The dolomitization of CaCO₃: an experimental study at 252–295°C     

Amitai Katz  Alan Matthews 《Geochimica et cosmochimica acta》1977,41(2):297-308

The results of experiments on the hydrothermal dolomitization of calcite (between 252 and 295°C) and aragonite (at 252°C) by a 2 M CaCl₂-MgCl₂ aqueous solution are reported and discussed. Dolomitization of calcite proceeds via an intermediate high (ca. 35 mole %) magnesian calcite, whereas that of aragonite is carried out through the conversion of the reactant into a low (5.6 mole %) magnesian calcite which in turn transforms into a high (39.6 mole %) magnesian calcite. Both the intermediate phases and dolomite crystallize through a dissolution-precipitation reaction. The intermediate phases form under local equilibrium within a reaction zone surrounding the dissolving reactant grains. The volume of the reaction zone solution can be estimated from Sr²⁺ and Mg²⁺ partitioning equations. In the case of low magnesian calcite growing at the expense of aragonite at 252°C, the total volume of these zones is in the range of 2 × 10^?5 to 2 × 10^?4 1., out of 5 × 10^?3 1., the volume of the bulk solution.The apparent activation energies for the initial crystallization of high magnesian calcite and dolomite are 48 and 49 kcal/mole, respectively.Calcite transforms completely into dolomite within 100 hr at 252°C. The overall reaction time is reduced to approximately 4 hr at 295°C. The transformation of aragonite to dolomite at 252°C occurs within 24 hr. The nature of the reactant dictates the relative rates of crystallization of the intermediate phases and dolomite. With calcite as reactant, dolomite growth is faster than that of magnesian calcite; this situation is reversed when aragonite is dolomitized.Coprecipitation of Sr²⁺ with dolomite is independent of temperature (within analytical error) between 252 and 295°C. Its partitioning, with respect to calcium, between dolomite and solution results in distribution coefficients in the range of 2.31 × 10^?2 to 2.78 × 10^?2.  相似文献   

Experimental studies of oxygen and hydrogen isotope fractionations between precipitated brucite and water at low temperatures     

《Geochimica et cosmochimica acta》1999,63(13-14):2009-2018

Oxygen and hydrogen isotope fractionation factors between brucite and water were experimentally determined by chemical synthesis techniques at low temperatures of 15° to 120°C. MgCl₂, Mg3N₂, and MgO were used as reactants, respectively, to produce brucite in aqueous solutions. All of the synthesis products were identified by x-ray diffraction (XRD) for crystal structure and by scanning electron microscope (SEM) for morphology. It is observed that oxygen isotope fractionations between brucite and water are temperature dependent regardless of variations in aging time, the chemical composition, and pH value of solutions. Brucites derived from three different starting materials yielded consistent fractionations with water at the same temperatures. These suggest that oxygen isotope equilibrium has been achieved between the synthesized brucite and water, resulting in the fractionation equation of 10³lnα=1.56×10⁶/T²−14.1. When the present results for the brucite–water system are compared with those for systems of gibbsite–water and goethite–water, it suggests the following sequence of ¹⁸O-enrichment in the M−OH bonds of hydroxides: Al³⁺ − OH > Fe³⁺ − OH > Mg²⁺ − OH.Hydrogen isotope fractionations between brucite and water obtained by the different synthesis methods have also achieved equilibrium, resulting in the fractionation equation of 10³lnα=−4.88×10⁶/T²−22.5. Because of the pressure effect on hydrogen isotope fractionations between minerals and water, the present calibrations at atmospheric pressure are systematically lower than fractionations extrapolated from hydrothermal exchange experiments at high temperatures of 510° to 100°C and high pressures of 1060 to 1000 bar. Comparison of the present results with existing calibrations involving other low-temperature minerals suggests the following sequence of D-enrichment in hydroxyl-bearing minerals: Al³⁺ − OH > Mg²⁺ − OH > Fe³⁺ − OH.  相似文献   

Magnesium stable isotope fractionation in marine biogenic calcite and aragonite   总被引：2，自引：0，他引：2  

