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1.
Graphitization and coarsening of organic material in carbonate-bearing metasedimentary rocks is accompanied by carbon isotope exchange which is the basis of a refractory, pressure-independent geothermometer. Comparison of observed isotopic fractionations between calcite and graphite (δ13CCal–Gr) with independent petrological thermometers provides the following empirical calibration over the range 400–800°C: δ13CCal–Gr= 5.81 times 106×T–2(K) - 2.61. This system has its greatest potential in marbles where calcite + graphite is a common assemblage and other geothermometers are often unavailable. The temperature dependency of this empirical calibration differs from theoretical calibrations; reasons for this are unclear but the new empirical calibration yields temperature estimates in better agreement with independent thermometry from several terranes and is preferred for geological applications. Both calcite-graphite isotopic thermometry and calcite-dolomite solvus thermometry are applied to marble adjacent to the Tudor gabbro in the Grenville Province of Ontario, Canada. The marble has undergone two metamorphic episodes, early contact metamorphism and later regional metamorphism. Values of δ13CCal–Gr decrease regularly from c. 8‰ in samples over 2 km from the pluton to values of 3–4‰ within 200 m of the contact. These samples appear to preserve fractionations from the early thermal aureole with the empirical geothermometer, and indicate temperatures of 450–500° C away from the intrusion and 700–750°C near the gabbro. This thermal profile around the gabbro is consistent with conductive heat flow models. In contrast, the distribution of Mg between calcite and dolomite has been completely reset during later regional metamorphism and yields uniform temperatures of c. 500°C, even at the contact. Graphite textures are important for interpreting the results of the calcite–graphite thermometer. Coarsening of graphite approaching the Tudor gabbro correlates with the decrease in isotopic fractionations and provides textural evidence that graphite crystallization took place at the time of intrusion. In contrast to isotopic exchange during prograde metamorphism, which is facilitated by graphitization, retrogressive carbon isotopic exchange appears to require recrystallization of graphite which is sluggish and easily recognized texturally. Resistance of the calcite–graphite system to resetting permits thermometry in polymetamorphic settings to see through later events that have disturbed other systems.  相似文献   

2.
The fractionation of 13C between calcite and graphite, Δ(Cc-Gr). is consistently small (2.6–4.8 permil) in 34 assemblages from upper amphibolite- and granulite-facies marbles of the Grenville Province. In 25 samples from the Adirondack Mountains, New York, it decreases regularly with increasing metamorphic temperature. The fractionations are independent of absolute δ13C values of calcite (?2.9 to +5.0). For T = 600–800°C, the Adirondack data are described by Δ(Cc-Gr) = ?0.00748T (°C) + 8.68. This good correlation between Δ and T suggests that carbon isotope equilibrium was attained in these high-grade marbles and that the theoretical calculations of this fractionation by Bottinga are approximately 2 permil too large in this temperature range. Because of the relatively high temperature sensitivity suggested by these results and by Bottinga's calculations, and the pressure independence of isotope fractionation, Δ(Cc-Gr) may provide a very good thermometer for high-grade marbles.Comparison of this field calibration for Δ(Cc-Gr) vs temperature with results from other terranes supports the utility of Δ(Cc-Gr) for geothermometry and suggests that graphite is much more sluggish to exchange than calcite, that exchange between calcite and graphite occurs at temperatures as low as 300°C, and that equilibrium may normally be attained only when peak metamorphic temperatures are greater than 500–600°C.Because 13C exchange is an unavoidable metamorphic process at temperatures above 300°C, high values of δ13C(Gr) in moderate- to high-grade carbonate-bearing rocks do not provide a sufficient criterion to infer an abiogenic origin for the graphite.  相似文献   

