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1.
The origin of monzonitic intrusions that are associated with Proterozoic massif-type anorthosite complexes is controversial. A detailed oxygen isotope study of the Sybille intrusion, a monzonitic intrusion of the Laramie Anorthosite Complex (Wyoming), indicates that either derivation from a basaltic magma of mantle origin with a metasedimentary component (∼20%) incorporated early in its magmatic history, or a partial melt of lower crustal rocks is consistent with the data. The oxygen isotope compositions of plagioclase, pyroxene and zircon from the Sybille monzosyenite, the dominant rock type in the Sybille intrusion, were analyzed in order to establish the isotopic composition of the source of the magma. Plagioclase δ18O values range from 6.77 to 9.17‰. We interpret the higher plagioclase δ18O values (average 8.69 ± 0.30‰, n = 19) to be magmatic in origin, lower plagioclase δ18O values (average 7.51 ± 0.44‰, n = 22) to be the result of variable subsolidus alteration, and pyroxene δ18O values (average 6.34 ± 0.38‰, n = 19) to be the result of closed-system diffusional exchange during cooling. Low magnetic zircons, which have been shown to retain magmatic oxygen isotope values despite high grade metamorphism and extensive subsolidus hydrothermal alteration, have δ18O values (7.40 ± 0.24‰, n = 11) which are consistent with our interpretation of the plagioclase and pyroxene results. Oxygen isotope data from all three minerals indicate that the magmatic oxygen isotope composition of the Sybille intrusion is enriched in 18O relative to the composition of average or “normal” mantle-derived magmas. This enrichment is approximately twice the oxygen isotope enrichment that could result from closed-system fractionation, rendering a closed-system, comag- matic petrogenetic model between the Sybille intrusion and the mantle-derived anorthositic lithologies of the Laramie Anorthosite Complex improbable. Received: 7 April 1998 / Accepted: 19 January 1999  相似文献   

2.
Oxygen exchange experiments have been performed between single crystals of sanidine feldspar and oxygen gas enriched in 18O, at temperatures in the range 869–1053 °C, total pressure 1 atmosphere, for times up to 28 days. Oxygen isotope diffusion profiles in a direction perpendicular to (001) were determined with an ion microprobe. The experimental data obey a single Arrhenius relationship of the form D = 8.4 × 10−11 exp. (−245 ± 15 kJ mol−1/RT) m2s−1. The results indicate that oxygen diffusion in anhydrous sanidine feldspar is marginally slower than oxygen diffusion in anhydrous anorthite. Comparison with published atomistic simulation studies suggests that oxygen transport in feldspar is by an interstitial mechanism. Received: 17 October 1997 / Accepted: 6 July 1998  相似文献   

3.
Mo-Bi mineralization occurs in subvertical and subhorizontal quartz-muscovite-± K-feldspar veins surrounded by early albitic and later K-feldspathic alteration halos in monzogranite of the Archean Preissac pluton, Abitibi region, Québec, Canada. Molybdenite is intergrown with muscovite in the veins or associated with K-feldspar in the alteration halos. Mineralized veins contain five main types of fluid inclusions: aqueous liquid and liquid-vapor inclusions, aqueous carbonic liquid-liquid-vapor inclusions, carbonic liquid and vapor inclusions, halite-bearing aqueous liquid and liquid-vapor inclusions, trapped mineral-bearing aqueous liquid and liquid-vapor inclusions. The carbonic solid in frozen carbonic and aqueous-carbonic inclusions melts in most cases at −56.7 ± 0.1 °C indicating that the carbonic fluid consists largely of CO2. All aqueous inclusion types and the aqueous phase in carbonic inclusions have low initial melting temperatures (≥70 °C), requiring the presence of salts other than NaCl. Leachate analyses show that the bulk fluid contains variable proportions of Na, K, Ca, Cl, and traces of Mg and Li. The following solids were identified in the fluid inclusions by SEM-EDS analysis: halite, calcite, muscovite, millerite (NiS), barite and antarcticite (CaCl2 · 6H2O). All are interpreted to be trapped phases except halite which is a daughter mineral, and antarcticite which formed during sample preparation (freezing). Aqueous inclusions homogenize to liquid at temperatures between 75 °C and 400 °C; the mode is 375 °C. Aqueous-carbonic inclusions homogenize to liquid or vapor between 210 °C and 400 °C. Halite-bearing aqueous inclusions homogenize by halite dissolution at approximately 170 °C. Aqueous inclusions containing trapped solids exhibit liquid-vapor homogenization at temperatures similar to those of halite-bearing aqueous inclusions. Temperatures of vein formation, based on oxygen isotopic fractionation between quartz and muscovite, range from 342 °C to 584 °C. The corresponding oxygen isotope composition of the aqueous fluid in equilibrium with these minerals ranges from 1.2 to 5.5 per mil with a mean of 3.9 per mil, suggesting that the liquid had a significant meteoric component. Isochores for aqueous fluid inclusions intersect the modal isotopic isotherm of 425 °C at pressures between 590 and 1900 bar. A model is proposed in which molybdenite was deposited owing to decreasing temperature and/or pressure from CO2-bearing, moderate to high salinity fluids of mixed magmatic-meteoric origin that were in equilibrium with K-feldspar and muscovite. These fluids resulted from the degassing of a monzogranitic magma and evolved through interaction with volcanic (komatiitic) and sedimentary country rocks. Received: 6 February 1997 / Accepted: 28 January 1998  相似文献   

