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1.
The experiments were conducted in the open CO2 system to find out the equilibrium fractionation between the carbonate ion and CO2(g). The existence of isotopic equilibrium was checked using the two-direction approach by passing the CO2−N2 gases with different δ13C compositions (− 1.5‰ and − 23‰) through the carbonate solution with δ13C = − 4.2‰. The ΔCO3T2−−CO2(g) equilibrium fractionation is given as 6.03 ± 0.17‰ at 25 °C. Discussion is provided about the significance of carbonate complexing in determination of ΔCO3T2−−CO2(g) and ΔHCO3T−−CO2(g) fractionations. Finally, an isotope numerical model of flow and kinetics of hydration and dehydroxylation is built to predict the isotopic behaviour of the system with time.  相似文献   

2.
Abstract: The densities of CO2 inclusions in minerals are commonly used to determine the crystallizing conditions of the host minerals. However, conventional microthermometry is difficult to apply for inclusions of small size (< 5–10 μm) or low density. Raman analysis is an alternative method for determining CO2 density, provided that the CO2 density–Raman shift relation is known. This study aims to establish this CO2 density–Raman shift relation by using CO2 inclusions synthesized in fused silica capillaries. By using this newly-developed synthetic technique, we formed pure CO2 inclusions, and their densities were determined by microthermometry. The Raman analysis showed that the relation between CO2 density (D in g/cm3) and the separations (Δ in cm?1) between the two main bands (i.e. Fermi diad bands) in CO2 Raman spectra can be represented by a cubic equation: D (g/cm3)=0.74203(?0.019Δ3+5.90332Δ2?610.79472Δ+21050.30165)?3.54278 (r2=0.99920). Our calculated D value for a given Δ is between those obtained from two previously-reported equations, which were derived from different experimental methods. An example was given in this study to demonstrate that the densities of natural CO2 inclusions that could not be derived from microthermometry could be determined by using our method.  相似文献   

3.
Fluid inclusions in quartz globules and quartz veins of a 3.8-3.7 Ga old, well-preserved pillow lava breccia in the northeastern Isua Greenstone Belt (IGB) were studied using microthermometry, Raman spectrometry and SEM Cathodoluminescence Imaging. Petrographic study of the different quartz segregations showed that they were affected by variable recrystallization which controlled their fluid inclusion content. The oldest unaltered fluid inclusions found are present in vein crystals that survived dynamic and static recrystallization. These crystals contain a cogenetic, immiscible assemblage of CO2-rich (+H2O, +graphite) and brine-rich (+CO2, +halite, +carbonate) inclusions. The gas-rich inclusions have molar volumes between 44.8 and 47.5 cm3/mol, while the brine inclusions have a salinity of ∼33 eq. wt% NaCl. Modeling equilibrium immiscibility using volumetric and compositional properties of the endmember fluids indicates that fluid unmixing occurred at or near peak-metamorphic conditions of ∼460 °C and ∼4 kbar. Carbonate and graphite were precipitated cogenetically from the physically separated endmember fluids and were trapped in fluid inclusions.In most quartz crystals, however, recrystallization obliterated such early fluid inclusion assemblages and left graphite and carbonate as solid inclusions in recrystallized grains. Intragranular fluid inclusion trails in the recrystallized grains of breccia cementing and crosscutting quartz veins have CO2-rich assemblages, with distinctly different molar volumes (either between 43.7 and 47.5 cm3/mol or between 53.5 and 74.1 cm3/mol), and immiscible, halite-saturated H2O-CO2-NaCl(-other salt) inclusions. Later intergranular trails have CH4-H2 (XH2 up to ∼0.3) inclusions of variable density (ranging from 48.0 to >105.3 cm3/mol) and metastable H2O-NaCl(-other salt?) brines (∼28 eq. wt% NaCl). Finally, the youngest fluid inclusion assemblages are found in non-luminescent secondary quartz and contain low-density CH4 (molar volume > 105.33 cm3/mol) and low-salinity H2O-NaCl (0.2-3.7 eq. wt% NaCl). These successive fluid inclusion assemblages record a retrograde P-T evolution close to a geothermal gradient of ∼30 °C/km, but also indicate fluid pressure variations and the introduction of highly reducing fluids at ∼200-300 °C and 0.5-2 kbar. The quartz globules in the pillow fragments only contain sporadic CH4(+H2) and brine inclusions, corresponding with the late generations present in the cementing and crosscutting veins. We argue that due to the large extent of static recrystallization in quartz globules in the pillow breccia fragments, only these relatively late fluid inclusions have been preserved, and that they do not represent remnants of an early, seafloor-hydrothermal system as was previously proposed.Modeling the oxidation state of the fluids indicates a rock buffered system at peak-metamorphic conditions, but suggests a change towards fluid-graphite disequilibrium and a logfH2/fH2O above the Quartz-Fayalite-Magnetite buffer during retrograde evolution. Most likely, this indicates a control on redox conditions and on fluid speciation by ultramafic rocks in the IGB.Finally, this study shows that microscopic solid graphite in recrystallized metamorphic rocks from Isua can be deposited inorganically from a fluid phase, adding to the complexity of processes that formed reduced carbon in the oldest, well-preserved supracrustal rocks on Earth.  相似文献   