3.
Carbon isotope thermometry in marbles of the Adirondack Mountains, New York   总被引：4，自引：1，他引：4  
Abstract Carbon isotope thermometry has been applied to coexisting calcite and graphite in marbles from throughout the Adirondack Mountains, New York. Eighty-nine calcite-graphite pairs from the amphibolite grade NW Adirondacks change systematically in temperature north-westwards from 680 to 640 to 670° C over a 30-km distance, reflecting transitions from amphibolite facies towards granulite facies to the north-west and to the south-east. Temperature contours based on calcite-graphite thermometry in the NW Adirondacks parallel mineral isograds, with the orthopyroxene isograd falling above 675° C, and indicate that regional metamorphic temperatures were up to 75° C higher than temperatures inferred from isotherms based on cation and solvus thermometry (Bohlen et al. 1985). Fifty-five calcite-graphite pairs from granulite grade marbles of the Central Adirondacks give regional metamorphic temperatures of 670–780° C, in general agreement with cation and solvus thermometry. Data for amphibolite and granulite grade marbles show a 12%oo range in δ13Ccal and δ13Cgr. A strong correlation between carbon isotopic composition and the abundance of graphite (Cgr/Crock) indicates that the large spread in isotopic compositions results largely from exchange between calcite and graphite during closed system metamorphism. The trends seen in δ13C vs. Cgr/Crock and δ13Ccal vs. δ13Cgr could not have been preserved if significant amounts of CO2-rich fluid had pervasively infiltrated the Adirondacks at any time. The close fit between natural data and calculated trends of δ13C vs. Cgr/Crock indicates a biogenic origin for Adirondack graphites, even though low δ13C values are not preserved in marble. Delamination of 17 graphite flakes perpendicular to the c-axis reveals isotopic zonation, with higher δ13C cores. These isotopic gradients are consistent with new graphite growth or recrystallization during a period of decreasing temperature, and could not have been produced by exchange with calcite on cooling due to the sluggish rate of diffusion in graphite. Samples located >2km from anorthosite show a decrease of 0.5-0.8%oo in the outer 100 μ of the grains, while samples at distances over 8 km show smaller core-to-rim decreases of c.0.2%oo. Correlation between the degree of zonation and distance to anorthosite suggests that the isotopic profiles reflect partial overprinting of higher temperature contact metamorphism by later granulite facies metamorphism. Core graphite compositions indicate contact metamorphic temperatures were 860–890° C within 1 km of the Marcy anorthosite massif. If samples with a significant contact metamorphic effect (Δ(cal-gr) <3.2%oo) are not included, then the remaining 38 granulite facies samples define the relation Δ13C(cal-gr) = 3.56 ± 106T-2 (K).  相似文献   

4.
Oxygen isotopic fractionation in the system quartz-albite-anorthite-water   总被引：1，自引：0，他引：1  
Oxygen isotopic fractionations have been determined between quartz and water, albite and water, and anorthite and water at temperatures from 300 to 825°C, and pressures from 1.5. to 25 kbar. The equilibrium quartz-feldspar fractionation curves can be approximated by the following equations: 1000ln αQ?PI = (0.46 + 0.55β)106T?2 + (0.02 + 0.85β) between 500 and 800°C 1000ln αQ?PI = (0.79 + 0.90β)106T?2 — (0.43 ? 0.30β) between 400 and 500°C where β is the mole-fraction of anorthite in plagioclase.Application of these isotopic thermometer calibrations to literature data on quartz and feldspar gives temperatures for some metamorphic rocks which are concordant with quartz-magnetite temperatures. Plutonic igneous rocks typically have quartz-feldspar fractionations which are substantially larger than the equilibrium values at solidus temperatures, indicating substantial retrograde exchange effects.  相似文献   

