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1.
Refinements have been made to achieve over 99% yield in the conversion of CO to CO2 in order to improve the reproducibility and accuracy of δ18 O measurements in sulfates. BaSO4 (10-15 mg) was mixed with an identical amount of spectrographic-grade graphite and loaded into a Pt boat. The mixture was gradually heated to 1100 °C to reduce sulfate to CO and CO2; the former gas was simultaneously converted to CO2 by a glow discharge between Pt electrodes immersed in a magnetic field (produced by a pair of external neodymium magnets). A small memory effect was noticed during the analysis (less than 0.3‰ per 10‰ difference in δ18 O between two subsequently analysed samples). The memory effect, however, was suppressed by repetitive preparation of the same specimen. CO2 produced in this way from sulfate reference samples was analysed on a dual inlet and triple collector mass spectrometer along with CO2 equilibrated with VSMOW, GISP and SLAP water reference samples. To avoid large departures of measured isotope ratios from 18O/16O of the working calibrator we used CO2 gas prepared from ocean water sulfate for this purpose. The calibrated δ18 O values (in ‰) obtained in this way for NBS-127, IAEA SO-5 and IAEA SO-6 reference materials were 8.73 ± 0.05, 12.20 ± 0.07 and -10.43 ± 0.12, respectively.  相似文献   

2.
The equilibrium constant, K a, of the association reaction to form ion pairs from charged solute species in supercritical solutions can be calculated from a model based on published equations. Log K a at constant pressure is a linear function of the inverse in the dielectric constant of the fluid times temperature. The dielectric properties of H2O and CO2 at supercritical pressures and temperatures can also be evaluated using the Kirkwood equation. Using Looyenga mixing rules, the dielectric constant of H2O–CO2 mixtures can be obtained and the change in log K a with addition of CO2 in aqueous solutions evaluated. These changes in log K a with addition of CO2 are consistent with measured changes of log K a with addition of Ar in supercritical H2O–Ar solutions.
Log K a of KCl and NaCl increase to an increasing extent as the mole fraction of CO2 increases in H2O–CO2 solutions. For instance, at 2 kbar and constant temperature between 400 and 600° C, log K a of KCl increases by about two orders of magnitude whilst that of NaCl increases by over four orders of magnitude as the CO2 mole fraction increases from 0.0 to 0.35. Such changes in log K a will have dramatic effects on the solubility of minerals in CO2-rich environments.  相似文献   

3.
The results are given for all the determinations made by the co-operating laboratories of major elements in the six NIMROC rock samples (granite, syenite, lujavrite, norite, pyroxenite and dunite) prepared by the National Institute for Metallurgy in 1966. Relevant statistical data are given for the sets of results for each major constituent, and recommended values for all constituents except Al203, Na20, K20and CO2 in dunite, Fe2O3, MgO and CO2 in the granite, Fe23 and CO2 in the norite and CO2 in the pyroxenite.
This report and that on the trace and minor elements issued in 1978 complete the revision of the recommended values. It is suggested that analysts should concentrate rather on those constituents for which the results have shown such a wide scatter that they can be of no usc for reference purposes, than on those for which the ualues are fairly well established.  相似文献   

4.
M.J. Bickle 《地学学报》1996,8(3):270-276
The seawater 87Sr/86Sr curve implies a 50–100 Myr episodicity in weathering rate which requires a corresponding variation in CO2 degassing from the solid earth to the atmosphere. It is proposed that this is caused by orogenesis, which both produces CO2 as a result of metamorphic decarbonation reactions, and consumes extra CO2 as a consequence of erosion-enhanced weathering. Global climate on the geological time-scale is therefore contTolled by the difference between the relatively large and variable orogenic-moderated degassing and weathering CO2 fluxes.  相似文献   

