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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.
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   

4.
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   

5.
The paper presents preliminary results of the use of a high resolution double-focussing, magnetic sector inductively coupled plasma-mass spectrometer (HR-ICP-MS) with ultraviolet laser ablation (LA) for the bulk analysis of geological materials fused with Li2B4O7. Detection limits are based on data from precision measurements of a fused SiO2 sample of high purity, and sensitivity data (cps/μg g-1) obtained on the Reference Material (RM) Syenite SY-2. For many trace elements, the detection limits are better than 0.05 μg g-1 using a sample to flux weight ratio of 1:7.
Calibration curves, which are based entirely on RMs, are established for Hf, Ta, Tb, Tm and Lu. They indicate that, even at this early stage in the development of the technique, data accurate to ˜ 25% can be collected. It is concluded that the method may prove to be a valuable supplement to XRF for low level element concentration measurements; it is also very practical, as the same sample discs can be used for both XRF and LA-ICP-MS analyses.  相似文献   

6.
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   

7.
Ijolite-carbonatite complexes are ubiquitously surrounded of an aureole of metasomatically altered rocks. The process of alteration is termed fenitization and is generally caused by peralkaline fluids emanating from cooling alkaline, i.e. ijolite and carbonatite magmas. Ijolites and carbonatites normally occur together and attempts to determine the source of the fenitizing fluids may therefore lead to controversial, if not erroneous, conclusions.
Mineralogical and chemical data of fenites from Oldoinyo Lengai (Tanzania), Fen (Norway), and Alnö (Sweden) are reviewed in the present paper in order to reveal the main factors controlling the fenitization around ijolite and carbonatite. Despite the overall alkaline nature of the process, variables such as XCO2 of the fluid, activity gradients of SiO2, Al2O3 and CaO, FeO/MgO ratio, f O2 and temperature gradients may differ, producing distinctive patterns of fenitization around the two magmatic sources. The ijolitic-type fluid has low XCO2, high activities of alkalies, SiO2 and Al2O3, and low activity of CaO. The f O2 evolves along the hm-mt buffer conditions and the temperature falls gradually with distance from the magmatic source. The carbonatitic-type fluid has high XCO2, high activities of alkalies and CaO, and low activities of SiO2 and Al2O3. Temperatures and f O2 are initially high, but decrease sharply with distance from the source. Moreover, the CO2-rich fluid may complex and transport the REE.  相似文献   

8.
The solid-solid reaction magnesiocarpholite = sudoite + quartz has been bracketed between 350 and 500°C, 6.3 and 7.8 kbar. Because it is impossible to synthesize end-member sudoite, all experiments were carried out using natural minerals as starting materials. Although mineral compositions were very close to those of the end-members, the effect of the fluorine content in carpholite was significant. Particularly in those experiments where sudoite grows at the expense of carpholite, electron microprobe analysis of the run products shows that a more stable F-rich carpholite crystallizes too, and consumes the fluorine released in solution by the breakdown of the original carpholite.
Our experimental results are combined, through a thermodynamic analysis, with a previous data set and with previous experimental data concerning the relative stability of chlorite, talc and magnesiocarpholite with excess of quartz and water as a function of P–T and AlAl(SiMg)-1 substitutions in phyllosilicates. This allows us to constrain the feasible thermodynamic parameters (H°f, sud; S ° sud) and (H°f,car; S °car) for the Mg end-members. Using the partition coefficients calculated from natural parageneses, we have computed a petrogenetic grid for the system FeO–MgO–Al2O3–SiO2–H2O. It demonstrates that parageneses involving sudoite and carpholite can be used as indicators of P–T conditions, up to 600° C, 8 kbar for sudoite, and at higher pressure for carpholite.  相似文献   

9.
This paper presents a two-stage anion-exchange procedure for tungsten extraction, an improved mass spectrometric procedure for tungsten analysis and a simplified chemical separation and TIMS procedure for the determination of Hf concentrations. The chemical separation of tungsten is based on its complexing properties with HF and H2O2. The blank level for a sample size of 300 mg is about 80 pg for tungsten. The procedure is designed for the high sensitivity of negative thermal ionisation mass spectrometry (NTIMS) provided by the use of Mg oxide as an emitter on Ir filaments. Tungsten can be readily measured with a high precision in various meteoritical material and especially in small W-poor silicate fractions. Samples containing as little as a few ng g-1 tungsten can be analysed reliably with this method.  相似文献   