5.
Amphibolite-grade metasediments from the Mgama Hills region, Kenya, contain conspicuous quantities of graphite, most probably derived from organic progenitor materials. The highest graphite contents (5.1–20.4%) are found in schists whereas calcite marbles intercalated in the sequence contain relatively low amounts (0.1–2.0%). The graphitic constituents are consistently enriched in 13C relative to common sedimentary organic material, with the highest isotopic ratios in graphite from the marbles (δ13C = ?7.3 ± 5.0%.; n = 10). Carbon isotope fractionations between calcite and graphite mostly vary between 3.3 and 7.1‰, which comes close to both empirically recorded and thermodynamically calculated fractionations in the temperature range of the upper amphibolite faciès (550–650°C). However, larger values occasionally encountered in the marbles suggest that complete isotopic equilibrium is not always attained in amphibolite-facies metamorphism.  相似文献   

6.
Carbon isotope fractionations between calcite and graphite in the Panamint Mountains, California, USA, demonstrate the importance of mass balance on carbon isotope values in metamorphosed carbon-bearing minerals while recording the thermal conditions during peak regional metamorphism. Interbedded graphitic marbles and graphitic calcareous schists in the Kingston Peak Formation define distinct populations on a δ13C(gr)–δ13C(cc) diagram. The δ13C values of both graphite and calcite in the marbles are higher than the values of the respective minerals in the schists. δ13C values in both rock types were controlled by the relative proportions of the carbon-bearing minerals: calcite, the dominant carbon reservoir in the marble, largely controlled the δ13C values in this lithology, whereas the δ13C values in the schists were largely controlled by the dominant graphite. This is in contrast to graphite-poor calcsilicate systems where carbon isotope shifts in carbonate minerals are controlled by decarbonation reactions. The marbles record a peak temperature of 531±30 °C of a Jurassic low-pressure regional metamorphic event above the tremolite isograd. In the schists there is a much wider range of recorded temperatures. However, there is a mode of temperatures at c. 435 °C, which approximately corresponds to the temperatures of the principal decarbonation metamorphic reactions in the schists, suggesting that the carbon exchange was set by loss of calcite and armouring of graphite by newly formed silicate minerals. The armouring may explain the relatively large spread of apparent temperatures. Although the modal temperature also corresponds to the approximate temperature of the Cretaceous retrograde event, retrograde exchange is thought less likely due to very slow exchange rates involving well-crystallized graphite, armouring of graphite by silicates during the earlier event, and because of other barriers to retrograde carbon exchange. Thus, only the calcite–graphite carbon isotope fractionations recorded by the marbles demonstrate the high-temperature conditions of the low-pressure Jurassic metamorphic event that was associated with the emplacement of granitic plutons to the west of the Panamint Mountains.  相似文献   

7.
Fractionations of carbon and oxygen isotopes and magnesium between coexisting dolomite and calcite have been determined for marbles and calcareous schists of a wide variety of metamorphic environments from Vermont and the Grenville Province of Ontario. Concordant equilibrium fractionations are given by 83% of the samples. Calibration of the isotopic thermometers using the Mg-calcite solvus thermometer gave in the temperature range: 650°>T°>100°C $$ \begin{gathered} 1,000\ln \alpha _{D - Ct}^{O^{18} } = 0.45 (10^6 T^{ - 2} ) - 0.40 \hfill \\ 1,000\ln \alpha _{D - Ct}^{O^{18} } = 0.18 (10^6 T^{ - 2} ) + 0.17. \hfill \\ \end{gathered} $$ These isotopic fractionation expressions differ significantly from the experimentally derived relations, including the dolomite-Mg-calcite C13 partial exchange experiments of this study. Temperature ranges obtained for the metamorphic zones of Vermont are: chlorite zone, 210° to 295° C; biotite zone, 255° to 400° C; staurolite-kyanite zone, 110° to 550° C. In amphibolite-facies rocks the quenched partition relations can be complex. The temperature of quench or recrystallization may be as large as 400° C below the inferred metamorphic maximum. Oxygen isotope disequilibrium in high grade rocks, particularly from the Chester dome area, Vermont, is characterized by large negative δO D 18 –δO Ct 18 values. The size of the equilibrium exchange system for carbon and oxygen isotopes and magnesium is small, less than a few inches across the inferred relict bedding. This is attributed to the lack of a mobile pore fluid except in systems undergoing decarbonation. C13/C12 ratios in Grenville and Vermont marbles and O18/O16 ratios in Grenville and greenschist-facies Vermont carbonates span the range of ancient limestones. Staurolite-kyanite zone calcareous schists and marbles from the Chester dome area, Vermont are depleted in O18(δO18=12 to 20‰) due to equilibrium or disequilibrium decarbonation and some partial exchange. Extrapolation of the dolomite-calcite fractionation expressions to 20° C indicates that dolomite is enriched in O18 by about 4.9‰ and in C13 by about 2.4‰.  相似文献   