5.
Carbon sources in arc volcanism, with implications for the carbon cycle   总被引：1，自引：0，他引：1  
New CO2/3 He data from the East Sunda Arc (Indonesia) confirm earlier observations that arc volcanic gases have higher CO2/3 He ratios than MOR environments.On average, > 80% of arc volcanic CO2 is recycled, exogene carbon. Addition of a few percent of carbonate-bearing sediments to the mantle wedge explains much of the carbon abundance andcarbon isotopic data of arc gases, but can not explain the He isotope observations. The CO2/3He in arc volcanoes is not strongly dependent on the composition of modem trough sediments (e.g. deep sea clays vs carbonate-rich sequences), and calcite veins in the hydrothermally altered subducted slab may provide a contribution to the recycled carbon flux of, arcs. The sum of globally deep-subducted sediment and slab carbon exceeds the estimated arc CO2 flux, and approximately 3.5 teramole of carbon may return annually to the mantle in convergent zones. The modem combined processes of MOR volcanism, slab alteration, and subduction volcanism do not produce a substantial carbon flux into the exosphere, and rate-changes in ocean floor spreading are unlikely to cause major changes in atmospheric CO2 as a result of changes in the volcanic CO2 fluxes. Intense pulses of flood basalt volcanism, however, may alter the CO2 contents of the atmosphere over the course of a millenium or so, and influence global climate.  相似文献   

6.
The CO2 atmospheric content has shown large variations over geological times. High contents (up to one order of magnitude more than present-day values) ultimately correspond to discrete episodes of mantle degassing, either juvenile, or subduction-related (carbon recycling). A number of arguments (e.g. the continuous volume increase of carbonate-bearing sediments with time) suggest that, throughout the Earth's history, juvenile CO2 has formed a major contribution to the global carbon budget of the Earth.
The absence of a direct relationship between major volcanic episodes and the average CO2 atmospheric content suggests that volcanoes might not be the only way by which mantle CO2 is transported to the surface. It is proposed that large quantities of juvenile CO2 could temporarily be stored in the lower continental crust during major episodes of granulite formation. These are primarily caused by magmatic underplating and they result in a vertical accretion of the crust by accumulation of CO2-bearing, mantle-derived magmas. Most of the CO2 migrates through the crust during post-metamorphic evolution and isostatic restoration of the normal continental thickness. However, large quantities of CO2 can still be present in some areas, notably as high-density fluids enclosed in minerals.  相似文献   

7.
Abstract Nearly pure CO2 fluid inclusions are abundant in migmatites although H2O-rich fluids are predicted from the phase equilibria. Processes which may play a role in this observation include (1) the effects of decompression on melt, (2) generation of a CO2-bearing volatile phase by the reaction graphite + quartz + biotite + plagioclase = melt + orthopyroxene + CO2-rich vapour, (3) selective leakage of H2O from CO2+ H2O inclusions when the pressure in the inclusion exceeds the confining pressure during decompression, and (4) enrichment of grain-boundary vapour in CO2 by subsolidus retrograde hydration reactions.  相似文献   

8.
High-density CO2-rich fluid inclusions from a sapphirine-bearing granulite (Hakurutale, Sri Lanka) have been studied by microthermometry, Raman spectrometry and SEM analysis. Based on textural evidence, two groups of inclusions can be identified: primary, negative crystal shaped inclusions (group I) and pseudo-secondary inclusions, which experienced a local, limited post-trapping modification (group II). Both groups contain magnesite as a daughter mineral, occurring in a relatively constant fluid/solid inclusion volume ratio (volsolid =0.15 total volume). CO2 densities for group I and II differ only slightly. Both groups contain a fluid, which was initially trapped at peak metamorphic conditions as a homogeneous (CO2+MgCO3) mixture. Thermodynamic calculations suggest that such a fluid (CO2+15 vol% MgCO3) is stable under granulite facies conditions. After trapping, magnesite separated upon cooling, while the remaining CO2 density suffered minor re-adjustments. A model isochore based on the integration of the magnesite molar volume in the CO2 fluid passes about 1.5–2 kbar below peak metamorphic conditions. This remaining discrepancy can be explained by the possible role of a small quantity of additional water.  相似文献   

9.
We present an approach for tracing the fate of anthropogenic CO2, compiling a large data set of stable organic carbon isotope ratios from surface sediments, plankton, and sinking matter in the Atlantic Ocean. The δ13C values of sinking matter are generally lower by 0.5–4.6‰ compared to the surface sediments. This difference increases with increasing latitude, which is explained by a stronger modern increase in surface water [CO2 (aq)] in the Southern Ocean relative to the Tropical/Subtropical Ocean. Preindustrial dissolved CO2 concentrations in Atlantic surface waters, estimated from the δ13Corg of surface sediments, are compared to recently measured surface water [CO2 (aq)] values taken from literature. We obtain only a slight increase in [CO2 (aq)] at lower latitudes but a significant change of about 7 ± 2 μ m in high latitudinal surface waters which we attribute to anthropogenic perturbation. Our results suggest that CO2 released by human activities has been stored in Southern Ocean surface waters.  相似文献   