4.
Crustal xenoliths from basanitic dikes and necks that intruded into continental sediments of the Cretaceous Salta Rift at Quebrada de Las Conchas, Provincia Salta, Argentina were investigated to get information about the age and the chemical composition of the lower crust. Most of the xenoliths have a granitoid composition with quartz-plagioclase-garnet-rutile ± K-feldspar as major minerals. The exceedingly rare mafic xenoliths consist of plagioclase-clinopyroxene-garnet ± hornblende. All xenoliths show a well equilibrated granoblastic fabric and the minerals are compositionally unzoned. Thermobarometric calculations indicate equilibration of the mafic xenoliths in the granulite facies at temperatures of ca. 900 °C and pressures of ca. 10 kbar. The Sm-Nd mineral isochron ages are 95.1 ± 10.4 Ma, 91.5 ± 13.0 Ma, 89.0 ± 4.2 Ma (granitoid xenoliths), and 110.7 ± 23.6 Ma (mafic xenolith). These ages are in agreement with the age of basanitic volcanism (ca. 130–100 and 80–75 Ma) and are interpreted as minimum ages of metamorphism. Lower crustal temperature at the time given by the isochrons was above the closure temperature of the Sm-Nd system (>600–700 °C). The Sm-Nd and Rb-Sr isotopic signatures (147Sm/144Nd = 0.1225–0.1608; 143Nd/144Ndt 0 = 0.512000–0.512324; 87Rb/86Sr = 0.099–0.172; 87Sr/86Srt 0 = 0.708188–0.7143161) and common lead isotopic signatures (206Pb/204Pb = 18.43–18.48; 207Pb/204Pb = 15.62–15.70; 208Pb/204Pb = 38.22 –38.97) of the granitoid xenoliths are indistinguishable from the isotopic composition of the Early Paleozoic metamorphic basement from NW Argentina, apart from the lower 208Pb/204Pb ratio of the basement. The Sm-Nd depleted mantle model ages of ca. 1.8 Ga from granitoid xenoliths and Early Paleozoic basement point to a similar Proterozoic protolith. Time constraints, the well equilibrated granulite fabric, P-T conditions and lack of chemical zoning of minerals point to a high temperature in a crust of nearly normal thickness at ca. 90 Ma and to a prominent thermal anomaly in the lithosphere. The composition of the xenoliths is similar to the composition of the Early Paleozoic basement in the Andes of NW Argentina and northern Chile. A thick mafic lower crust seems unlikely considering low abundance of mafic xenoliths and the predominance of granitoid xenoliths. Received: 21 July 1998 / Accepted: 27 October 1998  相似文献   

5.
A generalized approach for retrieving equilibrium isotope fractionations from natural rocks is proposed in which models of prograde reaction histories and retrograde diffusional exchange are used to identify coexisting minerals with similar isotope closure temperatures. Examples using literature data and new analyses from 32 natural amphibolite-facies schists demonstrate both the feasibility and limitations of obtaining equilibrium oxygen isotope fractionations from minerals in natural rocks. By screening samples according to the theoretical models, natural data are shown to have highly consistent mineral fractionations (±2σ reproducibilities of ±0.16 to 0.54‰) that within uncertainty reproduce experimental determinations among the minerals quartz, biotite, muscovite, and calcic amphibole. This correspondence indicates that the proposed theoretically-based selection criteria improve the likelihood of measuring equilibrium fractionations. The new data further corroborate the expected progressive enrichment of δ18O in the orthosilicates with increasing Al+Si relative to Fe+Mg: Δ(Ky-Grt) ∼1.05‰, Δ(St-Grt) ∼0.6‰, and Δ(St-Cld) ∼0.3‰ at 525–575 °C. In contrast, typical samples that fail to satisfy screening criteria exhibit fractionations involving quartz, biotite, and amphibole that are strongly disequilibrium because of exchange during cooling. Theoretical screening of samples prior to isotope analysis allows robust, independent assessment of theoretical and experimental determinations of equilibrium isotope fractionations. Received: 14 January 1997 / Accepted: 9 March 1998  相似文献   

