isotopic compositions of cherts (δD for hydroxyl hydrogen in the chert, δ18O for the total oxygen) have been determined for a suite of samples from the central and western United States. When plotted on a δD-δ18O diagram, Phanerozoic cherts define domains parallel to the meteoric water line which are different for different periods of geologic time. The elongation parallel to the meteoric water line suggests that meteoric waters were involved in the formation of many cherts.The existence of different chert δ-values for different geologic times indicates that once the granular microcrystalline quartz of cherts crystallizes its isotopic composition is preserved with time. An explanation for the change with time of the isotopic composition of cherts involving large changes with time in the isotopic composition of ocean water is unlikely since δ18O of the ocean would have had to decrease by about 3‰between Carboniferous and Triassic time and then increase about 5%.` from Triassic to Cretaceous time. Such isotopic changes cannot be accounted for by extensive glaciation, sedimentation of hydrous minerals, or input of water from the mantle into the oceans.The variation with time of the chert δ-values can be satisfactorily explained in terms of past climatic temperature fluctuations if the chert-water isotope fractionation with temperature is approximated by 1000 lnα = 3.09 × 106T?2 – 3.29. Crystallization temperatures so inferred suggest that the average climatic temperatures for the central and western U.S. decreased from about 34 to 20°C through the Paleozoic, increased to 35–40°C in the Triassic, and then decreased through the Mesozoic to Tertiary values of about 17°C. A few data for the Precambrian suggest the possibility that Earth surface temperatures may have reached about 52°C at 1.3 b.y. and about 70°C at 3 b.y.  相似文献   

7.
The dehydration of a natural goethite to hematite is accompanied by a systematic hydrogen isotope fractionation. Closed system dehydration at, and below, 250°C results in a significantly greater degree of isotopic fractionation than does open system dehydration. This relationship is apparently reversed at 300°C. Both processes produce a progressive decrease in the DH ratio of the mineral hydrogen with increasing degree of dehydration. At temperatures of 160°C to 250°C the closed system mineralvapor fractionation factor is independent of temperature, while above 250°C, it varies strongly with temperature. The mineral-vapor fractionation factor associated with open system dehydration appears to be independent of temperature over the interval 160°C to 300°C. The closed system DH fractionation suggests that natural goethite undergoing dehydration in the presence of water can isotopically exchange with that water.CO2 loss from goethite during dehydration is correlated with the loss of H2O. The CO3 is thought to be present in carbonates which exist as impurities in the goethite. Loss of both H2O and CO2 appears to be diffusion-controlled.  相似文献   

8.
《Geochimica et cosmochimica acta》1999,63(13-14):2009-2018
Oxygen and hydrogen isotope fractionation factors between brucite and water were experimentally determined by chemical synthesis techniques at low temperatures of 15° to 120°C. MgCl2, Mg3N2, and MgO were used as reactants, respectively, to produce brucite in aqueous solutions. All of the synthesis products were identified by x-ray diffraction (XRD) for crystal structure and by scanning electron microscope (SEM) for morphology. It is observed that oxygen isotope fractionations between brucite and water are temperature dependent regardless of variations in aging time, the chemical composition, and pH value of solutions. Brucites derived from three different starting materials yielded consistent fractionations with water at the same temperatures. These suggest that oxygen isotope equilibrium has been achieved between the synthesized brucite and water, resulting in the fractionation equation of 103lnα=1.56×106/T2−14.1. When the present results for the brucite–water system are compared with those for systems of gibbsite–water and goethite–water, it suggests the following sequence of 18O-enrichment in the M−OH bonds of hydroxides: Al3+ − OH > Fe3+ − OH > Mg2+ − OH.Hydrogen isotope fractionations between brucite and water obtained by the different synthesis methods have also achieved equilibrium, resulting in the fractionation equation of 103lnα=−4.88×106/T2−22.5. Because of the pressure effect on hydrogen isotope fractionations between minerals and water, the present calibrations at atmospheric pressure are systematically lower than fractionations extrapolated from hydrothermal exchange experiments at high temperatures of 510° to 100°C and high pressures of 1060 to 1000 bar. Comparison of the present results with existing calibrations involving other low-temperature minerals suggests the following sequence of D-enrichment in hydroxyl-bearing minerals: Al3+ − OH > Mg2+ − OH > Fe3+ − OH.  相似文献   

9.
The equilibrium fractionation factors between mirabilite (Na2SO4·10H2O) and saturated sodium sulphate solution at 25°C and 0°C and between ice and 2·5 molal sodium chloride solution at ?10°C have been measured. For mirabilite, the deuterium factors are 1·017 and 1·019, and the oxygen-18 factors are 1·0014 and 1·0020 at 25°C and 0°C, respectively. For ice, the factors are 1·024 for deuterium and 1·0022 for oxygen-18 at ?10°C. These fractionation factors are used to estimate the fractionation factors between ice and mirabilite and concentrated sea water at ?10°C. It is concluded that the average binding strengths of hydrogen in ice and mirabilite are very similar.  相似文献   

10.
Abstract: The origin of mineralizing fluids responsible for the Hishikari vein-type epithermal Au deposits was studied on the basis of the hydrogen isotopic ratio (δD) of the inclusion fluid from vein quartz and adularia. The origin of hydrothermal fluids was estimated by combination of the present δ values and the oxygen isotopic ratios (δ18O) previously reported by Shikazono and Nagayama (1993). The water in the fluid inclusions was extracted by means of decrepitation of quartz at 500°C. Hydrogen was obtained by reduction of the collected water with Zn shot at 450°C. The δD values were determined by mass spectrometer. The δD values of inclusion fluid obtained from quartz range from –61 to –114%. These are significantly lower than the δD value of the thermal water presently venting from the Hishikari deposits and that of local meteoric water. Hydrogen isotopic fractionation between water and amorphous silica, which might have initially precipitated from the hydrothermal fluids at least partly, is not a probable cause of this isotopic depletion, while some water might have been released from the initial hydrous amorphous silica during recrystallization to quartz observed presently. Thus, a part of ore fluids for the Hishikari deposits is supposed to have been originated from the water having anomalous δD values of lower than –100%. Such D depletion cannot be caused by simple oxygen-shift of meteoric water or by contribution of magmatic volatiles. The δD values of water released from the shale samples of the Shimanto–Supergroup, a major host to the Hishikari veins range from –132 to –148%. Therefore, the anomalous δD values of inclusion fluids from some vein quartz and adularia suggest that the water released from hydrous minerals of the sedimentary basement rocks by dehydration or the groundwater isotopically exchanged with sedimentary rocks at elevated temperatures during circulation, partly contributed to the hydrothermal fluids responsible for the Hishikari deposits.  相似文献   

11.
High temperature infrared spectra of hydrous microcrystalline quartz   总被引:1,自引:0,他引:1  
A series of in-situ high temperature infrared (IR) measurements of water in an agate sample and in a milky quartz has been conducted in order to understand the nature of water in silica at high temperatures (50–700?°C) and the dehydration behavior. IR absorption bands of water molecules trapped in the milky quartz showed a systematic decrease in intensities and a shift from 3425?cm?1 at 50?°C toward 3590?cm?1 at 700?°C without any loss of water. This indicates a change in IR absorption coefficients corresponding to different polymeric states of water at different temperatures. The broad 3430?cm?1 band in the agate sample also showed a systematic decrease in IR intensity and a band shift toward higher frequency with increasing temperature (~700?°C). This indicates that the agate sample also contains fluid inclusion-like water. For this agate sample, a dehydration of loosely hydrogen-bonded molecular water occurred at lower temperatures (<200?°C). At higher temperatures (>400?°C), sharp bands around 3660 and 3725?cm?1 (3740?cm?1 at 50?°C) due to surface silanols, appeared. This indicates dehydration of H2O molecules that are hydrogen bonded to surface silanols. SiOH species in the agate are divided into three groups, namely SiOH group located at structural defects, surface silanols hydrogen bonded to each other and free surface silanols. Former two dehydrate below 700?°C and the dehydration rate of the SiOH at structural defects is faster than the other. IR spectra show that SiOH species decrease continuously even after the dehydration of most of H2O molecules. All these results provide realistic bases for the change in physicochemical states of different OH species in silica at high temperatures.  相似文献   

12.
Fundamental knowledge of the isotopic fractionation between the hydration water and the mother solution and whether the primary information recorded in hydration water can be preserved or not in deposits or mines have long been unclear. In order to calculate the accurate hydrogen and oxygen isotopic fractionation factors between gypsum hydration water and its mother solution with new methods, to understand the mechanism of fractionation and synthetically assess the record-keeping abilities of the isotopic composition of hydration water during the process of diagenesis after deposition, experiments on the hydrogen and oxygen isotopic compositions of gypsum hydration water and its mother solution at different isothermal temperatures from 5 to 50°C were systematically conducted. In addition, samples from two typical gypsum deposits formed in different environmental conditions were also determined. Results show that during gypsum crystallisation, both hydrogen and oxygen isotopes show significant fractionation between the hydration water and the mother solution. The calculated hydrogen isotopic fractionation factors are <1, while the oxygen isotopic fractionation factors are >1 at temperatures from 5 to 50°C. The fractionation factors show no functional relationships with temperature. Isotopic compositions of gypsum hydration water in arid lake sediments can be used to trace the source of water and primary deposit environmental information. However, the isotopic composition of the gypsum hydration water can easily be altered by dissolution and secondary precipitation of gypsum during later diagenesis, particularly in areas with humid climate and abundant groundwater. A very careful assessment on record-keeping abilities of the primary isotopic composition of hydration water in gypsum during later diagenesis must be considered before application.  相似文献   

13.
Oxygen isotope fractionation was experimentally studied in the quartz-wolframite-water system from 200 to 420 °C. The starting wolframite was synthesized in aqueous solutions of Na2WO4 · 2H2O + FeCl2 · 4H2O or MnCl2 · 4H2O. The starting solutions range in salinity from 0 to 10 equivalent wt.% NaCl. Experiments were conducted in a gold-lined stainless steel autoclave, with filling degrees of about 50%. The results showed no significant difference in equilibrium isotope fractionation between water and wolframite, ferberite and huebnerite at the same temperature (310 °C ). The equilibrium oxygen isotope fractionation factors of wolframite and water tend to be equal with increasing temperature above 370 °C, but to increase significantly with decreasing temperature below 370 °C: 1000 ln αwf-H2o= 1.03×106T−2-4.91 (370 °C ±200 °C ) 1000 ln αwf-H2o = 0.21×106T −2-2.91 (420 °C -370 °C ±) This projects was financially supported by the National Natural Science Foundation of China.  相似文献   

14.
Stromatolites forming today on a small scale in hydrothermal environments are chemical and biological analogues of much larger Precambrian formations. Carbon isotopic composition varied as a function of CO2 concentration, pH, and species composition. Stratiform, layered stromatolites grew in silica-depositing springs at 55° to 70°C; they consisted mainly of a unicellular alga, Synechococcus, and a filamentous, photosynthetic bacterium, Chloroflexus. These thermophiles become enriched in 12C as the concentration of carbon dioxide in the effluent waters increases. At a concentration of 40 ppm total inorganic C, and δ13C of organic carbon was ~ ?12%., whereas at 900 ppm total inorganic C, the δ13C of similar species was ~ ?25%.. Conical stromatolites or conophytons (principally a filamentous, blue-green alga Phormidium and Chloroflexus) grew at 40°-55°C. In older, broader conophytons, Chloroflexus was the dominant organism. Their δ13C values were ~ ?18%. in a variety of hot springs. In carbonate-depositing springs, i.e., carbon dioxide saturated, conophytons and stromatolites consisting of a variety of blue-green algae and photosynthetic bacteria had the most negative δ13C values (to ?30%.). These carbon isotope ratios are directly comparable to carbon isotope ratios of kerogen from Precambrian stromatolites. The presence and activity of methanogenic bacteria or heterotrophic, aerobic and anaerobic bacteria did not alter significantly the δ13C of the original organic matter.The hydrogen isotopic fractionation between thermophilic organisms and water is 0 to ?74 for temperatures of 85° to 46°C, respectively. Acidophilic algae fractionated hydrogen isotopes to a lesser extent than did the photosynthetic organisms inhabiting neutral pH springs. Because organic matter retains some of its original isotopic signature, relationships of CO2 levels, pH, temperature, and species composition between modern stromatolites and their environment and those of the Precambrian can be inferred.  相似文献   

15.
钱雅倩  郭吉保 《地学前缘》1998,5(2):251-260
矿物水体系氢同位素平衡分馏系数和动力分馏系数是同位素地球化学研究中的重要参数。这些参数大多由实验测定。氢同位素分馏的实验研究主要包括矿物水体系氢同位素交换实验,交换实验前后矿物、水的氢同位素分析及分馏机理、平衡分馏、动力分馏理论研究。为确保氢同位素分馏系数和一系列动力学参数的准确可靠,实验中防止氢透过容器壁扩散,避免空气中水汽污染样品,正确控制实验温度等都很重要。本研究以石英管代替前人常用的金(银、铂)管作反应容器,建立了一套实验研究羟基矿物水体系氢同位素平衡分馏和动力分馏的新方法,并开展了电气石水、黑柱石水体系氢同位素分馏的实验研究。所得一系列参数的精度明显好于国外报道的资料。此研究方法可广泛应用于羟基矿物水体系的氢同位素分馏的实验研究。  相似文献   

16.
In this study, with the method of vacuum extraction, two evaporative processes of soil water and free water under equilibrium condition were simulated. For each sample, water vapor was condensed by liquid nitrogen and was collected in four time intervals. From the analysis of hydrogen and oxygen isotopic compositions of the water collected at different times, it was discovered that the isotope fractionation of soil water also follows the mode, which is just the same as the evaporative process of free water. The relationship between the stable hydrogen and oxygen isotopes in residual water showed that the simulative evaporation line was close to the global meteoric water line (GMWL) under the equilibrium condition at about 20°C. Comparison of the two types of evaporative processes indicated that the isotope fractionation and evaporation velocity of soil water were only slightly modified by the Van der Waals force.  相似文献   

17.
This study aims to quantify the effect of heating and freezing temperatures on the pore size distribution of saturated clays. Three kaolinite clay specimens were subjected to different temperatures: 20, 70, and ? 10 °C. Upon achieving the desired temperature for each specimen, the specimens were flash frozen in liquid nitrogen to preserve their microstructure. Each specimen was, then, freeze-dried for 24 h after which consecutive two-dimensional (2-D) SEM images were taken using a dual focused ion beam/scanning electron microscope. The produced 2-D images of each specimen were used to reconstruct three-dimensional tomographies of the specimens, which were analyzed to determine the pore size distribution at each temperature. Compared to the specimen at room temperature, the pores in the specimen subjected to ? 10 °C were larger; this is believed to be due to the formation of ice lenses inside the pores upon freezing and potential merging between initial pores to form larger pores. On the other hand, the heated specimen showed an increase in the volume of the smaller pores and a decrease in the volume of the larger pores compared to the specimen at room temperature. This opposite behavior between the small and large pores in the heated specimen is justified considering (1) the easier flow of water out of the larger pores compared to that in the smaller pores and (2) the anisotropic nature of the thermal expansion of the clay particles.  相似文献   

18.
The hydrogen isotopic composition of structural water in MnO(OH) minerals from manganese oxide and massive sulfide deposits (Kuroko) in Tertiary formations fall within a narrow range from -261 to -275 permil relative to standard mean ocean water (SMOW). The δD of two manganites from manganese deposits in Paleozoic formations were -236 and -298 permil, indicating a wider range than in those of Tertiary manganese deposits. The MnO(OH) minerals are more deuterium-depleted. than any other hydrothermal minerals reported to date. Hydrogen isotopic fractionation factors between manganite and water were experimentally determined to be 0.7894, 0.7958, and 0.8078 at 150°, 200°, and 250° C, respectively, under hydrothermal conditions at 500 bars. The present experimental results indicate that if manganites were formed at temperatures below 250° C under isotopic equilibrium conditions, then most manganite mineralization in the ore deposits must have precipitated from meteoric hydrothermal solutions.  相似文献   

19.
We studied calcite and rhodochrosite from exploratory drill cores (TH‐4 and TH‐6) near the Toyoha deposit, southwestern Hokkaido, Japan, from the aspect of stable isotope geochemistry, together with measuring the homogenization temperatures of fluid inclusions. The alteration observed in the drill cores is classified into four zones: ore mineralized zone, mixed‐layer minerals zone, kaolin minerals zone, and propylitic zone. Calcite is widespread in all the zones except for the kaolin minerals zone. The occurrence of rhodochrosite is restricted in the ore mineralized zone associated with Fe, Mn‐rich chlorite and sulfides, the mineral assemblage of which is basically equivalent to that in the Toyoha veins. The measured δ18OSMOW and δ13CPDB values of calcite scatter in the relatively narrow ranges from ?2 to 5‰ and from ?9 to ?5‰, respectively; those of rhodochrosite from 3 to 9‰ and from ?9 to ?5‰, excluding some data with large deviations. The variation of the isotopic compositions with temperature and depth could be explained by a mixing process between a heated surface meteoric water (100°C δ18O =?12‰, δ13C =?10‰) and a deep high temperature water (300°C, δ18O =?5‰, δ13C =?4‰). Boiling was less effective in isotopic fractionation than that of mixing. The plots of δ18O and δ13C indicate that the carbonates precipitated from H2CO3‐dominated fluids under the conditions of pH = 6–7 and T = 200–300°C. The sequential precipitation from calcite to rhodochrosite in a vein brought about the disequilibrium isotopic fractionation between the two minerals. The hydrothermal fluids circulated during the precipitation of carbonates in TH‐4 and TH‐6 are similar in origin to the ore‐forming fluids pertaining to the formation of veins in the Toyoha deposit.  相似文献   

20.
The Arzular mineralization is one of the best examples of epithermal gold deposits in the eastern Pontides orogenic belt.The mineralization is hosted by the subduction-related basaltic andesites and is mainly controlled by E-W and NE-SW trending fracture zones.The main ore minerals are galena, sphalerite,pyrite.chalcopyrite.tetrahedrite and gold.Homogenization temperatures of fluid inclusions are between 130 and 295℃ for quartz and between 90 and 133℃ for sphalerite.Sulphur isotope values obtained from pyrite,galena and sphalerite vary between 1.2‰ and 3‰.indicating that sulphur belongs to magmatic origin and was derived from the Lutetian non-adakitic granitic intrusions in the region.Oxygen isotope values are between 15.0‰ and 16.7‰ and hydrogen isotope values are between -87‰ and -91‰ The sulphur isotope thermometer yielded temperatures in the range of 244-291℃ for the ore formation.Our results support the hypothesis that the Arzular mineralization is a low-sulfidation epithermal gold deposit associated with non-adakitic subduction- related granitic magmas that were generated by slab window-related processes in a south-dipping subduction zone during the Lutetian.  相似文献   

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