8.
The heat capacity of natural chamosite (XFe=0.889) and clinochlore (XFe=0.116) were measured by differential scanning calorimetry (DSC). The samples were characterised by X-ray diffraction, microprobe analysis and Mössbauer spectroscopy. DSC measurements between 143 and 623?K were made following the procedure of Bosenick et?al. (1996). The fitted data for natural chamosite (CA) in J?mol?1?K?1 give: C p,CA = 1224.3–10.685?×?103?×?T ??0.5???6.4389?× 106?×T ??2?+?8.0279?×?108?×?T ??3 and for the natural clinochlore (CE): C p,CE = 1200.5–10.908?×?103?×T ??0.5?? 5.6941?×?106?×?T ??2?+?7.1166?×?108?×?T ??3. The corrected C p-polynomial for pure end-member chamosite (Fe5Al)[Si3AlO10](OH)8 is C p,CAcor = 1248.3–11.116?× 103?×?T ??0.5???5.1623?×?106?×?T ??2?+?7.1867?×?108×T ??3 and the corrected C p-polynomial for pure end-member clinochlore (Mg5Al)[Si3AlO10](OH)8 is C p,CEcor = 1191.3–10.665?×?103?×?T ??0.5???6.5136?×?106?×?T ??2?+ 7.7206?×?108?×?T ??3. The corrected C p-polynomial for clinochlore is in excellent agreement with that in the internally consistent data sets of Berman (1988) and Holland and Powell (1998). The derived C p-polynomial for chamosite (C p,CAcor) leads to a 4.4% higher heat capacity, at 300?K, compared to that estimated by Holland and Powell (1998) based on a summation method. The corrected C p-polynomial (C p,CAcor) is, however, in excellent agreement with the computed C p-polynomial given by Saccocia and Seyfried (1993), thus supporting the reliability of Berman and Brown's (1985) estimation method of heat capacities.  相似文献   

9.
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   

10.
The thermal expansivity of liquid GeO2 at temperatures just above the glass transition has been obtained using a combination of scanning calorimetry and dilatometry. The calorimetric and dilatometric curves of c p and dV/dT are normalized to the temperature derivative of fictive temperature versus temperature using the method of Webb et al. (1992). This normalization, based on the equivalence of relaxation parameters for volume and enthalpy, allows the completion of the dilatometric trace across the glass transition to yield liquid expansivity and volume. The values of liquid volume and expansivity obtained in this study are combined with high temperature densitometry determinations of the liquid volume of GeO2 by Sekiya et al. (1980) to yield a temperature-volume relation for GeO2 melt from 660 to 1400 °C. Liquid GeO2 shows a strongly temperature-dependent liquid molar expansivity, decreasing from 20.27 × 10?4 cm3 mol?1°C?1 to 1.97 × 10?4cm3 mol?1 °C?1 with increasing temperature. The coefficient of volume thermal expansion (α v ) decreases from 76.33 × 10?6 °C?1 to 2.46 × 10?6 °C?1 with increasing temperature. A qualitatively similar volume-temperature relationship, with α v decreasing from 335 × 10?6 °C?1 to 33 × 10?6 °C?1 with increasing temperature, has been observed previously in liquid B2O3. The determination of the glass transition temperature, liquid volume, liquid and glassy expansivities and heat capacities in this study, combined with compressibility data for glassy and liquid GeO2 from the literature (Soga 1969; Kurkjian et al. 1972; Scarfe et al. 1987) allows the calculation of the Prigogine-Defay ratio (Π), c p -c v and the thermal Grüneisen parameter (γ th) for GeO2. From available data on liquid SiO2 it is concluded that liquid GeO2 is not a good analog for the low pressure properties of liquid SiO2.  相似文献   