6.
Seeded, solid-media piston-cylinder runs of unusually long duration up to 31 days indicate growth or persistence of synthetic gedrite of the composition □Mg6Al[AlSi7O22](OH)2(=6:1:7), prepared from the purest chemicals available, at 10 kbar water pressure and 800 °C. Conversely, breakdown was observed at 11 kbar and 850 °C to aluminous enstatite, Al2SiO5, and a melt of the composition MgO·Al2O3·8SiO2. Thus, pure gedrite free of iron, sodium, and calcium is likely to have only a small PT stability field in the MASH system, estimated as 10 ± 1 kbar, 800 ± 20 °C, even though metastable growth of gedrite can be observed over a larger PT range. A second starting material with the anhydrous composition 5MgO · 2Al2O3 · 6SiO2 also yielded gedrite of the composition 6:1:7, together with more aluminous phases such as kyanite, corundum or sapphirine, thus suggesting that the end-member gedrite defined as □Mg5Al2[Al2Si6O22](OH)2(=5:2:6) by the IMA Commission on New Minerals and Mineral Names probably does not exist. With the use of this second starting material, which contains FeNaCa impurities, growth of 6:1:7-gedrite was observed over a still wider PT-range. Seeded runs indicate that the true stability field of such slightly impure 6:1:7-gedrites may also be larger than that of the pure MASH phase and extend at least to 15 kbar, 800 °C. There is, thus, a remarkable stabilization effect on the orthoamphibole structure by impurities amounting only to a total of less than one weight percent of oxides in the starting material. The gedrites synthesized are structurally well ordered amphiboles nearly free of chain multiplicity faults, as revealed by HRTEM. The X-ray diffraction work on the gedrites synthesized yielded the smallest cell volume yet reported for this phase. The small stability field of the pure MASH gedrite is intersected by the upper pressure stability limit of hydrous cordierite for excess-H2O conditions, thus leading to complicated phase relations for both gedrite and cordierite involving the additional phases aluminous enstatite, talc, quartz, Al2SiO5, melt and perhaps boron-free kornerupine. Received: 29 July 1998 / Accepted: 7 January 1999  相似文献   

7.
Oxygen and hydrogen stable isotope ratios of eclogite-facies metagabbros and metabasalts from the Cycladic archipelago (Greece) document the scale and timing of fluid–rock interaction in subducted oceanic crust. Close similarities are found between the isotopic compositions of the high-pressure rocks and their ocean-floor equivalents. High-pressure minerals in metagabbros have low δ18O values: garnet 2.6 to 5.9‰, glaucophane 4.3 to 7.1‰; omphacite 3.5 to 6.2‰. Precursor actinolite that was formed during the hydrothermal alteration of the oceanic crust by seawater analyses at 3.7 to 6.3‰. These compositions are in the range of the δ18O values of unaltered igneous oceanic crust and high-temperature hydrothermally altered oceanic crust. In contrast, high-pressure metabasalts are characterised by 18O-enriched isotopic compositions (garnet 9.2 to 11.5‰, glaucophane 10.6 to 12.5‰, omphacite 10.2 to 12.8‰), which are consistent with the precursor basalts having undergone low-temperature alteration by seawater. D/H ratios of glaucophane and actinolite are also consistent with alteration by seawater. Remarkably constant oxygen isotope fractionations, compatible with isotopic equilibrium, are observed among high-pressure minerals, with Δglaucophane−garnet = 1.37 ± 0.24‰ and Δomphacite−garnet = 0.72 ± 0.24‰. For the estimated metamorphic temperature of 500 °C, these fractionations yield coefficients in the equation Δ = A * 106/T 2 (in Kelvin) of Aglaucophane−garnet = 0.87 ± 0.15 and Aomphacite−garnet = 0.72 ± 0.24. A fractionation of Δglaucophane–actinolite = 0.94 ± 0.21‰ is measured in metagabbros, and indicates that isotopic equilibrium was established during the metamorphic reaction in which glaucophane formed at the expense of actinolite. The preservation of the isotopic compositions of gabbroic and basaltic oceanic crust and the equilibrium fractionations among minerals shows that high-pressure metamorphism occurred at low water/rock ratios. The isotopic equilibrium is only observed at hand-specimen scale, at an outcrop scale isotopic compositional differences occur among adjacent rocks. This heterogeneity reflects metre-scale compositional variations that developed during hydrothermal alteration by seawater and were subsequently inherited by the high-pressure metamorphic rocks. Received: 4 January 1999 / Accepted: 7 July 1999  相似文献   