F. Wombacher  A. Eisenhauer  N. Gussone  M. Regenberg  W.-Chr. Dullo 《Geochimica et cosmochimica acta》2011,75(19):5797-253

This survey of magnesium stable isotope compositions in marine biogenic aragonite and calcite includes samples from corals, sclerosponges, benthic porcelaneous and planktonic perforate foraminifera, coccolith oozes, red algae, and an echinoid and brachiopod test. The analyses were carried out using MC-ICP-MS with an external repeatability of ±0.22‰ (2SD for δ²⁶Mg; n = 37), obtained from a coral reference sample (JCp-1).Magnesium isotope fractionation in calcitic corals and sclerosponges agrees with published data for calcitic speleothems with an average Δ²⁶Mg_{calcite-seawater} = −2.6 ± 0.3‰ that appears to be weakly related to temperature. With one exception (Vaceletia spp.), aragonitic corals and sclerosponges also display uniform Mg isotope fractionations relative to seawater with Δ²⁶Mg_{biogenic aragonite-seawater} = −0.9 ± 0.2.Magnesium isotopes in high-Mg calcites from red algae, echinoids and perhaps some porcelaneous foraminifera as well as in all low-Mg calcites (perforate foraminifera, coccoliths and brachiopods) display significant biological influences. For planktonic foraminifera, the Mg isotope data is consistent with the fixation of Mg by organic material under equilibrium conditions, but appears to be inconsistent with Mg removal from vacuoles. Our preferred model, however, suggests that planktonic foraminifera synthesize biomolecules that increase the energetic barrier for Mg incorporation. In this model, the need to remove large quantities of Mg from vacuole solutions is avoided. For the high-Mg calcites from echinoids, the precipitation of amorphous calcium carbonate may be responsible for their weaker Mg isotope fractionation.Disregarding superimposed biological effects, it appears that cation light isotope enrichments in CaCO₃ principally result from a chemical kinetic isotope effect, related to the incorporation of cations at kink sites. In this model, the systematics of cation isotope fractionations in CaCO₃ relate to the activation energy required for cation incorporation, which probably reflects the dehydration of the cation and the crystal surface and bond formation at the incorporation site. This kinetic incorporation model predicts (i) no intrinsic dependence on growth rate, unless significant back reaction upon slow growth reduces the isotope fractionation towards that characteristic for equilibrium isotope partitioning (this may be observed for Ca isotopes in calcites), (ii) a small decrease of isotope fractionation with increasing temperature that may be amplified if higher temperatures promote back reaction and (iii) a sensitivity to changes in the activation barrier caused by additives such as anions or biomolecules or by the initial formation of amorphous CaCO₃.  相似文献   

Oxygen isotope salt effects at high pressure and high temperature and the calibration of oxygen isotope geothermometers     

Guixing Hu  Robert N. Clayton 《Geochimica et cosmochimica acta》2003,67(17):3227-3246

The influence of NaCl, CaCl₂, and dissolved minerals on the oxygen isotope fractionation in mineral-water systems at high pressure and high temperature was studied experimentally. The salt effects of NaCl (up to 37 molal) and 5-molal CaCl₂ on the oxygen isotope fractionation between quartz and water and between calcite and water were measured at 5 and 15 kbar at temperatures from 300 to 750°C. CaCl₂ has a larger influence than NaCl on the isotopic fractionation between quartz and water. Although NaCl systematically changes the isotopic fractionation between quartz and water, it has no influence on the isotopic fractionation between calcite and water. This difference in the apparent oxygen isotope salt effects of NaCl must relate to the use of different minerals as reference phases. The term oxygen isotope salt effect is expanded here to encompass the effects of dissolved minerals on the fractionations between minerals and aqueous fluids. The oxygen isotope salt effects of dissolved quartz, calcite, and phlogopite at 15 kbar and 750°C were measured in the three-phase systems quartz-calcite-water and phlogopite-calcite-water. Under these conditions, the oxygen isotope salt effects of the three dissolved minerals range from ∼0.7 to 2.1‰. In both three-phase hydrothermal systems, the equilibrium fractionation factors between the pairs of minerals are the same as those obtained by anhydrous direct exchange between each pair of minerals, proving that the use of carbonate as exchange medium provides correct isotopic fractionations for a mineral pair.When the oxygen isotope salt effects of two minerals are different, the use of water as an indirect exchange medium will give erroneous fractionations between the two minerals. The isotope salt effect of a dissolved mineral is also the main reason for the observation that the experimentally calibrated oxygen isotope fractionations between a mineral and water are systematically 1.5 to 2‰ more positive than the results of theoretical calculations. Dissolved minerals greatly affect the isotopic fractionation in mineral-water systems at high pressure and high temperature. If the presence of a solute changes the solubility of a mineral, the real oxygen isotope salt effect of the solute at high pressure and high temperature cannot be correctly derived by using the mineral as reference phase.  相似文献   