10.
Abstract. This study examined the effect of CO2 on NaCl solubility in hydrothermal fluid, with the synthetic fluid inclusion technique. Fluid inclusions of 30–40 wt% NaCl and 5 mol % CO2 were synthesized, and their halite dissolution temperatures, Tm(halite), were measured. The solubilities of NaCl in CO2-bearing aqueous fluid were obtained at 160–320C under vapor-saturated pressures. The Tm(halite) value in aqueous fluid with 5 mol % CO2 obtained in this study agrees with that of Schmidt et al. (1995), showing that 5 mol % CO2 reduces the solubility of NaCl by about 1 wt%.
Calculation of magnetite solubility suggests that 5–10 mol % CO2 decreases magnetite solubility by 4.5–8.9 % relative to the magnetite solubility in CO2-free solution. Therefore, an increase of CO2 content in ore-forming solutions may cause deposition of iron minerals and produce ore deposits.  相似文献   

11.
Abstract Deformed quartz veins in garnet-zone schist adjacent to the active Alpine Fault, New Zealand, have fluid inclusions trapped along quartz grain boundaries. Textures suggest that the inclusions formed in their present shapes during annealing of the deformed veins. Many of the inclusions are empty, but some contain carbon dioxide with densities that range from 0.16 to 0.80 g cm−3. No water, nitrogen or methane was detected. The inclusions are considerably more CO2-rich than either the primary metamorphic fluid (<5% CO2) or fluids trapped in fracture-related situations in the same, or related, rocks (<50% CO2). Enrichment of CO2 is inferred to have resulted from selective migration (wicking) of saline water from the inclusions along water-wet grain boundaries after cooling-induced immiscibility of a water-CO2 mixture. Inclusion volumes changed after loss of water. Non-wetting CO2 remained trapped in the inclusions until further percolation progressively removed CO2 in solution. This mechanism of fluid migration dominated in ductile quartz-rich rocks near, but below, the brittle-ductile transition. At deeper levels, hydraulic fracturing is also an important mechanism for fluid migration, whereas at shallower levels advection through open fractures dominates the fluid flow regime.  相似文献   

12.
The Geochemical Context of Gas Hydrate in the Eastern Nankai Trough   总被引：1，自引：0，他引：1  
Abstract. Geochemical studies for gas hydrate, gas and organic matter collected from gas hydrate research wells drilled at the landward side of the eastern Nankai Trough, offshore Tokai, Japan, are reported. Organic matter in the 2355 m marine sediments drilled to Eocene is mainly composed of Type III kerogen with both marine and terrigenous organic input. The gas hydrate-bearing shallow sediments are immature for hydrocarbon generation, whereas the sediments below 2100 mbsf are thermally mature. The origins of gases change from microbial to thermogenic at around 1500 mbsf.
Carbon isotope compositions of CH4 and CO2, and hydrocarbon compositions consistently suggest that the CH4 in the gas hydrate-bearing sediments is generated by microbial reduction of CO2. The δ13C depth-profiles of CH4 and CO2 suggest that the microbial methanogenesis is less active in the Nankai Trough sediments compared with other gas hydrate-bearing sediments where solid gas hydrate samples of microbial origin were recovered. Since in situ generative-potential of microbial methane in the Nankai Trough sediments is interpreted to be low due to the low total organic carbon content (0.5 % on the average) in the gas hydrate-bearing shallow sediments, upward migration of microbial methane and selective accumulation into permeable sands should be necessary for the high concentration of gas hydrate in discrete sand layers.  相似文献   

13.
On the basis of fluid inclusion evidence, pervasive influx of deep-seated CO2-rich fluids has been invoked to account for mid- to upper amphibolite facies (M2B) metamorphism on the island of Naxos (Cyclades, Greece). In this paper, mineral devolatilization and melt equilibria are used to constrain the composition of both syn- and post-peak-M2B fluids in the deepest exposed levels of the metamorphic complex. The results indicate that peak-M2B fluids were spatially and compositionally heterogeneous throughout the high-grade core of the complex, whereas post-peak-M2B fluids were generally water-rich. The observed heterogeneities in syn-M2B fluid composition are inconsistent with pervasive CO2-flushing models invoked by previous workers on the basis of fluid inclusion evidence. It is likely that few CO2-rich fluid inclusions on Naxos preserve fluids trapped under peak metamorphic conditions. It is suggested that many of these inclusions have behaved as chemically open systems during the intense deformation that accompanied the uplift of the metamorphic complex. A similar process may explain the occurrence of some CO2-rich fluid inclusions in granulite facies rocks.  相似文献   