4.
Graphite in deep crustal enderbitic (orthopyroxene + garnet + plagioclase + quartz) granulites (740°C, 8.9 kb) of Nilgiri hills, southern India were investigated for their spectroscopic and isotopic characteristics. Four types of graphite crystals were identified. The first type (GrI), which is interstitial to other mineral grains, can be grouped into two subtypes, GrIA and GrIB. GrIA is either irregular in shape or deformed, and rough textured with average δ13C values of −12.7 ± 0.4‰ (n = 3). A later generation of interstitial graphite (GrIB) shows polygonal crystal shapes and highly reflecting smooth surface features. These graphite grains are more common and have δ13C values of −11.9 ± 0.3‰ (n = 14). Both subtypes show well-defined Raman shifts suggesting a highly crystalline nature. Cores of interstitial graphite grains have, on average, lower δ13C values by ∼0.5‰ compared to that of the rim. The second type of graphite (GrII) occurs as solid inclusions in silicate minerals, commonly forming regular hexagonal crystals with a slightly disordered structure. The third type of graphite (GrIII) is associated with solid inclusions (up to 100 μm) that have decrepitation halos of numerous small (<15 μm) satellite fluid inclusions of pure CO2 with varying density (1.105 to 0.75 g/cm3). The fourth type of graphite (GrIV) is found as daughter crystals within primary type CO2-fluid inclusions in garnet and quartz. These fluid inclusions have a range of densities (1.05 to 0.90 g/cm3), but in general are significantly less dense than graphite-free primary, pure CO2 fluid inclusions (1.12 g/cm3). Raman spectral characteristics of graphite inside fluid inclusions suggest graphite crystallization at low temperature (∼ 500°C). The precipitation of graphite probably occurred during the isobaric cooling of CO2-rich peak metamorphic fluid as a result of oxyexsolution of oxide phases. The oxyexsolution process is evidenced by the magnetite-ilmenite granular exsolution textures and the systematic presence of numerous micron-sized rutile and other oxide inclusions in association with fluid inclusions within garnet, plagioclase, and quartz.The carbon isotope compositions of coexisting CO2 (in fluid inclusions) and graphite show a fractionation (α2CO−gr) of ∼6‰ in garnet, consistent with the existing theoretical estimates of α2CO−gr at 800°C. A subsequent generation of CO2 inclusions trapped in matrix quartz and quartz segregation have higher δ13C values, −4‰ and −2.9‰ respectively. Graphite in quartz segregations also has higher δ13C values (−9.8‰) than those in enderbite (−12.7‰). Micro-graphite crystals included in garnet, quartz (enderbite), and quartz (segregation) have average δ13C values of −11.1, −10.4, and −8.7‰ respectively, indicating progressive enrichment in 13C with a decrease in temperature of recrystallization of respective minerals. This progressive enrichment is also observed in carbon isotope compositions of fluid inclusion CO2, suggesting isotopic equilibrium during graphite precipitation from CO2 fluids. Thus, the carbon isotope record preserved in these rocks by the interstitial graphite, CO2 fluid in enderbite, graphite microcrystals, graphite in quartz segregation, and CO2 fluid in quartz segregation, suggests a temperature-controlled isotopic evolution. This evolution is in accordance with a closed system Rayleigh-type graphite precipitation process which progressively enriched residual CO2 in 13C.  相似文献   

5.
Granulite xenoliths within alkali olivine basalts of the Pali-Aike volcanic field, southern Chile, contain the mineral assemblage orthopyroxene + clinopyroxene + plagioclase + olivine + green spinel. These granulites are thought to be accidental inclusions of the lower crust incorporated in the mantle-derived basalt during its rise to the surface. Symplectic intergrowths of pyroxene and spinel developed between olivine and plagioclase imply that the reaction olivine+plagioclase = Al-orthopyroxene + Al-clinopyroxene + spinel (1) occurred during subsolidus cooling and recrystallization of a gabbroic protolith of the granulites.Examination of fluid inclusions in the granulites indicates the ubiquitous presence of an essentially pure CO2 fluid phase. Inclusions of three different parageneses have been recognized: Type I inclusions occur along exsolution lamellae in clinopyroxene and are thought to represent precipitation of structurally-bound C or CO2 during cooling of the gabbro. These are considered the most primary inclusions present. Type II inclusions occur as evenly distributed clusters not associated with any fractures. These inclusions probably represent entrapment of a free fluid phase during recrystallization of the host grains. IIa inclusions are found in granoblastic grains and have densities of 0.68–0.88 g/cm3. Higher density (=0.90–1.02 g/cm3) IIb inclusions occur only in symplectite phases. Secondary Type III CO2+glass inclusions with =0.47–0.78 g/cm3 occur along healed fractures where basalt has penetrated the xenoliths. Type III inclusions appear related to exsolution of CO2 from the host basalt during its ascent to the surface. These data suggest that CO2 is an important constituent of the lower crust under conditions of granulite facies metamorphism, indicated by Type I and II fluid inclusions, and of the mantle, as indicated by Type III inclusions.Correlation of fluid inclusion densities with P-T conditions calculated from both two-pyroxene geothermometry and reation (1) indicate emplacement of a gabbroic pluton at 1,200–1,300° C, 4–6 kb; cooling was accompanied by a slight increase in pressure due to crustal thickening, and symplectite formation occurred at 850±35° C, 5–7 kb. Capture of the xenoliths by the basalt resulted in heating of the granulites, and CO2 from the basalt was continuously entrapped by the xenoliths over the range 1,000–1,200° C, 4–6 kb. Examination of fluid inclusions of different generations can thus be used in conjunction with other petrologic data to place tight constraints on the specific P-T path followed by the granulite suite, in addition to indicating the nature of the fluid phase present at depth.  相似文献   