11.
The kinetics of zoned garnet porphyroblast growth is exemplified in a sample of garnet-staurolite-biotite schist from the northern Ladoga region. The diffusion-controlled porphyroblast growth was accompanied by a decrease in the kinetic coefficient during phase reactions. Even at insignificant (1–2°C) thermal overstepping, the leading role of diffusion as a factor that controls kinetics of porphyroblast growth in medium-grade metapelites is consistent with the parameters of metamorphic crystallization: T = 500–650°C, t = 1 Ma; D A1 app = 10?14 cm2/s, L = 0.2–0.6 cm, r = 1–3 mm, ΔC Al = 1.5 × 10?4–1.5 × 10?3 mol/cm3.  相似文献   

12.
Rats were raised on a variety of isotopically controlled diets comprising 20% C3, C4 or marine protein and C3 and/or C4 non-protein or energy (i.e. sucrose, starch and oil) macronutrients. Compound specific stable carbon isotope (δ13C) analysis was performed on the cholesterol isolated from the diet (n=7 ) and bone (n=15 ) of these animals and the values compared with bulk δ13C measurements of bone collagen and apatite. The dietary signals reflected by these three bone biochemical components were investigated using linear regression analysis. δ13C values of bone cholesterol were shown to reflect whole diet δ13C values, collagen to reflect mainly dietary protein values and apatite to reflect whole diet values. Further correlations between dietary protein-to-energy spacings (Δ13Cprot-engy = δ13Cprotein - δ13Cenergy) and whole diet-to-bone component fractionations (Δ13Cbcomp-wdiet = δ13Cbone component - δ13Cwhole diet) indicates that for hypothetical diets where protein δ13C values are equal to energy values, fractionations between whole diet and bone biochemical fractions are -3.3‰ for cholesterol, +5.4‰ for collagen and +9.5‰ for apatite. Moreover, the narrow range of variation observed in apatite-to-cholesterol spacings (Δ13Capat-bchol) suggests that cholesterol δ13C values can potentially also be used as an independent test for the isotopic integrity of apatite δ13C values. These insights into bone cholesterol, collagen and apatite dietary signals, diet-to-bone fractionations and bone component-to-bone component spacings provide the basis for more accurate interpretations of the dietary behaviour of archaeological populations and food webs when the δ13C analysis of bone is employed.  相似文献   

13.
The oxygen isotope fractionation accompanying the hydrothermal dolomitization of CaCO3 between 252 and 295°C has been investigated. Dolomitization (which occurs via the crystallization of one or more intermediate magnesian calcite phases) is characterised by a progressive lowering in δ8O, which smoothly correlates with the change in the Mg/(Mg + Ca) and the Sr(Mg + Ca) ratios and with the sequential phase formation. The data support the proposals of Katz and Matthews (1977) that (a) all reaction occurs by solution and reprecipitation, (b) intermediate phases and dolomite form sequentially and (c) the intermediate phases form within limited solution zones surrounding the dissolving precursor. Calculated volumes of the solution zone for the aragonite → low magnesian calcite transformation are within the range 3.7–6.7 × 10?5 liters (out of 5 × 10?3 liters, the volume of the bulk solution used in the present study), and agree well with those calculated from strontium and magnesium partitioning data. Dolomite precipitates in apparent isotopic equilibrium with the bulk solution. The temperature dependence of the fractionation is defined by the equation 1000 InαD-H2O = 3.06 × 106T?2 ? 3.24 Dolomite-water fractionations from this equation are significantly lower than those obtained by extrapolation of the Northrop And Clayton (1966) calibration. The reaction zone model can be applied to explain near zero dolomite-calcite oxygen isotope fractionations reported by Epsteinet al. (1964).  相似文献   