8.
The island of Salina comprises one of the most distinct calc-alkaline series of the Aeolian arc (Italy), in which calc-alkaline, high-K calc-alkaline, shoshonitic and leucite-shoshonitic magma series are developed. Detailed petrological, geochemical and isotopic (Sr, Nd, Pb, O) data are reported for a stratigraphically well-established sequence of lavas and pyroclastic rocks from the Middle Pleistocene volcanic cycle (430–127 ka) of Salina, which is characterized by an early period of basaltic volcanism (Corvo; Capo; Rivi; Fossa delle Felci, group 1) and a sequence of basaltic andesites, and andesites and dacites in the final stages of activity (Fossa delle Felci, groups 2–8). Major and trace element compositional trends, rare earth element (REE) abundances and mineralogy reveal the importance of crystal fractionation of plagioclase + clinopyroxene + olivine/ orthopyroxene ± titanomagnetite ± amphibole ± apatite in generating the more evolved magma types from parental basaltic magmas, and plagioclase accumulation in producing the high Al2O3 contents of some of the more evolved basalts. Sr isotope ratios range from 0.70410 to 0.70463 throughout the suite and show a well-defined negative correlation with 143Nd/144Nd (0.51275–0.51279). Pb isotope compositions are distinctly radiogenic with relatively large variations in 206Pb/204Pb (19.30–19.66), fairly constant 207Pb/204Pb (15.68–15.76) and minor variations in 208Pb/204Pb ratios (39.15–39.51). Whole-rock δ18O values range from +6.4 to +8.5‰ and correlate positively with Sr isotope ratios. Overall, the isotopic variations are correlated with the degree of differentiation of the rocks, indicating that only small degrees of crustal assimilation are overprinting the dominant evolution by crystal–liquid fractionation (AFC-type processes). The radiogenic and oxygen isotope composition of the Salina basalts suggests derivation from primary magmas from a depleted mantle source contaminated by slab-derived fluids and subducted sediments with an isotopic signature of typical upper continental crust. These magmas then evolved further to andesitic and dacitic compositions through the prevailing process of low-pressure fractional crystallization in a shallow magma reservoir, accompanied by minor assimilation of crustal lithologies similar to those of the Calabrian lower crust. Received: 29 November 1999 / Accepted: 16 April 2000  相似文献   

9.
The Géant Dormant gold mine is a sulfide-rich quartz vein gold deposit hosted by a volcano-sedimentary sequence and an associated felsic endogenous dome and dikes. The auriferous quartz-sulfide veins were preceded by two synvolcanic gold-bearing mineralizing events: early sulfidic seafloor-related and later disseminated pyrite in the felsic dome. This deposit differs from classical Archean auriferous quartz vein deposits by the low carbonate and high sulfide contents of the veins and by their formation prior to ductile penetrative deformation. The δ18O values of quartz associated with seafloor-related auriferous sulfides average 11.9 ± 0.6‰ (n = 3). The seafloor hydrothermal fluids had a δ18O value of 3.2‰ calculated at 250 °C. The oxygen isotope composition of quartz and chlorite from veins average 12.5 ± 0.3‰ (n = 20) and 5.9 ± 1.1‰ (n = 4) respectively. Assuming oxygen isotope equilibrium between quartz and chlorite, the veins formed at a temperature of ∼275 °C, which is consistent with the calculated temperature of 269 ± 10 °C from chlorite chemistry. The gold-bearing fluids had a δ18O value of 4.7‰ calculated at 275 °C. The δ34S values of sulfides from the three gold events range from 0.6 to 2.8‰ (n = 32) and are close to magmatic values. Sulfur isotope geothermometry constrains the sulfide precipitation in the gold-bearing veins at a temperature of ∼350 °C. The similarity of the isotope data, the calculated δ18O of the mineralizing fluids and the likely seawater fluid source suggest that the three mineralizing events are genetically related to a volcanogenic hydrothermal system. The high value of the auriferous fluids (δ18O = 4.7‰) is attributed to a significant magmatic fluid contribution to the evolved seawater-dominated convective hydrothermal system. The two-stage filling of veins at increasing temperature from quartz-chlorite (275 °C) to sulfides (350 °C) may reflect the progressive maturation of volcanogenic hydrothermal systems. These results, together with field and geochemical data, suggest that formation of gold-rich volcanogenic systems require specific conditions that comprise a magmatic fluid contribution and gold from arc-related felsic rocks, coeval with the mineralizing events. This study shows that some auriferous quartz-vein orebodies in Archean terranes are formed in volcanogenic rather than mesothermal systems. Received: 12 December 1998 / Accepted: 5 July 1999  相似文献   