6.
Fluid inclusions have recorded the history of degassing in basalt. Some fluid inclusions in olivine and pyroxene phenocrysts of basalt were analyzed by micro-thermometry and Raman spectroscopy in this paper. The experimental results showed that many inclusions are present almost in a pure CO2 system. The densities of some CO2 inclusions were computed in terms of Raman spectroscopic characteristics of CO2 Fermi resonance at room temperature. Their densities change over a wide range, but mainly between 0.044 g/cm3 and 0.289 g/cm3. Their micro-thermometric measurements showed that the CO2 inclusions examined reached homogenization between 1145.5℃ and 1265℃ . The mean value of homogenization temperatures of CO2 inclusions in basalts is near 1210℃. The trap pressures (depths) of inclusions were computed with the equation of state and computer program. Distribution of the trap depths makes it know that the degassing of magma can happen over a wide pressure (depth) range, but mainly at the depth of 0.48 km to 3.85 km. This implicates that basalt magma experienced intensive degassing and the CO2 gas reservoir from the basalt magma also may be formed in this range of depths. The results of this study showed that the depth of basalt magma degassing can be forecasted from CO2 fluid inclusions, and it is meaningful for understanding the process of magma degassing and constraining the inorganogenic CO2 gas reservoir.  相似文献   

7.
Three different types of carbonatite magma may be recognized in the Cambrian Fen complex, S.E. Norway: (1) Peralkaline calcite carbonatite magma derived from ijolitic magma; (2) Alkaline magnesian calcite carbonatite magma which yielded biotite-amphibole søvite and dolomite carbonatite; and (3) ferrocarbonatite liquids, related to (2) and/or to alkaline lamprophyre magma (damjernite). Apatite formed during the pre-emplacement evolution of (2) contains inclusions of calcite and dolomite, devitrified mafic silicate glass and aqueous fluid. All of these inclusions have a magmatic origin, and were trapped during a mid-crustal fractionation event (P4 kbars, T625° C), where apatite and carbonates precipitated from a carbonatite magma which coexisted with a mafic silicate melt. The fluid inclusions contain water, dissolved ionic species (mainly NaCl, with minor polyvalent metal salts) and in some cases CO2. Two main groups of fluid inclusions are recognized: Type A: CO2-bearing inclusions, of approximate molar composition H2O 88–90 CO 27-5 NaCl 5 (d=0.85–0.87 g/ cm3). Type B: CO2-free aqueous inclusions with salinities from 1 to 24 wt% NaCleq and densities betwen 0.7 and 1.0 g/cm3. More strongly saline type B inclusions (salinity ca. 35wt%, d=1.0 to 1.1 g/cm3) contain solid halite at room temperature and occur in overgrowths on apatite. Type A inclusions probably contain the most primitive fluid, from which type B fluids have evolved during fractionation of the magmatic system. Type B inclusions define a continuous trend from low towards higher salinities and densities and formed as a result of cooling and partitioning of alkali chloride components in the carbonatite system into the fluid phase. Available petrological data on the carbonatites show that the fluid evolution in the Fen complex leads from a regime dominated by juvenile CO2 + H2O fluids during the magmatic stage, to groundwater-derived aqueous fluids during post-magmatic reequilibration.  相似文献   