The geochemistry of the stable isotopes of silicon   总被引：1，自引：0，他引：1  

C.B Douthitt 《Geochimica et cosmochimica acta》1982,46(8):1449-1458

One hundred thirty two new measurements of the relative abundances of the stable isotopes of silicon in terrestrial materials are presented. The total variation of ^δ30Si found is 6.2%., centered on the mean of terrestrial mafic and ultramafic igneous rocks, δ³⁰Si = ?0.4%.. Igneous rocks show limited (1.1%.) variation; coexisting minerals exhibit small, systematic silicon isotopic fractionations that are roughly $\text{1}\text{3}$ the magnitude of concomitant oxygen isotopic fractionations at 1150°C. In both igneous minerals and rocks, δ³⁰Si shows a positive correlation with silicon content, as does δ¹⁸O. Opal from both sponge spicules and sinters is light, with $\text{}\text{?}\text{gd}{}^{30}\text{Si}\text{= ?2.3}$ and ?1.4%., respectively. Large ^δ30Si values of both positive and negative sign are reported for the first time from clay minerals (?2.3 to +1.8%.), opaline phytoliths (?1.4 to +2.8%.), and authigenic quartz (+ 1.4%.). All highly fractionated samples were precipitated from solution at low temperatures; however, aqueous silicon is not measurably fractionated relative to quartz at equilibrium. A kinetic isotope fractionation of ≈3.5%. is postulated to occur during the low temperature precipitation of opal and, possibly, poorly ordered phyllosilicates, with the silicate phase being enriched in ²⁸Si. This fractionation, coupled with a Rayleigh precipitation model, is capable of explaining most non-magmatic δ³⁰Si variations. Chert ^δ30Si values are largely inherited, but the primary opal ^δ30Si values can be modified by isotopic equilibration of silicate silicon and dissolved silicon during the transformation of opal into quartz.  相似文献   

Determination of the ⁸⁷Rb decay constant     

D.W. Davis  J. Gray  G.l. Gumming  H. Baadsgaard 《Geochimica et cosmochimica acta》1977,41(12):1745-1749

The decay constant ⁸⁷Rb has been redetermined by measuring the amount of radiogenic ⁸⁷Sr produced over a period of 19 years, in 20 g samples of purified RbClO₄, using isotope dilution techniques. The rubidium sample was spiked with ⁸⁴Sr and the nanogram quantities of strontium separated by coprecipitation with Ba(NO₃)₂. Analyses were carried out on a 25cm, 90° sector mass spectrometer equipped with a Spiraltron electron multiplier. Measurement of three independent ratios permitted continuous monitoring of the ion beam fractionation. The average of nine determinations gives a value for the decay constant of $\text{1.419(±0.012) × 10}{}^{\mathrm{?11}}\text{yr}{}^{\mathrm{?1}}\text{(2σ)}$. [$\text{τ}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{= 4.89(±0.04) × 10}{}^{10}\text{yr}$.]  相似文献   

Oxygen and sulfur isotope equilibria in the BaSO4HSO4−H2O system from 110 to 350°C and applications     

Minoru Kusakabe  Brian W. Robinson 《Geochimica et cosmochimica acta》1977,41(8):1033-1040