10.
In order to develop models simulating the crystallization of Fe-Ti oxides in natural lavas, we have processed published experimental data on magnetite-melt and ilmenite-melt equilibria. These data include 62 Mt-melt and 75 Ilm-melt pairs at temperatures 1040–1150 °C, oxygen fugacities from IW to NNO+2, and bulk compositions ranging from ferrobasalts to andesites and dacites. Five major cations (Fe3+, Fe2+, Ti4+, Mg2+ and Al3+) were considered for the purpose of describing Fe-Ti oxide saturation as a function of melt composition, temperature and oxygen fugacity at 1 atmosphere pressure. The empirically calibrated mineral-melt expression based on multiple linear regressions is: ln D i  = a/T + blog f O2 + c + d 1 X Na + d 2 X K + d 3 X P, where D i represents molar distribution coefficients of the given cations between Mt/Ilm and melt; X Na, X K, and X P are the molar fractions of Na, K, and P in the melt. The empirically calibrated Mt-melt and Ilm-melt equilibria equations allowed us to develop two models for calculating crystallization temperatures of the Fe-Ti oxides in the melts with an accuracy of 10–15 °C, and compositions with an accuracy of 0.5–2 mol%. These models have been integrated into the COMAGMAT-3.5 program, improving our ability to study numerically the effects of temperature and oxygen fugacity on the stability and phase equilibria of Fe-Ti oxides. Application of this approach to the tholeiitic series of Chazhma Sill from Eastern Kamchatka (Russia) indicates oxygen fugacity conditions near NNO + 0.5. Numerical simulation of fractional crystallization of an iron-enriched basaltic andesite parent at these oxidizing conditions accurately reproduces the FeO-SiO2 relations observed in the Chazhma suite. Received: 3 March 1998 / Accepted: 7 August 1998  相似文献   

11.
 The heat capacity of end-member titanite and (CaTiSiO5) glass has been measured in the range 328–938 K using differential scanning calorimetry. The data show a weak λ-shaped anomaly at 483 ± 5 K, presumably associated with the well-known low-pressure P21/a ⇆ A2/a transition, in good agreement with previous studies. A value of 0.196 ± 0.007 kJ mol−1 for the enthalpy of the P21/a ⇆ A2/a transition was determined by integration of the area under the curve for a temperature interval of 438–528 K, bracketing the anomaly. The heat capacity data for end-member titanite and (CaTiSiO5) glass can be reproduced within <1% using the derived empirical equations (temperature in K, pressure in bars):
The available enthalpy of vitrification (80.78 ± 3.59 kJ mol−1), and the new heat capacity equations for solid and glass can be used to estimate (1) the enthalpy of fusion of end-member titanite (122.24 ± 0.2 kJ mol−1), (2) the entropy of fusion of end-member titanite (73.85 ± 0.1 J/mol K−1), and (3) a theoretical glass transition temperature of 1130 ± 55 K. The latter is in considerable disagreement with the experimentally determined glass transition temperature of 1013 ± 3 K. This discrepancy vanishes when either the adopted enthalpy of vitrification or the liquid heat content, or both, are adjusted. Calculations using Eq. (2), new P−V−T data for titanite, different but also internally consistent thermodynamic data for anorthite, rutile, and kyanite, and experimental data for the reaction: anorthite + rutile = titanite + kyanite strongly suggest: (1) the practice to adjust the enthalpy of formation of titanite to fit phase equilibrium data may be erroneous, and (2) it is probably the currently accepted entropy of 129.2 ± 0.8 J/mol K−1 that may need revision to a smaller value. Received: 30 December 1999 / Accepted: 23 June 2000  相似文献   

12.
Differences between the δ18O values of Si- and Fe-rich immiscible liquids in the system Fe2SiO4-KAlSi2O6-SiO2 (Fa-Lc-Q) in isothermal experiments at 0.1 MPa have been determined experimentally to be 0.6 permil. The observed partition of 18O into the Si-rich liquid is consistent with previous experience with the preferential partition of 18O into Si-rich minerals in isothermal equilibrium with minerals of less polymerized structure. Crystallochemical principles affect the distribution of oxygen isotopes in coexisting isothermal liquids in the same way as they apply to isothermally coexisting crystals. The effects of Soret (thermal) diffusion on the distribution of oxygen isotopes in silicate liquids above the solvus in the system Fa-Lc-Q under conditions of an imposed temperature gradient of ca. 250 °C over 4 mm and at 2 GPa have also been investigated experimentally. Both the magnitude and the direction of separation of oxygen isotopes as a result of Soret diffusion are unexpected. For each of the silicate liquids, the cold end of the charge is enriched in 18O by up to 4.7 permil, and the highest δ18O values are associated with the most silica-poor compositions. The distribution of oxygen isotopes appears to be similar in each liquid, regardless of their chemical compositions, which is in contrast to the behaviour of cations whose distributions are compositionally dependent and characterized by strong crystallochemical effects wherein network-forming species such as Si and Al separate to the hot end and Mg, Fe and Ca are segregated preferentially to the cold end. Structural units in the melts are evidently less selective between oxygen isotopes than between cations, because oxygen redistribution over all possible sites in these units proceeds according to mass. Self-diffusion coefficients of oxygen in basaltic liquids estimated from the Soret experiments are in accord with those from other isotope tracer experiments, and comparable to those of Si. The possible effects of Soret diffusion on the oxygen isotopic composition of metasomatic veins in the mantle are examined in light of these data, and indicate that decay of the thermal gradients in the veins exceeds that of the diffusion of oxygen needed to produce variations in the δ18O values of mantle minerals. Variations in oxygen isotope ratios in most natural systems as a result of Soret effects are unlikely. Received: 6 January 1997 /  Accepted: 28 June 1998  相似文献   

13.
  The diffusivity of water has been investigated for a haplogranitic melt of anhydrous composition Qz28Ab38Or34 (in wt %) at temperatures of 800–1200°C and at pressures of 0.5–5.0 kbar using the diffusion couple technique. Water contents of the starting glass pairs varied between 0 and 9 wt %. Concentration-distance profiles for the different water species (molecular water and hydroxyl groups) were determined by near-infrared microspectroscopy. Because the water speciation of the melt is not quenchable (Nowak 1995; Nowak and Behrens 1995; Shen and Keppler 1995), the diffusivities of the individual species can not be evaluated directly from these profiles. Therefore, apparent chemical diffusion coefficients of water (D water) were determined from the total water profiles using a modified Boltzmann-Matano analysis. The diffusivity of water increases linearly with water content <3 wt % but exponentially at higher water contents. The activation energy decreases from 64 ± 10 kJ/mole for 0.5 wt % water to 46 ± 5 kJ/mole for 4 wt % water but remains constant at higher water contents. A small but systematic decrease of D water with pressure indicates an average activation volume of about 9 cm3/mole. The diffusivity (in cm2/s) can be calculated for given water content (in wt %), T (in K) and P (in kbar) by
in the ranges 1073 K ≤ T ≤ 1473 K; 0.5 kbar ≤ P≤ 5␣kbar; 0.5 wt % ≤ C water ≤ 6 wt %. The absence of alkali concentration gradients in the glasses after the experiments shows that interdiffusion of alkali and H+ or H3O+ gives no contribution to the transport of water in aluminosilicate melts. The H/D interdiffusion coefficients obtained at 800°C and 5 kbar using glass pieces with almost the same molar content of either water or deuterium oxide are almost identical to the chemical diffusivities of water. This indicates that protons are transported by the neutral component H2O under these conditions. Received: 26 March 1996 / Accepted: 23 August 1996  相似文献   

14.
Petrographic, electron microprobe, and bulk-rock geochemical analyses indicate that the distribution and composition of ferromagnesian silicates (biotite, garnet, and staurolite) in and adjacent to the metamorphosed Bleikvassli Zn–Pb–(Cu) volcanogenic massive sulfide deposit, Norway, are dependent upon the competing effects of f O2–f S2 and host-rock composition. The enrichment in magnesium content of these silicates within the orebody and at distances of as much as 5–10 m away is due to the increased f O2 and f S2 conditions imposed on the silicates in zones subject to minor hydrothermal alteration during regional metamorphism. Alternatively, within pelitic country rocks at distances >5–10 m from ore, the host-rock chemistry controls the composition of metamorphic silicate minerals. Also, country rocks within a few meters of ore are distinguished by the common presence of zinc-bearing staurolite (up to 9 wt% ZnO) coexisting with biotite ± garnet. Rocks in the Bleikvassli deposit were hydrothermally enriched in zinc and fluorine prior to metamorphism. The fluorine resides mainly in biotite, which is an additional contributing factor to the magnesium enrichment of that mineral due to Fe2+–F avoidance. Our inference that the sulfidation–oxidation halo around the Bleikvassli ore deposit is only meters in width contrasts with the view of Maiga (1983), who proposed the effects of sulfidation could be identified at distances >159 m from ore. It is evident that the delineation of a sulfidation–oxidation halo bordering a metamorphosed massive sulfide deposit must be done carefully in order to discriminate between the effects due to variations in primary rock composition versus those resulting from a sulfur and oxygen fugacity gradient between the massive sulfides and the sulfur-poor country rocks. Received: 1 March 1998 / Accepted: 3 May 2000  相似文献   

15.
The evolution of nephelinitic melts in equilibrium with mica-bearing liquidus assemblages and melting relations have been studied on two silica-undersaturated joins of the KAlSiO4– Mg2SiO4– Ca2SiO4– SiO2– F system at atmospheric pressure by quench runs in sealed platinum capsules. Fluorine has been added to the batch compositions by the direct exchange of fluorine for oxygen (2F− = O2−). The first join is the pseudo-ternary Forsterite – Diopside – KAlSiO3F2 system. Forsterite, diopside, F-phlogopite and leucite crystallisation fields and a fluoride-silicate liquid immiscibility solvus are present on the liquidus surface of the join. Sub-liquidus and sub-solidus phases include akermanite, cuspidine, spinel, fluorite and some other minor fluorine phases. The second system is the pseudo-binary Akermanite – F-phlogopite join that intersects the Forsterite – Diopside – KAlSiO3F2 join. Akermanite, forsterite, diopside, F-phlogopite, leucite and cuspidine are found to crystallise on the join. Forsterite (fo) and leucite (lc) are related to F-phlogopite (phl) by a reaction with the fluorine-bearing liquid: fo + lc + l = phl, and the reaction proceeds until forsterite or leucite are completely consumed. The reaction temperature and resulting phase association depend on batch composition. Thus, leucite is not stable in the sub-solidus of the Akermanite – F-phlogopite join, but is preserved in a part of the Forsterite – Diopside – KAlSiO3F2 system where forsterite reacts out, or does not crystallise at all. The phlogopite-in reaction has an important effect on the composition of the coexisting liquid. The liquids initially saturated in forsterite evolve to extremely Ca rich, larnite-normative residuals. The experimental data show that larnite-normative melilitolites can crystallise from evolved melilititic melts generated from “normal” melanephelinitic parental magmas with no normative larnite. The evolution towards melilitites requires fractionation of phlogopite-bearing assemblages under volatile pressure. Received: 3 June 1997 / Accepted: 5 January 1998  相似文献   

16.
 Foresighted and determined local authorities, purposeful exploration (i.e. by seismic reflection) and extensive testing led to the discovery of a substantial groundwater resource near the community of Seon (Switzerland) at a depth of 268–305 m. Production tests revealed a hydraulic conductivity of ∼5.10–5 m/s, transmissivity of ∼5.10–4 m2/s and a storage coefficient of ∼2% in the aquifer. Pumping up to 1500 l/min is sustainable; the water quality complies chemically and bacteriologically with drinking-water requirements. The residence time of several 103 years, determined by isotope techniques, guarantees protection from surface contamination. The elevated temperature of 19.5  °C of the produced water enables combined use for drinking water and space heating. The environmental benefits are substantial: the emission reduction amounts up to 780 tons/year CO2 and 1 ton/year SO2. Received: 21 September 1998 · Accepted: 10 February 1999  相似文献   

17.
The Hokko prospect is located in the Minamikayabe area southwestern Hokkaido, Japan, where gold-bearing quartz veins of Pliocene age are exposed at the surface. The alteration mineral assemblage is typical of low-sulfidation epithermal systems, with the quartz veins associated with adularia alteration overprinted on Late Miocene propylitic alteration. Fluid inclusion studies of the vein quartz reveal mean homogenization temperatures of approximately 220 °C, and the co-existence of low-salinity (<2 wt.% NaCl equivalent) and moderate salinity (2 to 12 wt.% NaCl equivalent) fluid inclusions within the same veins. The moderate salinity fluid inclusions (2–12 wt.% NaCl equivalent) typically have relatively low homogenization temperatures between 150° to 200 °C. The results obtained from stable isotope analysis of  δ18O in quartz vein material showed a gradual decrease in  δ18O signatures with increasing depth. The majority of the samples have calculated fluid source signatures (δ18OH2O) between −8.0 and −10.0‰, but there is a significant change in the composition above 185 m drill depth. The shallower samples in particular show a wide range of oxygen isotope signatures that are associated with the moderate salinity fluid inclusions. We interpret that low-salinity inclusions within the Hokko system represent the composition of the liquid phase of the fluid, before boiling, and that the moderate-salinity inclusions are representative of the residual liquid phase, after extensive non-adiabatic boiling and vapor loss in an open system. This mechanism resulted in the entrapment of fluids with variable salinities at the same time, and in close proximity to each other. This is also reflected in the  δ18OH2O values which become more variable and heavier where the moderate-salinity inclusions occur. Deposition of ore minerals within the Hokko vein system also occurred at this time as a result of boiling and gas loss. Received: 30 May 1997 / Accepted: 6 January 1998  相似文献   

18.
Carbon and oxygen isotopic profiles around a low pressure metasomatic wollastonite reaction front in a marble of the Hida metamorphic terrain, central Japan, display typical metamorphic fluid-enhanced isotopic zonations. Isotopic profiles obtained from detailed microscale analyses perpendicular to the chemical reaction front in calcite marble show that diffusion-enhanced isotopic exchange may control these profiles. Carbon and oxygen isotopic behaviour in grain boundaries is remarkably different. Oxygen isotopic troughs (18O depleted rims) around the calcite-grain boundaries are widely observed in this contact aureole, demonstrating that diffusion of oxygen in calcite grain boundary dominates over lattice diffusion in calcite. In contrast, no difference is observed in carbon isotopic profiles obtained from grain cores and rims. There is thus no specific role of the grain boundary for diffusion of carbonic species in the metamorphic fluid during transportation. Carbon chemical species such as CO2 and CO3 ions in metamorphic fluid migrate mainly through lattice diffusion. The carbon and oxygen isotope profiles may be modelled by diffusion into a semi-infinite medium. Empirically lattice diffusion of oxygen isotopes is almost six times faster than that of carbon isotopes, and oxygen grain-boundary diffusion is ten times faster than oxygen lattice diffusion. Oxygen isotopic results around the wollastonite vein indicate that migration of the metamorphic fluid into calcite marble was small and was parallel to the aquifer. From the stability of wollastonite and the attainment of oxygen isotopic equilibrium, we suggest that diffusion of oxygen occurred through an aqueous fluid phase. The timescale of formation of the oxygen isotopic profile around the wollastonite vein is calculated to be about 0.76 × 106 years using the experimentally determined diffusion constant. Received: 14 January 1997 / Accepted: 23 April 1998  相似文献   