8.
Small angle neutron scattering techniques have been applied to investigate the phase behavior of CO2 injected into coal and possible changes in the coal pore structure that may result from this injection. Three coals were selected for this study: the Seelyville coal from the Illinois Basin (Ro = 0.53%), Baralaba coal from the Bowen Basin (Ro = 0.67%), and Bulli 4 coal from the Sydney Basin (Ro = 1.42%). The coals were selected from different depths to represent the range of the underground CO2 conditions (from subcritical to supercritical) which may be realized in the deep subsurface environment. The experiments were conducted in a high pressure cell and CO2 was injected under a range of pressure conditions, including those corresponding to in-situ hydrostatic subsurface conditions for each coal. Our experiments indicate that the porous matrix of all coals remains essentially unchanged after exposure to CO2 at pressures up to 200 bar (1 bar = 105 Pa). Each coal responds differently to the CO2 exposure and this response appears to be different in pores of various sizes within the same coal. For the Seelyville coal at reservoir conditions (16 °C, 50 bar), CO2 condenses from a gas into liquid, which leads to increased average fluid density in the pores (ρpore) with sizes (r) 1 × 105 ≥ r ≥ 1 × 104 Å (ρpore ≈ 0.489 g/cm3) as well as in small pores with size between 30 and 300 Å (ρpore ≈ 0.671 g/cm3). These values are by a factor of three to four higher than the density of bulk CO2 (ρCO2) under similar thermodynamic conditions (ρCO2 ≈ 0.15 g/cm3). At the same time, in the intermediate size pores with r ≈ 1000 Å the average fluid density is similar to the density of bulk fluid, which indicates that adsorption does not occur in these pores. At in situ conditions for the Baralaba coal (35 OC, 100 bar), the average fluid density of CO2 in all pores is lower than that of the bulk fluid (ρpore / ρCO2 ≈ 0.6). Neutron scattering from the Bulli 4 coal did not show any significant variation with pressure, a phenomenon which we assign to the extremely small amount of porosity of this coal in the pore size range between 35 and 100,000 Å.  相似文献   

9.
The abundance of the doubly substituted CO2 isotopologue, 13C18O16O, in CO2 produced by phosphoric acid digestion of synthetic, inorganic calcite and natural, biogenic aragonite is proportional to the concentration of 13C-18O bonds in reactant carbonate, and the concentration of these bonds is a function of the temperature of carbonate growth. This proportionality can be described between 1 and 50 °C by the function: Δ47 = 0.0592 · 106 · T−2 − 0.02, where Δ47 is the enrichment, in per mil, of 13C18O16O in CO2 relative to the amount expected for a stochastic (random) distribution of isotopes among all CO2 isotopologues, and T is the temperature in Kelvin. This relationship can be used for a new kind of carbonate paleothermometry, where the temperature-dependent property of interest is the state of ordering of 13C and 18O in the carbonate lattice (i.e., bound together vs. separated into different CO32− units), and not the bulk δ18O or δ13C values. Current analytical methods limit precision of this thermometer to ca. ± 2 °C, 1σ. A key feature of this thermometer is that it is thermodynamically based, like the traditional carbonate-water paleothermometer, and so is suitable for interpolation and even modest extrapolation, yet is rigorously independent of the δ18O of water and δ13C of DIC from which carbonate grew. Thus, this technique can be applied to parts of the geological record where the stable isotope compositions of waters are unknown. Moreover, simultaneous determinations of Δ47 and δ18O for carbonates will constrain the δ18O of water from which they grew.  相似文献   

10.
Partitioning of Ni in calcite, CaCO3, was evaluated with the aim of collecting data on partition and distribution coefficients and to enhance understanding about the interaction of Ni with the calcite surface and further incorporation into the bulk. This information will aid in the interpretation of geological processes for safety assessment of waste repositories and contamination of groundwater. Coprecipitation experiments were carried out by the constant addition method at 25 °C and pCO2 = 1 and 10−3.5 atm. Ni was moderately partitioned from solution into calcite. For dilute solid solutions (XNi < 0.001), Ni partition coefficients were estimated to be ∼1 and found to be weakly dependent on calcite precipitation rate in the range of 3-230 nmol m−2 s−1. Ni molar fraction in the solid is directly proportional to Ni concentration in the solution. The fit of the data to such a model is good evidence that Ni is taken up as a true solid solution, not simply by physical trapping.  相似文献   

11.
To understand possible volcanogenic fluxes of CO2 to the Martian atmosphere, we investigated experimentally carbonate solubility in a synthetic melt based on the Adirondack-class Humphrey basalt at 1-2.5 GPa and 1400-1625 °C. Starting materials included both oxidized and reduced compositions, allowing a test of the effect of iron oxidation state on CO2 solubility. CO2 contents in experimental glasses were determined using Fourier transform infrared spectroscopy (FTIR) and Fe3+/FeT was measured by Mössbauer spectroscopy. The CO2 contents of glasses show no dependence on Fe3+/FeT and range from 0.34 to 2.12 wt.%. For Humphrey basalt, analysis of glasses with gravimetrically-determined CO2 contents allowed calibration of an integrated molar absorptivity of 81,500 ± 1500 L mol−1 cm−2 for the integrated area under the carbonate doublet at 1430 and 1520 cm−1. The experimentally determined CO2 solubilities allow calibration of the thermodynamic parameters governing dissolution of CO2 vapor as carbonate in silicate melt, KII, (Stolper and Holloway, 1988) as follows: , ΔV0 = 20.85 ± 0.91 cm3 mol−1, and ΔH0 = −17.96 ± 10.2 kJ mol−1. This relation, combined with the known thermodynamics of graphite oxidation, facilitates calculation of the CO2 dissolved in magmas derived from graphite-saturated Martian basalt source regions as a function of P, T, and fO2. For the source region for Humphrey, constrained by phase equilibria to be near 1350 °C and 1.2 GPa, the resulting CO2 contents are 51 ppm at the iron-wüstite buffer (IW), and 510 ppm at one order of magnitude above IW (IW + 1). However, solubilities are expected to be greater for depolymerized partial melts similar to primitive shergottite Yamato 980459 (Y 980459). This, combined with hotter source temperatures (1540 °C and 1.2 GPa) could allow hot plume-like magmas similar to Y 980459 to dissolve 240 ppm CO2 at IW and 0.24 wt.% of CO2 at IW + 1. For expected magmatic fluxes over the last 4.5 Ga of Martian history, magmas similar to Humphrey would only produce 0.03 and 0.26 bars from sources at IW and IW + 1, respectively. On the other hand, more primitive magmas like Y 980459 could plausibly produce 0.12 and 1.2 bars at IW and IW + 1, respectively. Thus, if typical Martian volcanic activity was reduced and the melting conditions cool, then degassing of CO2 to the atmosphere may not be sufficient to create greenhouse conditions required by observations of liquid surface water. However, if a significant fraction of Martian magmas derive from hot and primitive sources, as may have been true during the formation of Tharsis in the late Noachian, that are also slightly oxidized (IW + 1.2), then significant contribution of volcanogenic CO2 to an early Martian greenhouse is plausible.  相似文献   

12.
Stepped heating and crushing experiments have been used to investigate the noble gas and halogen degassing behaviour of quartz in detail. Samples with diverse character were selected from the Eloise and Osborne, Iron Oxide Copper Gold (IOCG) ore deposits, and the Railway Fault, 13 km south of the Mt Isa Mine, in the Proterozoic Mt Isa Inlier of northeast Australia. Quartz has been shown to have a bimodal degassing profile. The first degassing mode at temperatures of <700 °C is caused by thermally induced mechanical decrepitation of fluid inclusions. Changes in the Br/Cl, I/Cl, Ar/Cl and 40Ar/36Ar composition of gas released at different temperatures up to 700 °C can be related to the decrepitation of different types of fluid inclusion observed by microthermometry. These variations with temperature permit deconvolution of the complex fluid inclusion assemblages associated with the IOCG samples; the ultra high salinity, multi solid (MS) and liquid-vapour-daughter (LVD) fluid inclusions, with a predominantly primary origin, decrepitate at higher temperatures than lower salinity liquid-vapour (LV) and monophase (M) fluid inclusions that have a predominantly secondary origin. Three of the IOCG samples have primary MS and LVD fluid inclusions characterized by molar Br/Cl values of between 0.25 × 10−3 and 0.66 × 10−3, I/Cl between 0.37 × 10−6 and 5.0 × 10−6, 40Ar/36Ar values of <1000 and low 36Ar concentrations of 0.7-1.0 × 10−6 cm3 cm−3H2O. These low values are most easily explained by the involvement of halite dissolution water in IOCG genesis. One of the IOCG samples has Br/Cl of 1.3-2.0 × 10−3 and I/Cl of 10 × 10−6, similar to juvenile magmatic fluids in Phanerozoic Porphyry Copper Deposits. This sample also has a higher 36Ar concentration of 3.5 × 10−6 cm3 cm−3H2O and a slightly elevated 40Ar/36Ar of 2236. Step heating reveals limited and non-systematic variation within the more homogenous population of LV fluid inclusions from the Railway Fault. The samples have mean values of 8.1 × 10−3 for Br/Cl; 9.4-12 × 10−6 for I/Cl; <2000 for 40Ar/36Ar; and 4.7-4.8 × 10−6 cm3 cm−3H2O for 36Ar concentration. The Br/Cl values are similar to those previously reported for basinal brines present in silicic alteration at the Mt Isa Mine and the additional data can be explained by interaction of such a bittern brine with fine grained sedimentary rocks in the sub-surface. The second mode of quartz degassing occurs between 1200 and 1450 °C and releases a greater volume of gas than the first degassing mode. Several lines of evidence, including microscope observations, indicate that the gas released at high temperature is also from the fluid inclusion reservoir. However, its release may be triggered by a metastable phase transition of quartz (∼1200 °C) and caution is required in interpretation of the fluid compositions obtained at these temperatures. The data provide an improved understanding of fluid inclusion decrepitation behaviour that is different to that obtained in lower temperatures experiments designed by other workers to investigate H-isotope fractionation.  相似文献   

13.
Petrological and geochemical study of volatile bearing phases (fluid inclusions, amphibole, and nominally anhydrous minerals) in a spinel lherzolite xenolith suite from Quaternary lavas at Injibara (Lake Tana region, Ethiopian plateau) shows compelling evidence for metasomatism in the lithospheric mantle in a region of mantle upwelling and continental flood basalts. The xenolith suite consists of deformed (i.e., protogranular to porphyroclastic texture) Cl-rich pargasite lherzolites, metasomatized (LILE and Pb enrichment in clinopyroxene and amphibole) at T ? 1000 °C. Lherzolites contain chlorine-rich H2O-CO2 fluid inclusions, but no melt inclusions. Fluid inclusions are preserved only in orthopyroxene, while in olivine, they underwent extensive interaction with the host mineral. The metasomatic fluid composition is estimated: XCO2 = 0.64, XH2O = 0.33, XNa = 0.006, XMg = 0.006, XCl = 0.018, (salinity = 14-10 NaCl eq. wt.%, aH2O = 0.2, Cl = 4-5 mol.%). Fluid isochores correspond to trapping pressures of 1.4-1.5 GPa or 50-54 km depth (at T = 950 °C). Synchrotron sourced micro-infrared mapping (ELECTRA, Trieste) shows gradients for H2O-distribution in nominally anhydrous minerals, with considerable enrichment at grain boundaries, along intragranular microfractures, and around fluid inclusions. Total water amounts in lherzolites are variable from about 150 up to 400 ppm. Calculated trace-element pattern of metasomatic fluid phases, combined with distribution and amount of H2O in nominally anhydrous minerals, delineate a metasomatic Cl- and LILE-rich fluid phase heterogeneously distributed in the continental lithosphere. Present data suggest that Cl-rich aqueous fluids were important metasomatic agents beneath the Ethiopian plateau, locally forming a source of high water content in the peridotite, which may be easily melted. High Cl, LILE, and Pb in metasomatic fluid phases suggest the contribution of recycled altered oceanic lithosphere component in their source.  相似文献   

14.
From July to November 2009, concentrations of CO2 in 78 samples of ambient air collected in 18 different interior spaces on a university campus in Dallas, Texas (USA) ranged from 386 to 1980 ppm. Corresponding δ13C values varied from −8.9‰ to −19.4‰. The CO2 from 22 samples of outdoor air (also collected on campus) had a more limited range of concentrations from 385 to 447 ppm (avg. = 408 ppm), while δ13C values varied from −10.1‰ to −8.4‰ (avg.=-9.0‰). In contrast to ambient indoor and outdoor air, the concentrations of CO2 exhaled by 38 different individuals ranged from 38,300 to 76,200 ppm (avg. = 55,100 ppm), while δ13C values ranged from −24.8‰ to −17.7‰ (avg. = −21.8‰). The residence times of the total air in the interior spaces of this study appear to have been on the order of 10 min with relatively rapid approaches (∼30 min) to steady-state concentrations of ambient CO2 gas. Collectively, the δ13C values of the indoor CO2 samples were linearly correlated with the reciprocal of CO2 concentration, exhibiting an intercept of −21.8‰, with r2 = 0.99 and p < 0.001 (n = 78). This high degree of linearity for CO2 data representing 18 interior spaces (with varying numbers of occupants), and the coincidence of the intercept (−21.8‰) with the average δ13C value for human-exhaled CO2 demonstrates simple mixing between two inputs: (1) outdoor CO2 introduced to the interior spaces by ventilation systems, and (2) CO2 exhaled by human occupants of those spaces. If such simple binary mixing is a common feature of interior spaces, it suggests that the intercept of a mixing line defined by two data points (CO2 input from the local ventilation system and CO2 in the ambient air of the room) could be a reasonable estimate of the average δ13C value of the CO2 exhaled by the human occupants. Thus, such indoor spaces appear to constitute effective “sample vessels” for collection of CO2 that can be used to determine the average proportions of C3 and C4-derived C in the diets of the occupants. For the various groups occupying the rooms sampled in this study, C4-derived C appears to have constituted ∼40% of the average diet.  相似文献   

15.
Measurements of the dissolution rate of diopside (r) were carried out as a function of the Gibbs free energy of the dissolution reaction (ΔGr) in a continuously stirred flow-through reactor at 90 °C and pH90 °C = 5.05. The overall relation between r and ΔGr was determined over a free energy range of −130.9 < ΔGr < −47.0 kJ mo1−1. The data define a highly non-linear, sigmoidal relation between r and ΔGr. At far-from-equilibrium conditions (ΔGr ? −76.2 kJ mo1−1), a rate plateau is observed. In this free energy range, the rates of dissolution are constant, independent of [Ca], [Mg] and [Si] concentrations, and independent of ΔGr. A sharp decrease of the dissolution rate (∼1 order of magnitude) occurs in the transition ΔGr region defined by −76.2 < ΔGr ? −61.5 kJ mo1−1. Dissolution closer to equilibrium (ΔGr > −61.5 kJ mo1−1) is characterised by a much weaker inverse dependence of the rates on ΔGr. Modeling the experimental r-ΔGr data with a simple classical transition state theory (TST) law as implemented in most available geochemical codes is found inappropriate. An evaluation of the consequences of the use of geochemical codes where the r-ΔGr relation is based on basic TST was carried out and applied to carbonation reactions of diopside, which, among other reactions with Ca- and Mg-bearing minerals, are considered as a promising process for the solid state sequestration of CO2 over long time spans. In order to take into account the actual experimental r-ΔGr relation in the geochemical code that we used, a new module has been developed. It reveals a dramatic overestimation of the carbonation rate when using a TST-based geochemical code. This points out that simulations of water-rock-CO2 interactions performed with classical geochemical codes should be evaluated with great caution.  相似文献   

16.
Micro-Raman spectroscopy, even though a very promising technique, is not still routinely applied to analyse H2O in silicate glasses. The accuracy of Raman water determinations critically depends on the capability to predict and take into account both the matrix effects (bulk glass composition) and the analytical conditions on band intensities. On the other hand, micro-Fourier transform infrared spectroscopy is commonly used to measure the hydrous absorbing species (e.g., hydroxyl OH− and molecular H2O) in natural glasses, but requires critical assumptions for the study of crystal-hosted glasses. Here, we quantify for the first time the matrix effect of Raman external calibration procedures for the quantification of the total H2O content (H2OT = OH− + H2Om) in natural silicate glasses. The procedures are based on the calibration of either the absolute (external calibration) or scaled (parameterisation) intensity of the 3550 cm−1 band. A total of 67 mafic (basanite, basalt) and intermediate (andesite) glasses hosted in olivines, having between 0.2 and 4.8 wt% of H2O, was analysed. Our new dataset demonstrates, for given water content, the height (intensity) of Raman H2OT band depends on glass density, reflectance and water environment. Hence this matrix effect must be considered in the quantification of H2O by Raman spectroscopy irrespective of the procedure, whereas the parameterisation mainly helps to predict and verify the self-consistency of the Raman results. In addition, to validate the capability of the micro-Raman to accurately determine the H2O content of multicomponent aluminosilicate glasses, a subset of 23 glasses was analysed by both micro-Raman and micro-FTIR spectroscopy using the band at 3550 cm−1. We provide new FTIR absorptivity coefficients (ε3550) for basalt (62.80 ± 0.8 L mol−1 cm−1) and basanite (43.96 ± 0.6 L mol−1 cm−1). These values, together with an exhaustive review of literature data, confirm the non-linear decline of the FTIR absorptivity coefficient (ε3550) as the glass depolymerisation increases. We demonstrate the good agreement between micro-FTIR and micro-Raman determination of H2O in silicate glasses when the matrix effects are properly considered.  相似文献   

17.
Fluid inclusions were studied in samples from the Ashanti, Konongo-Southern Cross, Prestea, Abosso/Damang and Ayanfuri gold deposits in the Ashanti Belt, Ghana. Primary fluid inclusions in quartz from mineralised veins of the Ashanti, Prestea, Konongo-Southern Cross, and Abosso/Damang deposits contain almost exclusively volatile species. The primary setting of the gaseous (i.e. the fluid components CO2, CH4 and N2) fluid inclusions in clusters and intragranular trails suggests that they represent the mineralising fluids. Microthermometric and Raman spectroscopic analyses of the inclusions revealed a CO2 dominated fluid with variable contents of N2 and traces of CH4. Water content of most inclusions is below the detection limits of the respective methods used. Aqueous inclusions are rare in all samples with the exception of those from the granite-hosted Ayanfuri mineralisation. Here inclusions associated with the gold mineralisation contain a low salinity (<6 eq.wt.% NaCl) aqueous solution with variable quantities of CO2. Microthermometric investigations revealed densities of the gaseous inclusions of 0.65 to 1.06 g/cm3 at Ashanti, 0.85 to 0.98 g/cm3 at Prestea, up to 1.02 g/cm3 at Konongo-Southern Cross, and 0.8 to 1.0 g/cm3 at Abosso/Damang. The fluid inclusion data are used to outline the PT ranges of gold mineralisation of the respective gold deposits. The high density gaseous inclusions found in the auriferous quartz at Ashanti and Prestea imply rather high pressure trapping conditions of up to 5.4 kbar. In contrast, mineralisation at Ayanfuri and Abosso/Damang is inferred to have occurred at lower pressures of only up to 2.2 kbar. Mesothermal gold mineralisation is generally regarded to have formed from fluids characterized by H2O > CO2 and low salinity ( ±  6 eq.wt.%NaCl). However, fluid inclusions in quartz from the gold mineralisations in the Ashanti belt point to distinctly different fluid compositions. Specifically, the predominance of CO2 and CO2 >> H2O have to be emphasized. Fluid systems with this unique bulk composition were apparently active over more than 200␣km along strike of the Ashanti belt. Fluids rich in CO2 may present a hitherto unrecognised new category of ore-forming fluids. Received: 30 May 1996 / Accepted: 8 October 1996  相似文献   

18.
We report oxygen- and magnesium-isotope compositions of Ca,Al-rich inclusions (CAIs) from several Rumuruti (R) chondrites measured in situ using a Cameca ims-1280 ion microprobe. On a three-isotope oxygen diagram, δ17O vs. δ18O, compositions of individual minerals in most R CAIs analyzed fall along a slope-1 line. Based on the variations of Δ17O values (Δ17O = δ17O − 0.52 × δ18O) within individual inclusions, the R CAIs are divided into (i) 16O-rich (Δ17O ∼ −23-26‰), (ii) uniformly 16O-depleted (Δ17O ∼ −2‰), and (iii) isotopically heterogeneous (Δ17O ranges from −25‰ to +5‰). One of the hibonite-rich CAIs, H030/L, has an intermediate Δ17O value of −12‰ and a highly fractionated composition (δ18O ∼ +47‰). We infer that like most CAIs in other chondrite groups, the R CAIs formed in an 16O-rich gaseous reservoir. The uniformly 16O-depleted and isotopically heterogeneous CAIs subsequently experienced oxygen-isotope exchange during remelting in an 16O-depleted nebular gas, possibly during R chondrite chondrule formation, and/or during fluid-assisted thermal metamorphism on the R chondrite parent asteroid.Three hibonite-bearing CAIs and one spinel-plagioclase-rich inclusion were analyzed for magnesium-isotope compositions. The CAI with the highly fractionated oxygen isotopes, H030/L, shows a resolvable excess of 26Mg (26Mg∗) corresponding to an initial 26Al/27Al ratio of ∼7 × 10−7. Three other CAIs show no resolvable excess of 26Mg (26Mg∗). The absence of 26Mg∗ in the spinel-plagioclase-rich CAI from a metamorphosed R chondrite NWA 753 (R3.9) could have resulted from metamorphic resetting. Two other hibonite-bearing CAIs occur in the R chondrites (NWA 1476 and NWA 2446), which appear to have experienced only minor degrees of thermal metamorphism. These inclusions could have formed from precursors with lower than canonical 26Al/27Al ratio.  相似文献   

19.
Experimental studies on the stability of several Mg-sulfate hydrates including epsomite (MgSO4·7H2O), hexahydrite (MgSO4·6H2O), starkeyite (MgSO4·4H2O), and kieserite (MgSO4·H2O) as a function of temperature and relative humidity are in poor agreement with calculations based on thermodynamic properties of these substances taken from the literature. Therefore, we synthesized four different MgSO4 hydrates and measured their enthalpies of formation by solution calorimetry at T = 298.15 K. The resulting enthalpies of formation from the elements are:
•
ΔfH0298 (epsomite) = −3387.7 ± 1.3 kJmol−1
•
ΔfH0298 (hexahydrite) = −3088.1 ± 1.1 kJmol−1
•
ΔfH0298 (sanderite, MgSO4·2H2O) = −1894.9 ± 1.3 kJmol−1
•
ΔfH0298 (kieserite) = −1612.4 ± 1.3 kJmol−1
Using mathematical programming (MAP) techniques, standard thermodynamic values consistent both with our calorimetric data and previously published humidity brackets could be derived:
•
Epsomite: ΔfH0298 = −3388.7 kJmol−1, S0298 = 371.3 Jmol−1 K−1, ΔfG0298 = −2871.0 kJmol−1
•
Hexahydrite: ΔfH0298 = −3087.3 kJmol−1, S0298 = 348.5 Jmol−1 K−1, ΔfG0298 = −2632.3 kJmol−1
•
Starkeyite: ΔfH0298 = −2496.1 kJmol−1, S0298 = 259.9 Jmol−1 K−1, ΔfG0298 = −2153.8 kJmol−1
•
Kieserite: ΔfH0298 = −1611.5 kJmol−1, S0298 = 126.0 Jmol−1 K−1, ΔfG0298 = −1437.9 kJmol−1
Additionally, heat capacity measurements and standard entropy determinations of several magnesium sulfate hydrate minerals from the literature are analyzed and judged against estimates obtained from a linear combination of the heat capacities of MgSO4 and hexagonal ice. The results of the MAP analysis are compared to these estimates to conclude that heat capacity and entropy correlate well with the number of waters of hydration. However, even the good correlation is not good enough to capture the fine variations in these properties. Consequently, their experimental measurement is inevitable if reliable thermodynamic data are sought. Our MAP thermodynamic data show that epsomite, hexahydrite, and kieserite have stability fields in the T-%RH space. Starkeyite is metastable. Although no MAP data could have been derived for pentahydrite (MgSO4·5H2O) and sanderite, their transient existence suggest that both of them are metastable as well.  相似文献   

20.
Sorption of Ni(II) onto chlorite surfaces was studied as a function of pH (5–10), ionic strength (0.01–0.5 M) and Ni concentration (10−8–10−6 M) in an Ar atmosphere using batch sorption with radioactive 63Ni as tracer. Such studies are important since Ni(II) is one of the major activation products in spent nuclear fuel and sorption data on minerals such as chlorite are lacking. The sorption of Ni(II) onto chlorite was dependent on pH but not ionic strength, which indicates that the process primarily comprises sorption by surface complexation. The maximum sorption was at pH ∼ 8 (Kd = ∼10−3 cm3/g). Desorption studies over a period of 1–2 weeks involving replacement of the aqueous solution indicated a low degree of desorption. The acid–base properties of the chlorite mineral were determined by titration and described using a non-electrostatic surface complexation model in FITEQL. A 2-pK NEM model and three surface complexes, Chl_OHNi2+, Chl_OHNi(OH)+ and Chl_OHNi(OH)2, gave the best fit to the sorption results using FITEQL. The high Kd values and low degree of desorption observed indicate that under expected groundwater conditions, a large fraction of Ni(II) that is potentially leachable from spent nuclear fuel may be prevented from migrating by sorption onto chlorite surfaces.  相似文献   

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