14.
Calc-silicate granulites from the Bolingen Islands, Prydz Bay, East Antarctica, exhibit a sequence of reaction textures that have been used to elucidate their retrograde P–T path. The highest temperature recorded in the calc-silicates is represented by the wollastonite- and scapolite-bearing assemblages which yield at least 760°C at 6 kbar based on experimental results. The calc-silicates have partially re-equilibrated at lower temperatures (down to 450°C) as evidenced by the successive reactions: (1) wollastonite + scapolite + calcite = garnet + CO2, (2) wollastonite + CO2= calcite + quartz, (3) wollastonite + plagioclase = garnet + quartz, (4) scapolite = plagioclase + calcite + quartz, (5) garnet + CO2+ H2O = epidote + calcite + quartz, and (6) clinopyroxene + CO2+ H2O = tremolite + calcite + quartz.
The reaction sequence observed indicates that a CO2 was relatively low in the wollastonite-bearing rocks during peak metamorphic conditions, and may have been further lowered by local infiltration of H2O from the surrounding migmatitic gneisses on cooling. Fluid activities in the Bolingen calc-silicates were probably locally variable during the granulite facies metamorphism, and large-scale CO2 advection did not occur.
A retrograde P–T path, from the sillimanite stability field ( c. 760°C at 6 kbar) into the andalusite stability field ( c. 450°C at <3 kbar), is suggested by the occurrence of secondary andalusite in an adjacent cordierite–sillimanite gneiss in which sillimanite occurs as inclusions in cordierite.  相似文献   

15.
Abstract. Laser Raman microprobe analysis was performed on the fluid inclusions from the Honko-Sanjin zone in the Hishikari epithermal gold deposit, southern Kyushu, Japan. Gas concentrations of fluid inclusions through the zone were below detection limits (e.g., 5 mmole/kg H2O for CO2), with an exception at shallow portion in which the CO2/N2 mole ratio was determined to be 5.3. Boiling of hydrothermal solutions probably separated gases from ore fluids at the deep portion of the deposit, and migration of gases to shallow portion resulted in CO2-rich steam-heated water and related acid alteration.  相似文献   

16.
A sequence of regional metamorphic isograds indicating a range from prehnite-pumpellyite to lower amphibolite facies was mapped in metabasites near Flin Flon, Manitoba. The lowest grade rocks contain prehnite + pumpellyite and are cut by younger brittle faults containing epidote + chlorite + calcite. Isobaric temperature- X CO2 and pressure-temperature (constant X CO2) diagrams were calculated to quantify the effects of CO2 in the metamorphic fluid on the stability of prehnite-pumpellyite facies minerals in metabasites containing excess quartz and chlorite. Prehnite and, to a lesser extent, pumpellyite are stable only in fluids with X co2 <0.002. For X co2>0.002, epidote + chlorite + calcite assemblages are stable. Our calculated phase relations are consistent with regional metamorphism in the Flin Flon area in the presence of an H2O-rich fluid and a more CO2-rich fluid in the later fault zones. We believe that the potential effects of small amounts of CO2 in the metamorphic fluid should be assessed when considering the pressure-temperature implications of mineral assemblages in low-grade metabasites.  相似文献   

17.
Results of electron microprobe and microthermometric studies of samples collected from the Bouvet Triple Junction Region (BTJR) during a joint Russian-Italian geological expedition on the R/V Academician Nikolaj Strakhov (1994) have revealed new data on the composition of basaltic magmas and oceanic hydrothermal fluids connected with magmatic processes. Detailed analysis of basaltic glasses shows that the modem Mid-Atlantic Ridge (MAR) rift valley is composed of normal mid-ocean ridge basalts with low concentrations of K2 O and TiOz (N-MORB), while its flanks are more enriched with these components approaching E-MORB. A marked influence of the Bouvet hot spot volcanism on magma generation on the South-West Indian Ridge (SWIR) near Bouvet Island is observed. Basaltic melts in this area belong to alkalic and transitional series and have maximum contents of K2O, TiO2, H2O.
Microthermometric analyses of fluid inclusions in the samples from the BTJR have revealed major differences in the oceanic hydrothermal fluid systems on the MAR and near SWIR, which depends on the peculiarities of magma. In the area of the MAR (with dry melts) only H2O solution inclusions in quartz were found; thus, seawater is probably the only primary source of hydrothermal fluids (NaCl + MgCl2+ H2O; T = 170–200°C). In the SWIR area (with the high content of water in melts) syngenetic liquid CO2 and H2O solution inclusions in quartz indicate the influence of the magmatic fluid component on the ore-forming water/carbon dioxide solutions (NaCl + CaC12+ H2O + CO2; T = 200–310 °C; P = 900–1700 bar).  相似文献   