Oxygen isotope exchange between BaSO₄ and H₂O from 110 to 350°C was studied using 1 m H₂SO₄-1 m NaCl and 1 m NaCl solutions to recrystallize the barite. The slow exchange rate (only 7% exchange after 1 yr at 110°C and 91% exchange after 22 days at 350°C in 1 m NaCl solution) prompted the use of the partial equilibrium technique. However, runs at 300 and 350°C were checked by complete exchange experiments. The temperature calibration curve for the isotope exchange is calculated giving most weight to the high temperature runs where the partial equilibrium technique can be tested. Oxygen isotope fractionation factors (α) in 1 m NaCl solution (110–350°C), assuming a value of 1.0407 for α_CO2H2O at 25°C, are: .These data, when corrected for ion hydration effects in solution (Truesdell, 1974), give the fractionation factors in pure water: .In the 1 m H₂SO₄-1 m NaCl runs, sulfur isotope fractionation between HSO^?₄ and BaSO₄ is less than the detection limit of 0.4%. A barite-sulfide geothermometer is obtained by combining HSO^?₄H₂S and sulfide-H₂S calibration data.Barite in the Derbyshire ore field, U.K., appears to have precipitated in isotopic equilibrium with water and sulfur in the ore fluid at temperatures less than 150°C. At the Tui Mine, New Zealand, the barite-water geothermometer indicates temperatures of late stage mineralization in the range 100–200°C. A temperature of 350 ± 20°C is obtained from the barite-pyrite geothermometer at the Yauricocha copper deposit, Peru, and oxygen isotope analyses of the barite are consistent with a magmatic origin for the ore fluids.  相似文献   

Effects of cation substitutions in garnet and pyroxene on equilibrium oxygen isotope fractionations   总被引：3，自引：0，他引：3  

M. J. KOHN  & J. W. VALLEY 《Journal of Metamorphic Geology》1998,16(5):625-639

High-grade metamorphic rocks were used to explore oxygen isotope fractionations between pyroxene and garnet, and to investigate the effects on fractionation factors of the cation substitutions Fe³⁺Al_?1 and Ca(Fe,Mg)_?1. Recrystallized, granulite facies (725 °C) wollastonite ores from the northern Adirondack highlands contain essentially only the minerals clinopyroxene (a Di–Hd solid solution)+garnet (a Grs–Adr solid solution)±wollastonite, and exhibit a systematic dependence of measured fractionations on the Fe³⁺ content of calcic garnet: Δ(Cpx–CaGrt)=(0.14±0.12)+(0.78±0.20)X_Adr and Δ(Wo–CaGrt)=(0.15±0.22)+(0.57±0.33)X_Adr. In eclogites formed at T ≤650 °C, measured compositions of Ca-poor garnet and omphacite combined with experimental data indicate that Ca-poor, Fe-rich garnet is enriched in ¹⁸O compared to both diopside and grossular: extrapolating to 1000 K, Δ(Alm–Di)≈c. 0.2 and Δ(Alm–Grs)≈c. 0.5. Orthopyroxene and clinopyroxene from Gore Mountain, New York, show a constant fractionation that is independent of rock type, as expected if they have the same closure temperature. These data imply Δ(Opx-Cpx)≈c. 0.7 at 1000 K. Measured fractionations among Ca-poor garnet, orthopyroxene, clinopyroxene and hornblende in the Gore Mountain rocks further indicate an ¹⁸O enrichment in Ca-poor garnet over Grs (≈c. 0.5 at 1000 K). The new measurements are indistinguishable from expected equilibrium values based on experiments for the minerals enstatite, diopside, grossular, wollastonite and feldspar, but consistently indicate a significant isotope effect for the simple octahedral cation substitutions Fe³⁺Al_?1 (Grs vs. Adr) and Ca(Fe,Mg)_?1 (Ca-poor garnet vs. Grs; Opx vs. Cpx). Neither cation substitution has been directly investigated for its effect on ¹⁸O/¹⁶O fractionation with experiments in silicates. Chemical characterization of minerals is required prior to petrological interpretation of oxygen isotope trends.  相似文献   

An experimental and theoretical determination of oxygen isotope fractionation in the system magnetite-H₂O from 300 to 800°C     

David R. Cole  Juske Horita  John W. Valley  Dorothy W. Coffey 《Geochimica et cosmochimica acta》2004,68(17):3569-3585