14.
Abstract ‘Peak’metamorphic carbon isotope fractionations between calcite and graphite (ΔCal–Gr) in marbles and calc-silicates from the Cucamonga granulite terrane (San Gabriel Mountains, California) range from 3.48 to 2.90%. The data are used to test three previously published calibrations of the calcite–graphite carbon isotope thermometer. An empirical calibration of the calcite–graphite carbon isotope thermometer gives temperatures of 700–750°C; a theoretical–experimental calibration of the system gives temperatures of 760°–870°C; an experimental calibration gives temperatures of 870–1300°C. Temperatures calculated using the empirical calibration are in agreement with those calculated from garnet-based cation exchange thermometry when uncertainty is considered. Temperatures calculated using the theoretical–experimental calibration overlap the upper range of cation exchange thermometry temperatures and range to 50°C higher. The experimental calibration yields temperatures from 50 to 480°C higher than those from cation exchange thermometry. Moreover, temperatures from the experimental calibration are also inconsistent with mineral and melt equilibria in the granulite phase assemblage. Despite the better agreement between cation exchange thermometry and the empirical calibration of the calcite–graphite system, temperatures calculated using the theoretical–experimental calibration may be real peak metamorphic temperatures. If retrograde diffusion partially reset garnet-based cation exchange thermometers by c. 50°C, then the cation exchange temperatures are consistent with those from the theoretical–empirical calibration. Thermometric evidence from biotite dehydration melting equilibria is consistent with either the empirical calibration if melting was fluid-present, or the theoretical–experimental calibration if melting was fluid-absent.  相似文献   

15.
Fourteen ureilites were analyzed for stable C isotopic composition using stepped combustion. The δ13C values over the temperature range 500 to 1000°C are fairly constant for any particular meteorite although there are differences between samples. The similarity in combustion temperatures of pure diamond (600–1000δC) and pure graphite (600–800°C) makes it difficult to ascertain the relative proportions of either component within each sample. However, the constant δ13C values observed over the range 500 to 1000°C strongly suggests that ureilite diamond and graphite have the same isotopic composition. This would seem to confirm that the diamond in ureilites formed from the graphite during a process, presumably an impact event, which did not fractionate C isotopes.There is a variation in C isotopic composition of graphite/diamond intergrowths among ureilites, which is not continuous—the samples fall into two groups, with δ13C values clustered around ?10%. and ?2%. PDB. These groups are also distinguishable on the basis of the Fe content of their olivines, which may reflect the existence of more than one ureilite parent body. The brecciated ureilite North Haig has a δ13C value of ?6.5%. and it is thus possible that this sample contains components from mixed parent materials.Nitrogen abundance and stable isotope measurements were made on five samples using stepped combustion analysis. Nitrogen concentrations range from 25 to 150 ppm and CN ratios are substantially less than for carbonaceous chondrites. Variation in N isotopic composition is wide and there is evidence of different ratios in diamond/graphite, silicate and metal.  相似文献   

16.
The solubility of quartz in water from 25° to 900°C at specific volume of the solvent ranging from about 1 to 10 and from 300° to 600°C at specific volume of the solvent ranging from about 10 to 100 is given by an empirically derived equation of the form: log m = A + B(log V) + C(log V)2 where m is the molal silica concentration, V is the specific volume of pure water, and A = ?4.66206 + 0.0034063T + 2179.7T?1 ? 1.1292 × 106T?2 + 1.3543 × 108T?3B = ?0.0014180T— 806.97T?1C = 3.9465 × 10?4T T is temperature in kelvins. The experimental data used in formulating the empirical relation ranged in pressure from 1 bar at 25°C to about 10,000 bars at 900°C, and the lowest pressure in the low-density steam region was about 30 bars. According to the above equation, the average difference in molality between 518 measured and calculated solubilities is ?0.016 m with a standard deviation of 0.089.  相似文献   