10.
Determinations of the absolute age of cleavage formation can provide fundamental information about the evolution of orogenic belts. However, when applied to cleavages in slates and phyllites, conventional dating methods are complicated by problems related to mineral separation and the presence of multiple cleavage generations. In situ high-spatial-resolution 40Ar/39Ar laser microprobe geochronology and microstructural observations indicate that the age of cleavage formation in slates and phyllites can be constrained by analysing zones of tightly packed cleavage domains. Three regionally developed cleavages (S2, S3, and S4) are present in the northern Taconic Allochthon of Vermont and New York. Representative samples were studied from a variety of localities where these cleavages, which are defined by white micas, are well developed. In the suite of samples, only S3 and S4 are expressed as domains that are sufficiently wide and spatially isolated in thin section to permit quantitative 40Ar/39Ar geochronology. Mean 40Ar/39Ar laser microprobe ages for these domains are 370.7 ± 1.0 Myr for S3 and 345.5 ± 1.7 Myr for S4. Because estimates of the Ar closure temperature for white micas are substantially higher than the inferred growth temperatures of the micas defining S3 and S4, these values are interpreted as periods since cleavage formation. This interpretation is consistent with independent geochronological constraints on the age of the Acadian orogeny in the region.  相似文献   

11.
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   

12.
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   

13.
Topaz granite is alkali-feldspar granite that contains essential albite, quartz, K-feldspar, lithium-mica, and topaz. As a group topaz granites are characterized by their extreme enrichment in F (up to 3 wt%) and a wide variety of lithophile elements. They can be subdivided into a 'low-P2O5 subtype' (P2O5 < 0.1 wt%, Al2O3 < 14.5 wt%, SiO2 > 73 wt%) and a 'high-P2O5 subtype' (P2O5 > 0.4 wt%, Al2O3 > 14.5 wt%, SiO2 < 73 wt%), the δ18O values of which indicate a dichotomy of source rock: the low-P2O5 subtype (δ18O < 10‰) having a meta-igneous protolith and the high-P2O5 subtype (δ18O > 10 ‰) a source with a significant component of pelitic material. The unusually high F contents enhance the efficacy of melt segregation and crystal-melt fractionation and so facilitate extreme differentiation in topaz granite magmas. Very low melt volumes restrict the bulk composition of the partial melts regardless of the nature of the source; and extreme fractionation forces them along a path of magmatic convergence, to produce a group of granitic rocks with near-minimum compositions so enriched in a variety of lithophile elements (Li, Nb, Ta, Sn) that economic mineralization often results.  相似文献   

14.
The chemical analysis by EMPEDS of 140 samples in cores from six Red Sea troughs and basins has led to the discovery in the Nereus Deep of high vanadium concentrations (up to 1.3% V2O3) in several bulk samples, and to the isolation of a major magnetite phase. This vanado-magnetite, remarkable for its high content of vanadium (mean = 1.45% V2O3) and its lack of titanium, is frequently zoned, the V-content decreasing toward the outer zones. Oxides with up to 42% V2O3, have also been found. Since the origin of the magnetite is clearly authigenic, its high vanadium and low titanium concentrations are traced back to the differential hydrothermal leaching of Fe—Ti-oxides which occur profusely in basic eruptive rock clasts, actually present in some of the overlying seams.  相似文献   

15.
Low-pressure granulite facies metasedimentary gneisses exposed in MacRobertson Land, east Antarctica, include hercynitic spinel-bearing metapelitic gneisses. Peak metamorphic mineral assemblages include spinel + rutile + ilmenite + sillimanite + garnet, spinel + ilmenite + sillimanite + garnet + cordierite, ortho-pyroxene + magnetite + ilmenite + garnet, spinel + cordierite + biotite + ilmenite and orthopyroxene + cordierite + biotite, each with quartz, K-feldspar and melt. The presence of garnet + biotite- and cordierite + orthopyroxene-bearing assemblages implies crossing tie-lines in AFM projection for the K2O-FeO-MgO-Al2O3-SiO2-H2O (KFMASH) system. This apparent contradiction, and the presence of spinel, rutile and ilmenite in the assemblages, is acounted for by using the KFMASH-TiO2-O2 system, i.e. AFM + TiO2+ Fe2O3. We derive a petrogenetic grid for this system, applicable to low-pressure granulite facies metamorphic conditions. Retrograde assemblages are interpreted from corona textures on hercynitic spinel and Fe-Ti oxides. The relative positions of the peak and retrograde metamorphic assemblages on the petrogenetic grid suggest that corona development occurred during essentially isobaric cooling.  相似文献   

16.
For studies of mass-dependent fractionation of calcium isotopes in natural materials, the 48Ca/42Ca ratio is a superior choice to the conventionally measured 44Ca/40Ca ratio for two important reasons. These are (1) mass-dependent fractionation can be determined free from the effects of inherited or ingrown radiogenic 40Ca and (2) this ratio increases the spread of measured isotopic masses by 50%, resulting in statistically better resolution of fractionation, assuming similar precision. A third, though strictly technical, advantage is the inherent ability of a mass spectrometer to measure ratios close to unity (48Ca/42Ca) more precisely than very small or large ratios (44Ca/40Ca). However, because of the very low natural abundance of both 48Ca and 42Ca, their ratio has been very difficult to measure, the only attempt so far being on a high mass resolution MC-ICP-MS with a precision of 0.33%. We report here determination of the 48Ca/42Ca ratio by the more commonly available and user-friendly multi-collector TIMS using a 43Ca-46Ca double-spike, with a significantly better precision of 0.18% (2s). The 48Ca/40Ca or 44Ca/40Ca ratio can also be measured in the same mass spectrometer run to provide complementary information on any radiogenic component.  相似文献   