Oxygen isotope fractionations have been determined between magnetite and water from 300 to 800°C and pressures between 10 and 215MPa. We selected three reaction pathways to investigate fractionation: (a) reaction of fine-grained magnetite with dilute aqueous NaCl solutions; (b) reduction of fine-grained hematite through reaction with dilute acetic acid; and (c) oxidation of fine iron power in either pure water or dilute NaCl solutions. Effective use of acetic acid was limited to temperatures up to about 400°C, whereas oxide-solution isotope exchange experiments were conducted at all temperatures. Equilibrium ¹⁸O/¹⁶O fractionation factors were calculated from the oxide-water experiments by means of the partial isotope exchange method, where generally four isotopically different waters were used at any given temperature. Each run product was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and on a limited basis, high-resolution transmission electron microscopy (HRTEM) and Mössbauer spectroscopy. Results from the microscopic examinations indicate the formation of well-crystallized octahedra and dodecahedra of magnetite where the extent of crystallization, grain size, and grain habit depend on the initial starting material, P, T, solution composition, and duration of the run.The greatest amount of oxygen isotope exchange (∼90% or greater) was observed in experiments where magnetite either recrystallized in the presence of 0.5 m NaCl from 500 to 800°C or formed from hematite reacted with 0.5 m acetic acid at 300, 350 and 400°C. Fractionation factors (10³ ln α_mt-H2O) determined from these partial exchange experiments exhibit a steep decrease (to more negative values) with decreasing temperature down to about 500°C, followed by shallower slope. A least-squares regression model of these partial exchange data, which accounts for analytical errors and errors generated by mass balance calculations, gives the following expression for fractionation that exhibits no minimum: 1000lnα_lmt-lw=−8.984(±0.3803)x+3.302(±0.377)x²—0.426(±0.092)x³ with an R² = 0.99 for 300 ≤ T≤ 800°C (x = 10⁶/T²). The Fe oxidation results also exhibit this type of temperature dependence but shifted to slightly more negative 10³ ln α values; there is the suggestion that a kinetic isotope effect may contribute to these fractionations. A theoretical assessment of oxygen isotope fractionation using β-factors derived from heat capacity and Mössbauer temperature (second-order Doppler) shift measurements combined with known β-factors for pure water yield fractionations that are somewhat more negative compared to those determined experimentally. This deviation may be due to the combined solute effects of dissolved magnetite plus NaCl (aq), as well as an underestimation of β_mt at low temperatures. The new magnetite-water experimental fractionations agree reasonably well with results reported from other experimental studies for temperatures ≥ 500°C, but differ significantly with estimates based on quasi-theoretical and empirical approaches. Calcite-magnetite and quartz-magnetite fractionation factors estimated from the combination of magnetite β’s calculated in this study with those for calcite and quartz reported by Clayton and Kieffer (1991) agree very closely with experimentally determined mineral-pair fractionations.  相似文献   

Isotopic fractionations associated with phosphoric acid digestion of carbonate minerals: Insights from first-principles theoretical modeling and clumped isotope measurements   总被引：2，自引：0，他引：2  

Weifu Guo  Jed L. Mosenfelder  John M. Eiler 《Geochimica et cosmochimica acta》2009,73(24):7203-7131