18.
This work presents the results of a fluid inclusion study of an amphibolite-granulite facies transition in West Uusimaa, S.W. Finland. Early fluid-inclusions in the granulite facies area are characteristically carbonic (CO2), in contrast to predominantly aqueous early inclusions in the amphibolite facies area. These early inclusions can be related to peak metamorphic conditions (750-820°C and 3-5 kbar for peak granulite facies metamorphism). Relatively young CO2 inclusions with low densities (<0.8g/cm3) indicate that the first part of the cooling history of the rocks was characterized by a near isothermal uplift.
N2-CH4 inclusions, with compositions ranging between pure CH4 and pure N2 (Raman spectral analysis), were found in the whole area. They are probably syn- or even pre-early inclusions. Only nearly critical homogenizing inclusions have been found (low density). Pressure estimates, based on densities of early fluid inclusions, show that the rapid transition of amphibolite towards granulite facies metamorphism is virtually isobaric. Granulite facies metamorphism in West Uusimaa is a thermal event, probably induced by the influx of hot, CO2-bearing fluids.  相似文献   

19.
Abstract Quartz-hosted, synthetic CO2-H2O fluid inclusions behave as open systems with respect to diffusional transfer of hydrogen during laboratory-simulated metamorphic re-equilibration at 650, 750 and 825°C and 1.5 kbar total pressure with fO2 defined by the C-CH4 buffer. Microthermometry and Raman spectroscopy show that the initial CO2-H2O inclusions become CO2-CH4-H2-H2O
inclusions after diffusive influx of hydrogen from the reducing confining medium. Measurable changes are observed in inclusion compositions after only 15 days of re-equilibration, implying significant hydrogen mobility at still lower temperatures over geological time spans. Results of synthetic inclusion re-equilibrium experiments have profound implications for the interpretation of natural fluid-inclusion data; failure to account for potential hydrogen migration in inclusions from high-temperature geological environments may lead to erroneous estimates of P-T, and/or the compositions of metamorphic fluids.  相似文献   

20.
Abstract Three types of mineral associations are described from calc-silicate granulites from the Eastern Ghats, India, where geothermobarometry in associated rocks suggests extremely high P–T conditions of metamorphism ( c . 9 ± 1 kbar, 950° C). These mineral associations are: (i) calcite + quartz + scapolite + plagioclase, (ii) calcite + scapolite + wollastonite + porphyroblastic garnet + coronal garnet and (iii) calcite + quartz + wollastonite + scapolite + porphyroblastic garnet + coronal garnet, all coexisting with K-feldspar, titanite and clinopyroxene. The first two associations evolved through nearly isobaric cooling retrograde paths, whereas the third evolved through a nearly isothermal decompression path followed by an isobaric cooling retrograde path. Textural and compositional characteristics suggest the following mineral reactions in the calc-silicate granulites: calcite + quartz = wollastonite + CO2, calcite + plagioclase = scapolite, calcite + scapolite + wollastonite = porphyroblastic garnet ± quartz + CO2, CaTs + wollastonite = coronal garnet (association ii) and wollastonite + scapolite = coronal garnet (association iii) + quartz + CO2. Andradite content in garnet was buffered by the redox equilibria wollastonite + hedenbergite + O2= andradite + quartz (association iii) and wollastonite + andradite + CaTs + scapolite = hedenbergite + calcite + grossular + O2 (association ii). The contrasting mineral parageneses have been ascribed to interplay of variables such as X CO2, f O2, f HCl in the fluid, bulk Na content and the nature of the retrograde P–T–X CO2 paths through which the rocks evolved.  相似文献   

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