17.
High-resolution natural abundance stable carbon isotope analyses across annual growth rings in evergreen trees reveal a cyclic increase and decrease in the measured carbon isotopic composition (δ13C), but the causes of this pattern are poorly understood. We compiled new and published high-resolution δ13C data from across annual growth rings of 33 modern evergreen trees from 10 genera and 15 globally distributed sites to quantify the parameters that affect the observed δ13C pattern. Across a broad range of latitude, temperature, and precipitation regimes, we found that the average, measured seasonal change in δ13C (Δδ13Cmeas, ‰) within tree rings of evergreen species reflects changes in the carbon isotopic composition of atmospheric carbon dioxide (Δδ13CCO2) and changes in seasonal precipitation (ΔP) according to the following equation: Δδ13Cmeas = Δδ13CCO2 - 0.82(ΔP) + 0.73; R2 = 0.96. Seasonal changes in temperature, pCO2, and light levels were not found to significantly affect Δδ13Cmeas. We propose that this relationship can be used to quantify seasonal patterns in paleoprecipitation from intra-ring profiles of δ13C measured from non-permineralized, fossil wood.  相似文献   

18.
Subsolidus phase relations in the system CaO-Al2O3-SiO2 (CAS) were experimentally determined with tight reversals of several univariant curves and with 14 equilibration experiments containing the assemblage pyroxene + anorthite, where pyroxene is a binary solid solution of Ca-Tschermak (CaTs-CaAl2SiO6) and Ca-Eskola (CaEs-Ca0.5AlSi2O6) endmembers.Reversals were obtained on the following reactions (bar, °C): 3An = Gr + 2Ky + Q (P = 22T ? 700), 3An + Cor = Gr + 3Ky (P = 21.8T ? 950), 3CaTs= Gr + 2Cor(P = 55T ? 53900), and 6CaTs(1 ? x)CaEsx = 2(1 ? 2x)Gr + 4(1 ? 2x)Cor + 9xAn. Observed slopes indicate 9.8 J/mol · K of Al-Si disorder in Ca-Tschermak pyroxene and 5.3 J/mol·K of Al-Si disorder in anorthite, at 1300°C. It is suggested that Al-Si disorder in anorthite increases by 1.9 J/mol · K from 700°C to 1300°C.Compositions of CaTs-CaEs pyroxene in equilibrium with anorthite and PbO-rich liquid were experimentally determined at 1400–1430°C and 22.7–30.8 kbar. Microprobe measurements gave compositions which are consistent with an ideal pyroxene solution and the following parameters for the reaction 3An = 2CaTs + 2CaEs (J, bar, K): 2RTln(XCaTs · XCaEs) + 60200 + 86.4T ? (5.06 + 13 × 10?7P)P = 0, resulting in ΔH0j = ?39.8 kJ/mol and S0 = 461.8 J/mol · K for the Ca-Eskola endmember at 1300°C. The obtained properties of the Ca-Eskola component are necessary for thermobarometry based on pyroxene bearing assemblages containing plagioclase, quartz, or kyanite.  相似文献   