Phosphoric acid digestion has been used for oxygen- and carbon-isotope analysis of carbonate minerals since 1950, and was recently established as a method for carbonate ‘clumped isotope’ analysis. The CO₂ recovered from this reaction has an oxygen isotope composition substantially different from reactant carbonate, by an amount that varies with temperature of reaction and carbonate chemistry. Here, we present a theoretical model of the kinetic isotope effects associated with phosphoric acid digestion of carbonates, based on structural arguments that the key step in the reaction is disproportionation of H₂CO₃ reaction intermediary. We test that model against previous experimental constraints on the magnitudes and temperature dependences of these oxygen isotope fractionations, and against new experimental determinations of the fractionation of ¹³C-¹⁸O-containing isotopologues (‘clumped’ isotopic species). Our model predicts that the isotope fractionations associated with phosphoric acid digestion of carbonates at 25 °C are 10.72‰, 0.220‰, 0.137‰, 0.593‰ for, respectively, ¹⁸O/¹⁶O ratios (1000 lnα^∗) and three indices that measure proportions of multiply-substituted isotopologues . We also predict that oxygen isotope fractionations follow the mass dependence exponent, λ of 0.5281 (where ). These predictions compare favorably to independent experimental constraints for phosphoric acid digestion of calcite, including our new data for fractionations of ¹³C-¹⁸O bonds (the measured change in Δ₄₇ = 0.23‰) during phosphoric acid digestion of calcite at 25 °C.We have also attempted to evaluate the effect of carbonate cation compositions on phosphoric acid digestion fractionations using cluster models in which disproportionating H₂CO₃ interacts with adjacent cations. These models underestimate the magnitude of isotope fractionations and so must be regarded as unsucsessful, but do reproduce the general trend of variations and temperature dependences of oxygen isotope acid digestion fractionations among different carbonate minerals. We suggest these results present a useful starting point for future, more sophisticated models of the reacting carbonate/acid interface. Examinations of these theoretical predictions and available experimental data suggest cation radius is the most important factor governing the variations of isotope fractionation among different carbonate minerals. We predict a negative correlation between acid digestion fractionation of oxygen isotopes and of ¹³C-¹⁸O doubly-substituted isotopologues, and use this relationship to estimate the acid digestion fractionation of for different carbonate minerals. Combined with previous theoretical evaluations of ¹³C-¹⁸O clumping effects in carbonate minerals, this enables us to predict the temperature calibration relationship for different carbonate clumped isotope thermometers (witherite, calcite, aragonite, dolomite and magnesite), and to compare these predictions with available experimental determinations. The success of our models in capturing several of the features of isotope fractionation during acid digestion supports our hypothesis that phosphoric acid digestion of carbonate minerals involves disproportionation of transition state structures containing H₂CO₃.  相似文献   

Sorption of noble gases by solids,with reference to meteorites. I. Magnetite and carbon     

Jongmann Yang  Roy S. Lewis  Edward Anders 《Geochimica et cosmochimica acta》1982,46(6):841-860

To simulate trapping of meteoritic noble gases by solids, 18 samples of Fe₃O₄ were synthesized in a noble gas atmosphere at 350–720 K by the reactions: 3Fe + 4H₂O → Fe₃O₄ + 4H₂ (Ne, Ar, Kr, Xe) 3Fe + 4CO → Fe₃O₃ + 4C + carbides (Xe only) Phases were separated by selective solvents (HgCl₂, HCl). Noble gas contents were analyzed by mass spectrometry, or, in runs where 36 d Xe¹²⁷ tracer was used, by γ-counting. Surface areas, as measured by the BET method, ranged from 1 to 400 m²/g. Isotopic fractionations were below the detection limit of 0.5%/m.u.Sorption of Xe on Fe₃O₄ and C obeys Henry's Law between $\text{1 × 10}{}^{\mathrm{?8}}$ and $\text{4 × 10}{}^{\mathrm{?5}}$ atm, but shows only a slight temperature dependence between 650 and 720 K ($\text{ΔH}{}_{\mathrm{sol}}\text{= ?4 ± 2}\text{kcal/mole}$). The mean distribution coefficient K_Xe is $\text{0.28 ± 0.09}$ cc STP/g atm for Fe₃O₄ and only a factor of $\text{1.2 ± 0.4}$ greater for C; such similarity for two cogenetic phases was predicted by Lewis et al. (1977). Stepped heating and etching experiments show that 20–50% of the total Xe is physically adsorbed and about 20% is trapped in the solid. The rest is chemisorbed with $\text{ΔH}{}_{\mathrm{s}}\text{? ?13}\text{kcal/mole}$. The desorption or exchange half-time for the last two components is >10² yr at room temperature.Etching experiments showed a possible analogy to “Phase $\text{Q}$” in meteorites. A typical carbon + carbide sample, when etched with HNO₃, lost 47% of its Xe but only 0.9% of its mass, corresponding to a ~0.6 Å layer. Though this etchable, surficial gas component was more thermolabile than $\text{Q}$ (release $\text{T}$ below 1000°C, compared to 1200–1600°C), another experiment shows that the proportion of chemisorbed Xe increases upon moderate heating (1 hr at 450°C). Apparently adsorbed gases can become “fixed” to the crystal, by processes not involving volume diffusion (recrystallization, chemical reaction, migration to traps, etc.). Such mechanisms may have acted in the solar nebula, to strengthen the binding of adsorbed gases.Adsorbed atmospheric noble gases are present in all samples, and dominate whenever the noble gas partial pressure in the atmosphere is greater than that in the synthesis. Many of the results of Lancet and Anders (1973) seem to have been dominated by such an atmospheric component; others are suspect for other reasons, whereas still others seem reliable. When the doubtful samples of Lancet and Anders are eliminated or corrected, the fractionation pattern—as in our samples—no longer peaks at Ar, but rises monotonically from Ne to Xe. No clear evidence remains for the strong temperature dependence claimed by these authors.  相似文献   