17.
A simple and reliable method to separate rare earth elements (REE) from Mg, Fe, K, Na, Ca and Ba in ultramafic rocks has been developed, thereby concentrating their abundances. The sample (0.3 g) was digested with HF and HNO3 in a PTFE bomb, placed in a stainless steel container and, after drying, the insoluble residue was dissolved in 6 ml of 10% v/v HNO3. Following the addition of 50% triethanolamine and 30% m/v NaOH solution, the REE were precipitated along with Mg(OH)2, such that the majority of Fe, K and Na in the solution could be separated by centrifuging. The precipitate was dissolved in 1 ml HNO3 and a buffer solution of NH4Cl/NH4OH at pH = 9.0 was added to precipitate the REE along with any remaining Fe as Fe(OH)3, and so achieve separation from Mg, Ca and Ba, which remained in the solution. In this way, REE could be separated from major elements and were concentrated by a factor of about 60. The recovery of REE was more than 95% using this method. Four ultramafic rock reference materials, PCC-1 (USGS), JP-1 (GSJ), DZE-1, DZE-2 (IGGE) and one new proficiency testing sample GeoPT12 (GAS Serpentinite) were analysed by ICP-MS using indium as an internal standard. The quantitation limits were about 0.02–0.2 ng g−1. Smooth chondrite-normalised REE patterns were obtained with a precision for REE determination of about 2–9%.  相似文献   

18.
中国第二次北极科学考察路线上温室气体瓶采样结果分析   总被引：2，自引：0，他引：2  
张东启  徐建中  汤洁  温民 《冰川冻土》2006,28(3):319-323
用气相色谱和非红外色散分析方法,分析了中国第二次北极科学考察路线上采集到的气体样品中温室气体(CO2和CH4)的浓度,对不同纬度带上CO2和CH4平均浓度变化特征进行了研究.结果表明:海洋表面不同纬度带上CO2的浓度呈现出随纬度升高而减小的趋势,这与全球范围内CO2的年平均浓度的地理分布特征相反,显示了海洋对CO2气体的吸收作用.45°N以北的海洋表面,CH4浓度有随纬度升高而增大的趋势,这与全球范围内CH4的年平均浓度的地理分布特征相同;中纬度近海岸地区温室气体浓度变化无明显规律,可能受到区域或局地气团的影响较大.  相似文献   

19.
Abstract Microprobe analysis of the continuous chemical evolution of coexisting biotite-garnet and biotite-garnet-staurolite has been undertaken from interbedded micaschists of the volcanodetrital group of the Vilaine. A thermobarometric study using pertinent mineralogical equilibria reveals a complex P-T evolution, continuous throughout time, from high pressure, medium temperature (kyanite zone) to medium pressure, high temperature (sillimanite zone), then low pressure, medium temperature (andalusite zone). The T, P, fH2o and XH2o variations have been calculated from coexisting biotite-garnet pairs, and from the equilibria: paragonite (in white mica) + quartz ± albite (in plagioclase) + Al silicate + H2O; and, 3 anorthite ± grossular + 2 Alsilicate + quartz. The P-T evolution is correlated with the continuous change in composition of minerals (using P–XMg and T–XMg diagrams) and with the evolution of assemblages. This continuous P-T-time evolution, correlated with the successive formation of S1-S2 foliations, allows us to propose a P-T-time-deformation path for the micaschists and to relate the growth of its mineral components to tectonic processes.  相似文献   

20.
A new petrogenetic grid is presented for the system NCKFMASH (Na2O–CaO–K2O–FeO–MgO–Al2O3–SiO2–H2O), in which Ca is incorporated in garnet, and CaAlNa−1Si−1 solid solution is considered for both the plagioclase and white-mica structures. A compatibility diagram for plagioclase-bearing metapelitic assemblages within the NCKFMASH system also has been derived. A dominant feature of the NCKFMASH grid is the singularities and associated singular reactions which occur along plagioclase+margarite- and plagioclase+paragonite-bearing univariant equilibria. The singularities represent compositional coplanarities which occur in response to the CaAlNa−1Si−1 substitution occurring at different rates in plagioclase and white-mica. This is controlled by a fundamental difference in the mixing within the two mineral structures. The singularities give rise to a number of intriguing phase diagram features, including azeotropes. From the results presented here, it is predicted that the occurrence of margarite and paragonite in pelitic rocks is controlled by equilibria related to the singularities. The presence of these white-micas is strongly dependent upon bulk composition, and plagioclase-bearing, margarite/paragonite-free assemblages, typical of Barrovian-type terranes, are predicted for bulk compositions of Mg/(Mg+Fe)≈0.4 and Ca/(Ca+Na)≈0.4 at for example 5.5  kbar.  相似文献   

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