19.
 The variation of the oxygen content in olivines, (Fe x Mg1− x )2SiO4, with 0.2 ≤ x ≤ 1.0, was investigated by thermogravimetric measurements. Mass changes occurring upon oxygen activity changes were measured as a function of oxygen activity and cationic composition at 1130 and 1200 °C. During the measurements the samples were in direct contact with gases containing CO, CO2 and N2 and, at a few spots at the bottom of the sample stack, also with SiO2. By fitting experimental data of mass changes to equations derived using point defect thermodynamics, it was shown for olivines with 0.2 ≤ x ≤ 1.0 at 1130 °C and 0.2 ≤ x ≤ 0.7 at 1200 °C within the oxygen activity ranges investigated that the observed variations in the oxygen contents are compatible with cation vacancies and Fe3+ ions on M sites and Fe3+ ions on silicon sites as majority defects if it is assumed that only three types of point defects occur as majority defects. Different cases were considered, closed systems, taking into account that ξ=[Si]/([Si]+[Fe]+[Mg]) is not necessarily equal to 1/3, and olivines in equilibrium with SiO2 or pyroxenes. The oxygen content variations observed in this study are significantly smaller than those reported previously in the literature. It is proposed that these differences are related to the dissolution of Fe into noble metal containers used as sample holders in earlier studies and/or to the presence of secondary phases. Received: 1 November 1995 / Accepted: 15 September 2002 Acknowledgements This work was supported by the Cornell Center for Materials Research (CCMR), a Materials Research Science and Engineering Center of the National Science Foundation (DMR-0079992). The authors thank Mr. Daniel M. DiPasquo and Mr. Jason A. Schick for helping in experimental work.  相似文献   

20.
The crystal structures of 212 experimentally synthesized, igneous clinopyroxenes were modeled from electronprobe chemical data. The coexisting melts span a wide range of petrologically relevant, dry and hydrous compositions, characterized by variable enrichment in silica and alkalis. Experimental conditions pertain to Earth's crust and uppermost mantle (P = 0–24 kbar; garnet absent) and a variety of f O2 values (from CCO-buffered to air-buffered) and mineral assemblages (Cpx ± Opx ± Pig ± Ol ± Plag ± Spl ± Mt ± Amp ± Ilm). Unit-cell volume (Vcell) versus M1-polyhedron volume (VM1) relations were investigated over a range of pressures and temperatures using data derived from structure modeling and corrected for thermal expansivity and compressibility. The relationships between pressure and clinopyroxene structural parameters were found to be dependent on the nature of the coexisting melt. To reduce compositional effects, only clinopyroxenes belonging to mildly alkaline (MA) and tholeiitic (TH) series were considered. Pressure was modeled as a linear function of Vcell, VM1, and Mg/(Mg + Fe2+)Cpx ratio. A calibration based on the whole data set (MA + TH) reproduced the experimental pressures within 1.4 kbar at the 1-σ level. The maximum residuals were 3.5 kbar and 3.9 kbar for MA- and TH-clinopyroxenes, respectively. Better statistics were obtained by considering MA- and TH-clinopyroxenes separately. A calibration based on the 69 MA-clinopyroxenes reproduced the experimental pressures within 1.1 kbar (1σ) and with a maximum residual of 2.7 kbar. A calibration based on the 143 TH-clinopyroxenes reproduced the experimental pressures within 1.0 kbar (1σ) and with a maximum residual of 3.4 kbar. When these geobarometers are applied to natural samples for which P is unknown, the correction for compressibility is necessarily made through a trial-and-error procedure. This expedient propagates an additional error that increases the above uncertainties and residuals by a factor of about 2. Applications to natural, igneous rocks for which the pressures of crystallization could be constrained based on experimental, petrological or geological evidence yielded pressure estimates that reproduced the expected values to within ca. 2 kbar. Compared to the MA-formulation, the TH-formulation appears to be less robust to variations in magma composition. When applied to high-pressure (>10 kbar) clinopyroxenes synthesized from very low Na (Na2O < 1.5%) melts, the latter geobarometer can underestimate P by as much as 6 kbar. Calculation of P through the present geobarometers requires clinopyroxene major-element composition and an independent, accurate estimate of crystallization T. Underestimating T by 20 °C propagates into a 1-kbar increase in calculated P. The proposed geobarometers are incorporated in the CpxBar software program, which is designed to retrieve the pressure of crystallization from a clinopyroxene chemical analysis. Received: 11 June 1998 / Accepted: 12 November 1998  相似文献   

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