Chemistry and isotope ratios of sulfur in basalts and volcanic gases at Kilauea volcano,Hawaii     

Hitoshi Sakai  Thomas J. Casadevall  James G. Moore 《Geochimica et cosmochimica acta》1982,46(5):729-738

Eighteen basalts and some volcanic gases from the submarine and subaerial parts of Kilauea volcano were analyzed for the concentration and isotope ratios of sulfur. By means of a newly developed technique, sulfide and sulfate sulfur in the basalts were separately but simultaneously determined. The submarine basalt has 700 ± 100 ppm total sulfur with δ³⁴S_Σs of $\text{0.7 ± 0.1 ‰}$. The sulfate/sulfide molar ratio ranges from 0.15 to 0.56 and the fractionation factor between sulfate and sulfide is $\text{+7.5 ± 1.5‰}$. On the other hand, the concentration and δ³⁴S_Σs values of the total sulfur in the subaerial basalt are reduced to 150 ± 50 ppm and $\text{?0.8 ± 0.2‰}$, respectively. The sulfate to sulfide ratio and the fractionation factor between them are also smaller, 0.01 to 0.25 and +3.0‰, respectively. Chemical and isotopic evidence strongly suggests that sulfate and sulfide in the submarine basalt are in chemical and isotopic equilibria with each other at magmatic conditions. Their relative abundance and the isotope fractionation factors may be used to estimate the $\text{?o}{}_2$ and temperature of these basalts at the time of their extrusion onto the sea floor. The observed change in sulfur chemistry and isotopic ratios from the submarine to subaerial basalts can be interpreted as degassing of the SO₂ from basalt thereby depleting sulfate and ³⁴S in basalt.The volcanic sulfur gases, predominantly SO₂, from the 1971 and 1974 fissures in Kilauea Crater have δ³⁴S values of 0.8 to 0.9%., slightly heavier than the total sulfur in the submarine basalts and definitely heavier than the subaerial basalts, in accord with the above model. However, the δ³⁴S value of sulfur gases (largely SO₂) from Sulfur Bank is 8.0%., implying a secondary origin of the sulfur. The δ³⁴S values of native sulfur deposits at various sites of Kilauea and Mauna Loa volcanos, sulfate ions of four deep wells and hydrogen sulfide from a geothermal well along the east rift zone are also reported. The high δ³⁴S values (+5 to +6%._o) found for the hydrogen sulfide might be an indication of hot basaltseawater reaction beneath the east rift zone.  相似文献   

Carbon isotopic thermometry calibrated by dolomite-calcite solvus temperatures   总被引：1，自引：0，他引：1  