19.
We have studied trapping of radioactive 127Xe in three types of carbon: carbon black (lamp black  LB), pyrolyzed polyvinylidene chloride (PVDC), and pyrolyzed acridine (C13H9N). A total of 86 samples were exposed to Xe at T between 100 and 1000°C, for times between 5 min and 240 hours, at pxe ~ 5 × 10?7 atm. Excess gas phase and loosely sorbed Xe were pumped away and the remaining, tightly bound Xe was measured by γ-spectrometry.At 100°C,× >90% of the Xe desorbs within a few minutes' pumping but a small amount remains even after 4000 min. Distribution coefficients for this tightly bound Xe are ~1 × 10?2, 1 and 10 ccSTP/g atm for LB, acridine and PVDC carbons. The tightly bound Xe consists of two components. One occurs over the entire range 100–1000°C, becoming less abundant at high T; it appears to be physisorbed. The other occurs only at T > 500°C and is probably due to volume diffusion. The adsorbed component in LB has an apparent ΔH between ?2.3 and ?5.7 kcal/mole. The diffused component, which occurs in LB and possibly in acridine carbon, has an activation energy Q = 27 ± 8 kcal/mole and a diffusion coefficient D = 1.3 × 10?17 cm2/sec at 1000°C. These values are comparable to those found for other types of amorphous carbon (Morrisonet al., 1963; Nakai et al., 1960).The low-T component displays two paradoxical features: low ΔHads, in the range for Xe physisorbed on carbon, but exceedingly long adsorption or desorption times (~103 min at 100–400 or 1000°C). Although these long times seem to suggest a high energy process such as chemisorption, our results are best explained by a model that invokes physisorption within a labyrinth of micropores—of atomic dimensions—known to exist in amorphous carbons. The long adsorption/desorption times reflect either the long distances (~5 cm) Xe atoms must migrate by random walk to enter or leave the labyrinth, or the long times needed for Xe atoms to traverse tight spots or constricted pores that connect interior and exterior surfaces of the carbon (activated entry). Both variants of this model predict long equilibration times for the observed ΔHads of ?2 to ?6 kcal/mole. Apparently, xenon can be tightly trapped in carbon without resorting to high-energy bonding or to exotic mechanisms.These results suggest that “planetary” type noble gases in meteorites, located at or near grain surfaces of amorphous carbon, may be trapped by adsorption in micropores, whereas components such as CCFXe, which are uniformly distributed in their carrier phases, may be trapped by mechanisms such as volume diffusion or ion implantation.  相似文献   

20.
The heat capacities of lawsonite, margante, prehnite and zoisite have been measured from 5 to 350 K with an adiabatic-shield calorimeter and from 320 to 999.9 K with a differential-scanning calorimeter. At 298.15 K, their heat capacities, corrected to end-member compositions, are 66.35, 77.30, 79.13 and 83.84 cal K?1 mol?1; their entropies are 54.98, 63.01, 69.97 and 70.71 cal K?1 mol?1, respectively. Their high-temperature heat capacities are described by the following equations (in calories, K, mol): Lawsonite (298–600 K): Cp° = 66.28 + 55.95 × 10?3T ? 15.27 × 105T?2 Margarite (298–1000 K): Cp° = 101.83 + 24.17 × 10?3T ? 30.24 × 105T?2 Prehnite (298–800 K): Cp° = 97.04 + 29.99 × 10?3T ? 25.02 × 105T?2 Zoisite (298–730 K): Cp° = 98.92 + 36.36 × 10?3T ? 24.08 × 105T?2 Calculated Clapeyron slopes for univariant equilibria in the CaO-Al2O3-SiO2-H2O system compare well with experimental results in most cases. However, the reaction zoisite + quartz = anorthite + grossular + H2O and some reactions involving prehnite or margarite show disagreements between the experimentally determined and the calculated slopes which may possibly be due to disorder in experimental run products. A phase diagram, calculated from the measured thermodynamic values in conjunction with selected experimental results places strict limits on the stabilities of prehnite and assemblages such as prehnite + aragonite, grossular + lawsonite, grossular + quartz, zoisite + quartz, and zoisite + kyanite + quartz. The presence of this last assemblage in eclogites indicates that they were formed at moderate to high water pressure.  相似文献   

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