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1.
Mineralogical and hydrogen isotopic studies have been made on clay minerals occurring in the Ohnuma geothermal area, northeastern Japan. Here, clay minerals such as smectite, kaolinite, dickite, sericite, and chlorite were formed by hydrothermal alteration of Miocene rocks. A chemical equilibrium can be assumed to be attained from the fact that the amount of expandable layer in the interstratified chlorite/smectite decreases and the polytype of sericite changes from 1M to 2M1 with increasing depth and temperature. The hydrogen isotopic composition (D/H) of the clay minerals is lighter than that of the geothermal and local meteoric waters by about 20–40‰. The hydrogen isotopic fractionation factors αmineral-water are as follows: 0.972–0.985 for kaolinite and dickite, 0.973–0.977 for sericite, and 0.954–0.987 for chlorite. In the temperature range from 100 to 250°C, the hydrogen isotopic fractionation factors between these minerals and water are not sensitive to the temperature. αchlorite-water depends on the kind of octahedrally coordinated cations which lie close to the hydroxyl groups; it becomes large with an increase of Mg content of chlorite.  相似文献   

2.
Studies of the effect of dissolved salts on the oxygen isotope activity ratio of water have been extended to 275°C. Dehydrated salts were added to water of known isotope composition and the solutions were equilibrated with CO2 which was sampled for analysis. For comparison similar studies were made using pure water. Results on water nearly coincide with earlier calculations. Salt effects diminish with increasing temperature only for solutions of MgCl2 and LiCl. Other salt solutions show complex behavior due to the temperature-dependent formation of ion pairs of changing character. Equilibrium fractionations (103 ln α) between 1 molal solutions and pure water at 25, 100, and 275°C are: NaCl 0.0, ?1.5, +1.0; KCl 0.0, ?1.0, +2.0; LiCl ?1.0, ?0.6, ?0.5; CaCl2 ?0.4, ?1.8, +0.8; MgCl2 ?1.1, ?0.7, ?0.3; MgSO4 ?1.1, +0.1, ?; NaF (0.8 m) 0.0, ?1.5, ?0.3; and NH4Cl (0.55 m) 0.0, ?1.2, ?1.3. These effects are significant in the isotope study of hot saline fluids responsible for ore deposition and of fluids found in certain geothermal systems. Minor modification of published isotope geothermometers may be required.  相似文献   

3.
Calculated univariant equilibria and oxygen isotope compositions of silicates and carbonates support the proposal that the “Mottled Zone Event” is a low-pressure (1–25 atm), high-temperature (200° < T < 1300°C) metamorphism of calcareous siliceous sediments in which the thermal energy is provided by combustion of organic matter. δ18O of silicates decreases systematically with increasing metamorphic grade from averages of 18.1‰ in protolith shales, to 16.6‰ in grossular-diopside-zeolite rocks, 15.6‰ in wollastonite and anorthite-diopside-gehlenite-grossular fels, 14.1‰ in spurrite-brownmillerite marbles and 11.7‰ in the highest-grade larnite-gehlenite-brownmillerite assemblages. Decarbonation is the principal mechanism influencing the oxygen isotope compositions. The progressive decrease of δ18O in silicates can be modelled as a Rayleigh distillation of CO2 approximately 16‰ enriched in 18O relative to whole rock assemblages i.e., of initial isotopic composition 8.5‰ heavier than the parent carbonates. The mineral assemblage of one sample with an unusual granoblastic texture is in apparent isotopic equilibrium at a temperature of 540°C.  相似文献   

4.
Nitrogen isotope fractionations have been measured in Fischer-Tropsch and Miller-Urey reactions in order to determine whether these processes can account for the large15N/14N ratios found in organic matter in carbonaceous chondrites. Polymeric material formed in the Fischer-Tropsch reaction was enriched in15N by only 3‰ relative to the starting material (NH3). The15N enrichment in polymers from the Miller-Urey reaction was 10–12‰. Both of these fractionations are small compared to the 80–90‰ differences observed between enstatite chondrites and carbonaceous chondrites. These large differences are apparently due to temporal or spatial variations in the isotopic composition of nitrogen in the solar nebula, rather than to fractionation during the production of organic compounds.  相似文献   

5.
D/H fractionation factors between serpentine (clinochrysotile) and water were experimentally determined to be: 1000 In αser-w = 2.75 × 10 7/T2 ? 7.69 × 104/T + 40.8 in the temperature range from 100 to 500°C. The present results do not support the semi-empirical fractionation factors employed by Wenner and Taylor [1] for the interpretation of δD values of natural serpentines. About 100 serpentines from the Japanese Islands have δD values from ?110 to ?40‰ SMOW, with antigorite being from ?40 to ?60‰. The results are in accord with the two conclusions by Wenner and Taylor [1,2], that is, the presence of a latitude ?δD correlation and the more uniform and higher δD values of antigorite than chrysotile and lizardite.According to the present fractionation factors, almost none of the continental lizardite-chrysotile serpentines could have formed at a temperature below 500°C under equilibrium with fluids of δD values similar to the present-day local meteoric waters. The fluid responsible for oceanic serpentinization could be either a mixture of oceanic and magmatic water or oceanic water alone. However, full interpretation of the δD values of natural serpentines should wait until kinetic behaviors of hydrogen isotopes in serpentinization are better understood.  相似文献   

6.
A sulfur isotope fractionation of 20.0 ± 0.2‰ was measured between aqueous sulfide and sulfate at 300°C and 1000 bars using gold-cell hydrothermal solution equipment. The value is 2‰ smaller than previously published values. Rates of exchange were determined as a function of pH and total sulfur content. Initial mean 34S concentration was changed to approach equilibrium from two directions. Half-times ranged from 3.4 to 8.2 days, with shorter times obtained for more acid and more concentrated solutions.The sulfate-sulfide isotope temperature scale based on theory should be revised according to this new fractionation factor. The rate data permit assessment of the extent to which equilibrium may be attained in some natural systems. For example, the lack of agreement between temperatures based on sulfide mineral pairs and sulfide-sulfate mineral pairs from Kuroko ore deposits of Japan might imply that the residence time of sulfate and sulfide in Kuroko solutions was not longer than 1000 years, if the present kinetic data are correct. Geothermal systems such as the Wairakei system of New Zealand may reach sulfur isotope equilibrium between sulfate and sulfide in 300 years at 300°C, but would be increasingly removed from equilibrium at lower temperatures if residence times were 300 years or less.  相似文献   

7.
The fractionation of the oxygen isotopes between water molecules from different sites in CuSO4 · 5H2O has been measured for crystallization temperatures of 25, 40 and 50°C. The temperature dependence found provides a basis for the determination of crystallization temperatures from such intracrystalline oxygen isotope effects; also for hydrated crystals of mineralogical and geological interest. Necessary suppositions for the application of this method are discussed.  相似文献   

8.
A theoretical model is derived in which isotopic fractionations can be calculated as a function of variations in dissolved carbonate species on CO2 degassing and calcite precipitation. This model is tested by application to a calcite-depositing spring system near Westerhof, Germany. In agreement with the model,13C of the dissolved carbonate species changes systematically along the flow path. The difference in δ values between the upper and lower part of the stream is about 1‰. The13C content of the precipitated calcite is different from that expected from the theoretical partitioning. The isotopic composition of the solid CaCO3 is similar to that of the dissolved carbonate, though in theory it should be isotopically heavier by about 2.4‰. The18O composition of dissolved carbonate and H2O is constant along the stream. Calculated calcite-water temperatures differ by about +5°C from the observed temperatures demonstrating isotopic disequilibrium between the water and precipitated solid. This is attributed to kinetic effects during CaCO3 deposition from a highly supersaturated solution, in which precipitation is faster than equilibration with respect to isotopes.Plant populations in the water have virtually no influence on CO2 degassing, calcite saturation and isotopic fractionation. Measurements of PCO2, SC and13C within a diurnal cycle demonstrate that metabolic effects are below the detection limit in a system with a high supply-rate of dissolved carbonate species. The observed variations are due to differences in CO2 degassing and calcite precipitation, caused by continuously changing hydrodynamic conditions and carbonate nucleation rates.  相似文献   

9.
Oxygen isotope exchange between anhydrite and water was studied from 100 to 550°C, using the partial equilibrium method. The exchange rate was extremely low in NaCl solution. In the lower-temperature range, acid solutions were used to produce sufficient reaction to determine the oxygen isotope fractionation factors. The fractionation factors obtained in the present study are definitely different from those given by Lloyd [8]. They are similar to those for the HSO4?-water system studied by Mizutani and Rafter [19], and are consistently 2‰ higher than those of the barite-water system by Kusakabe and Robinson [5]. The temperature dependence of the oxygen isotope fractionation factors was calculated by the least squares method in which the weight was taken to be inversely proportional to the experimental error. The fractionation is given by:103lnαanhydrite-water=3.21×(103/T)2?4.72Available δ18O values of natural anhydrite were used to test the validity of this expression. It is shown that this newly revised geothermometer can be successfully applied to natural hydrothermal anhydrite.  相似文献   

10.
Increasing use is being made of sulphide minerals in isotope geothermometry. Sulphur isotope fractionation factors for34S exchange between sphalerite (ZnS) and galena (PbS) have been calculated for various temperatures between 0 and 1000°C. The reduced partition function ratios have been calculated using a “shell” model for the forces derived from inelastic neutron scattering studies of the lattice dynamics of sphalerite and galena. A new formalism of the current theory has been developed which enables the accuracy of the calculation to be determined.The Zn34S—Pb34S equilibrium constant obtained by the shell model calculations is 1.0060 to 100°C, 1.0031 at 250°C and 1.0005 at 1000°C, in agreement with experimental determinations.  相似文献   

11.
The Tieluping silver deposit, located in the NE-trending faults within the metamorphic basement of the Xiong'er Mountain, is a typical altered fracture type deposit. Its ore-forming process includes three stages with temperatures concentrated at 373°C, 223°C and 165°C respectively. With δD=90‰,\(\delta ^{13} C_{CO_2 } \)=2.0‰ and δ{si18}O=8094‰, the early stage fluid was generated from reworking and metamorphism of the carbonate rich formation; the late one, with δD=?70‰,\(\delta ^{13} C_{CO_2 } \)=-1.2‰, δ18O=1.89‰, was meteoric hydrothermal solution; and the middle. δD=?109‰,\(\delta ^{13} C_{CO_2 } \)=0.1‰, δ18O=1.79‰, might be a hybrid mixed by reworking-metamorphic fluid and meteoric hydrothermal solution. Crystallized rapidly in the condition of fluid-boiling and fluid-mixing, the middle stage minerals have far more fluid inclusions with higher content of ions, higher ratios of H2O/CO2 and KN/MC. Consequently, they have much more ore elements such as gold compared with those of the early and late stages. It was the northward intracontinental subduction along the Machaoying fault during the Mesozoic collision between the South China and North China paleocontinents that intrigued large-scale fluidization and magmatism and led to the appearance of more than 10 large and medium hydrothermal deposits, including the Tieluping silver deposit. The study on ore-forming fluidization of the Tieluping silver deposit proves the CPMF model.  相似文献   

12.

The Tieluping silver deposit, located in the NE-trending faults within the metamorphic basement of the Xiong'er Mountain, is a typical altered fracture type deposit. Its ore-forming process includes three stages with temperatures concentrated at 373°C, 223°C and 165°C respectively. With δD=90‰,\(\delta ^{13} C_{CO_2 } \)=2.0‰ and δ{si18}O=8094‰, the early stage fluid was generated from reworking and metamorphism of the carbonate rich formation; the late one, with δD=−70‰,\(\delta ^{13} C_{CO_2 } \)=-1.2‰, δ18O=1.89‰, was meteoric hydrothermal solution; and the middle. δD=−109‰,\(\delta ^{13} C_{CO_2 } \)=0.1‰, δ18O=1.79‰, might be a hybrid mixed by reworking-metamorphic fluid and meteoric hydrothermal solution. Crystallized rapidly in the condition of fluid-boiling and fluid-mixing, the middle stage minerals have far more fluid inclusions with higher content of ions, higher ratios of H2O/CO2 and KN/MC. Consequently, they have much more ore elements such as gold compared with those of the early and late stages. It was the northward intracontinental subduction along the Machaoying fault during the Mesozoic collision between the South China and North China paleocontinents that intrigued large-scale fluidization and magmatism and led to the appearance of more than 10 large and medium hydrothermal deposits, including the Tieluping silver deposit. The study on ore-forming fluidization of the Tieluping silver deposit proves the CPMF model.

  相似文献   

13.
This paper reports a detailed geochemical study of thermal occurrences as observed in the edifice and on the flanks of Mendeleev Volcano, Kunashir Island in August and September 2015. We showed that three main types of thermal water are discharged there (neutral chloride sodium, acid chloride sulfate, and acid sulfate types); these waters exhibit a zonality that is typical of volcano-hydrothermal island arc systems. Spontaneous and solfataric gases have relatively low 3He/4He ratios, ranging between 5.4Ra and 5.6Ra, and δ13C-CO2 between –4.8‰ and –3.1‰, and contain a light isotope of carbon in methane (δ13C ≈ –40‰). Gas and isotope geothermometers yield relatively low temperatures around 200°C. The isotope compositions in all types of water are similar to that of local meteoric water. The distribution of microcomponents varies among different types. The isotope composition of dissolved Sr varies considerably, from 0.7034 as observed in Kunashir rocks on an average to 0.7052 in coastal springs, which may have resulted from admixtures of seawater. The total hydrothermal transport rates of magmatic Cl and SO4, as observed for Mendeleev Volcano, are 7.8 t/d and 11.6 t/d, respectively. The natural outward transport of heat by the volcano’s hydrothermal system is estimated as 21 MW.  相似文献   

14.
13C and ΣCO2 data from the North and South Atlantic, the Antarctic, and the North and South Pacific are given. The δ13C of the ΣCO2 in the deep water (～3000m) decreases from 1.7‰ in the North Atlantic to ?0.10‰ in the North Pacific. This change is attributed to the addition of about 158 μmoles of CO2 per kg of seawater. The in-situ oxidation of organic matter accounts for 83% of this increase in ΣCO2, while the remainder is attributed to dissolution of calcium carbonate.The δ13C of the dissolved CO2 in mid-latitude surface water samples is controlled by a quasi-steady-state equilibrium with atmospheric CO2 at a mean temperature of 16°C. The δ13C and ΣCO2 values of Antarctic surface water samples suggest that these waters are derived from a mixture of North Atlantic deep water and equilibrated surface water.  相似文献   

15.
Rocks of the Miocene Macquarie Island ophiolite, south of New Zealand, have oxygen and carbon isotopic compositions comparable to those of seafloor rocks. Basalt glass and weathered basalts have δ18O values at 5.8–6.0‰ and 7.9–9.5‰, respectively, similar to drilled seafloor rocks including samples from the Leg 29 DSDP holes near Macquarie Island. Compared to the basalt glass, the greenschist to amphibolite facies metaintrusives are depleted in18O (δ18O=3.2–5.9‰) similar to dredged seafloor samples, whereas the metabasalts are enriched (δ18O=7.1–9.7‰). Although the gabbros are only slightly altered in thin-section they have exchanged oxygen with a hydrothermal fluid to a depth of at least 4.5 km. There is an approximate balance between18O depletion and enrichment in the exposed ophiolite section. The carbon isotopic composition of calcite in the weathered basalts (δ13C=1.0–2.0‰) is similar to those of drilled basalts, but the metamorphosed rocks have low δ13C values (?14.6 to 0.9‰).These data are compatible with two seawater circulation regimes. In the upper regime, basalts were weathered by cold seawater in a circulation system with high water/rock ratios (?1.0). Based on calcite compositions weathering temperatures were less than 20°C and the carbon was derived from a predominantly inorganic marine source. As previously suggested for the Samail ophiolite, it is postulated that the lower hydrothermal regime consisted of two coupled parts. At the deeper levels, seawater circulating at low water/rock ratios (0.2–0.3) and high temperatures (300–600°C) gave rise to18O-depleted gabbro and sheeted dikes via open system exchange reactions. During reaction the seawater underwent a shift in oxygen isotopic composition (δ18O=1.0–5.0‰) and subsequently caused18O enrichment of the overlying metabasalts. In the shallower part of the hydrothermal regime the metabasalts were altered at relatively high water/rock ratios (1.0–10.0) and temperatures in the range 200–300°C. The relatively low water/rock ratios in the hydrothermal regime are supported by the low δ13C values of calcite, interpreted as evidence of juvenile carbon in contrast to the inorganic marine carbon found in the weathered basalts.  相似文献   

16.
Oxygen and hydrogen isotopic compositions were measured on 12 serpentine and 2 actinolite samples from the Troodos ophiolite complex, Cyprus. The single analyzed antigorite(δD= ?60, δ18O= 7.1) is isotopically similar to all previously analyzed antigorites from ultramafic bodies. However, although their D/H ratios are relatively “normal”(δD= ?70to?92), the δ18O values of most of the Troodos lizardite-chrysotile serpentines (+12.6 to +14.1) are much higher than the 2.0–9.3‰ range typically found in such serpentines. Such high δ18O values have previously been found only in the serpentine-like mineraloids termed “deweylites”, which apparently formed at Earth-surface temperatures, and in a single sample from Vourinos, Greece that is in contact with high-18O limestone. The Troodos lizardite-chrysotile samplescannot have formed by reaction with heated ocean waters, but instead must have formed in contact with large amounts of some type of meteoric, metamorphic, or formation water, either (1) at very low temperatures in a near-surface environment, or (2) at about 100°C from waters that were abnormally enriched in18O(δ18O ≈ +4 to +8). The latter possibility seems most plausible inasmuch as extensive evaporites were deposited throughout the Mediterranean Sea during the late Miocene, and this would have been accompanied by strong18O enrichments of the local meteoric waters. Heated ocean waters, however, probably were responsible for the formation of the actinolitic amphiboles(δ18O= 4.6 to 5.5; δD= ?51to?46) from the gabbro and ultramafic zones in the Troodos complex. The amphiboles must have formed at considerably higher temperatures and at an earlier stage than the lizardite-chrysotile serpentinization.  相似文献   

17.
Calculation of oxygen isotope fractionation in hydroxyl-bearing silicates   总被引：33，自引：0，他引：33  
The modified increment method has been applied to the calculation of oxygen isotope fractionation factors for hydroxyl-bearing silicate minerals. The order of 18O enrichment obtained in common rock-forming minerals is: pyrophyllite > kaolinite > tourmaline talc > prehnite topaz > illite > phengite > lepidolite muscovite staurolite > epidote > glaucophane > serpentine chlorite > tremolite > hornblende > phlogopite biotite > humite > norbergite > ilvaite. Hydroxyl-bearing silicates are enriched in 18O relative to hydroxyl groups but depleted in 18O relative to anhydrous counterparts.

Three sets of self-consistent fractionation factors: between quartz and the hydroxyl-bearing silicate minerals, between calcite and the silicate minerals, and between the silicate minerals and water, have been calculated for a temperature range of 0–1200°C. The fractionation factors calculated for mineral pairs are applicable to isotopic geothermometry in igneous, metamorphic and sedimentary petrology. They can be used as a test of isotopic equilibrium or disequilibrium in natural mineral assemblages over all temperature ranges of geological interest. The difference in oxygen isotope composition between the hydroxyl-bearing mineral and the OH group is quantitatively demonstrated to be temperature dependent and, therefore, can be used as a single-mineral geothermometer.  相似文献   


18.
Graeme L. Scott 《Island Arc》2004,13(2):370-386
Abstract The influence of major active faults on rock alteration and stable isotope geochemistry is described for the Tongonan geothermal field, Leyte, the Philippines. In the Pliocene, acid alteration with characteristic iron enrichment (3 g/100 g) and calcium depletion (2 g/100 g) occurred along a Riedel shear fault in the Malitbog sector, and initial minor acid alteration also occurred along a similar shear in the Mahiao sector. Later, sodium metasomatism (5 g/100 g) coincided with the highest aquifer chloride (10 000 mg/kg) as a result of dissociation of saline magmatic fluids discharging through the reservoir rocks in the Upper Mahiao. The incursion of magmatic fluids (possibly δD 35‰, δ18O +7‰) set up a vigorous convection cell of meteoric water, which focused around low‐angle (L) shears centered in the Sambaloran sector. Meteoric water (δD ?35 to ?40‰, δ18O ?6 ± 1‰) depleted the reservoir in silica (6 g/100 g) and potassium (1–2 g/100 g). It also completely exchanged oxygen isotopes rapidly (within months) at high temperatures (300–400°C), and now does so continuously with fractured isotopically fresh or incompletely altered rock at small scales (centimeters or less) exposed by a 2 cm/year creep around the L shears to form a new component called geothermal water. Geothermal water mixes with meteoric water at lower temperatures (<300°C) to create the characteristic shift in δ18O of 6‰ at near constant δD (?35 ± 5‰). The 10‰ variation in δD is due to groundwater recharge derived from rain falling on steep terrain (5‰) and to enrichment of deuterium in boiling saline solutions (5‰); it is not due to two‐component mixing of meteoric with magmatic water. The low (～1) isotopic water/rock (W/R) ratios calculated from oxygen isotopes in previously published reports are meaningless, because the water contains four components (predominantly geothermal and meteoric water; <10% magmatic and rock water). W/R ratios of up to 1500 calculated from spring and rock chemistry are more realistic and, with a flow rate of approximately 50 L/s through a 30 km3 reservoir, can account for the estimated 3 My age of the system.  相似文献   

19.
Three rocks representing the calc-alkaline rock series gabbro-tonalite-granite or basalt-andesite-rhyolite were reacted with varying percentages of water in sealed capsules between 600 and 1300°C and pressures to 36 kbars, corresponding to depths of more than 120 km within the earth. For each rock we present complete P-T diagrams with excess water, and the water-undersaturated liquids surface projected from P-T-XH2O space mapped with contours for constant H2O contents and with the fields for near-liquidus minerals. All changes in liquidus and solidus slopes can be correlated with changes in mineralogy from less dense to more dense, or with expansion of crystallization fields, without appeal to changes in molar volume of H2O in liquid and vapor phases. The results indicate that tholeiites and andesites of the calc-alkaline series with compositions similar to the rocks studied are not primary magmas from mantle peridotite at depths greater than about 50 km. Primary andesitic magmas from shallower levels would require very high water contents and we do not believe such magmas could normally reach the surface. The liquids results are consistent with the derivation of andesites with little dissolved water as primary magmas from subducted ocean crust (quartz eclogite), but multi-stage models are preferred. Temperatures required for the generation of andesites by fusion of continental crust are higher than considered reasonable. The evidence precludes the generation of primary rhyolites or granites from the mantle of subducted oceanic crust at mantle depths. Primary rhyolite or granite magmas with moderate water contents (saturated or undersaturated) can be generated in the crust at reasonable temperatures, and could reach near-surface levels before vesiculation. Water-undersaturated granite liquid with residual crustal minerals could constitute plutonic magmas of intermediate composition.  相似文献   

20.
We performed pan evaporation experiments with the objective of exploring the behaviour of the long-standing Craig–Gordon (C–G) stable isotope model for evaporation under different conditions of air turbulence. The water lost through evaporation was automatically replenished so that a steady isotopic composition was reached, the value of which depended on the isotopic composition of the replenishment water and environmental parameters like temperature, relative humidity and isotopic composition of the atmospheric vapour, and the air turbulence index. The pans were exposed to artificial winds ranging from 0 to 2.5 m/s to change the air turbulence index, which governs the repartition between vapour transported by molecular diffusion and turbulent diffusion. Our data revealed that for wind speeds >0.5 m/s the isotopic composition of the evaporating water deviated from that predicted by the C–G model. This deviation was hypothetically attributed to microdroplets of liquid water removed by the wind without any isotopic fractionation. Isotope mass balance equations allowed us to quantify this water loss, which at wind speeds of ~2 m/s reached 10% of the total evaporation losses. An alternative kinetic evaporation model was proposed whereby the equilibrium layer and the atmospheric laminar layer above the evaporating water of the C–G model were destroyed by the wind and evaporated water molecules were directly injected into the atmosphere. In this model, the isotopic fractionations were due to the slower kinetics of hydrogen bond breakage between molecules in liquid water when heavy isotopes are involved. Accordingly, our data suggested that for isotope water balance studies where winds are frequently above 2 m/s, the C–G model may be inadequate without appropriate corrections for spray vaporization, or the introduction of appropriate kinetic isotope fractionation factors.  相似文献   

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