Hideki Wada  Kazuhiro Suzuki 《Geochimica et cosmochimica acta》1983,47(4):697-706

The temperature dependence of carbon isotopic fractionations between calcite and graphite, and between dolomite and graphite are calibrated by the calcite-dolomite solvus geothermometry using marbles collected from the contact metamorphic aureole in the Kasuga area, central Japan. The carbon isotopic fractionations (Δ¹³C_Cc-Gr and Δ¹³C_DoGr) systematically decrease with increasing metamorphic temperature. The concordant relationships between the fractionations and solvus temperatures are approximately linear with T^?2 over the temperature range. 400° to 680°C: Δ¹³C_CcGr (%.) = 5.6 × 10⁶ × T^?2 (K) ? 2.4 Δ¹³C_DoGr (%.) = 5.9 × 10⁶ × T^?2 (K) ? 1.9 These systematic relationships between fractionation and temperature suggest that carbon isotopic equilibria between carbonates and graphite were attained in many cases. The equation for the calcite-graphite system has a slope steeper than Bottinga's (1969) results. It is, however, in good agreement with that of Valley and O'Neil (1981) in the temperature range from 600° to 800°C.Because of the relatively high sensitivity to temperature, these isotopic geothermometers are useful for determining the temperatures in moderate- to high-grade metamorphosed carbonate rocks.  相似文献   

13C12C exchange between calcite and graphite: A possible thermometer in Grenville marbles     

J.W Valley  James R O&#x;Neil 《Geochimica et cosmochimica acta》1981,45(3):411-419

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   

Ca isotopes in refractory inclusions     

Franz R Niederer  D.A Papanastassiou 《Geochimica et cosmochimica acta》1984,48(6):1279-1293

We report measurements of the absolute isotope abundance of Ca in Ca-Al-rich inclusions from the Allende and Leoville meteorites. Improved high precision measurements are reported also for ⁴⁶Ca. We find that nonlinear isotope effects in Ca are extremely rare in these inclusions. The absence of nonlinear effects in Ca, except for the effects in FUN inclusions, is in sharp contrast to the endemic effects in Ti. One fine-grained inclusion shows an excess of ⁴⁶Ca of (7 ± 1)%., which is consistent with addition of only ⁴⁶Ca or of an exotic (1) component with ⁴⁶Ca¹ ~ ⁴⁸Ca¹. FUN inclusion EK-1-4-1 shows a small ⁴⁶Ca excess of (3.3 ± 1.0)%.; this confirms that the exotic Ca components in EK-1-4-1 were even more deficient in ⁴⁶Ca relative to ⁴⁸Ca than is the case for normal Ca. The Ca in the Ca-Al-rich inclusions shows mass dependent isotope fractionation effects (as deduced from the absolute ${}^{40}\text{Ca}{}^{44}\text{Ca}$) which have a range from ?3.8 to +6.7%. per mass unit difference. This range is a factor of 20 wider than the range previously established for bulk meteorites and for terrestrial and lunar samples. Ca and Mg isotope fractionation effects in the Ca-Al-rich inclusions are common and attributed to kinetic isotope effects which imply the production of the inclusions by complex sequences of condensation, vaporization and recondensation. A correlation was found between Ca and Mg isotope fractionation effects and inclusion type. A possible correlation between isotope fractionation and rare earth element abundance patterns is discussed.  相似文献   

Oxygen isotope fractionation between zoisite and water     

Alan Matthews  Julian R. Goldsmith  Robert N. Clayton 《Geochimica et cosmochimica acta》1983,47(3):645-654

Oxygen isotope fractionations between zoisite and water have been studied at 400–700°C, PH₂O = 13.4 kbar, using the three-isotope method described by Matsuhisaet al. (1978) and Matthewset al. (1983a). The zoisite-waier exchange reaction takes place extremely slowly and consequently direct-exchange calibration of equilibrium ${}^{18}\text{O}{}^{16}\text{O}$ fractionation factors was possible only at 600 and 700°C. Fractionation factors at 400–600°C were determined from samples hydrothermally crystallized from a glass of the anhydrous zoisite composition. At 600°C, both exchange procedures gave identical fractionations within experimental error. Scanning electron microscope studies showed that the zoisite-water exchange reaction occurs largely by solution-precipitation mass-transfer mechanisms. The slow kinetics of zoisite-water exchange may be typical of hydrous silicates, since additional experiments on tremolite-water and chlorite-water exchange also showed very low rates. When the zoisite-water fractionation factors determined in this study are combined with the quartz and albite-water data of Matsuhisaet al. (1979) and the calcite-water data of O'Nellet al. (1969), mineral-pair fractionations are obtained for which the coefficients “A” in the equation 1000 In α = A × 10⁶T^?2 are: