Noble gases in E-chondrites     

Jane Crabb  Edward Anders 《Geochimica et cosmochimica acta》1981,45(12):2443-2464

Noble gas data are reported for 12 E-chondrites. Combined with literature data, they show that K-Ar ages are >4 Æ for 14 out of 18 meteorites, yet U, Th-He ages are often shorter, perhaps due to late, mild reheating. Cosmic-ray exposure ages differ systematically between types 4 and 6, with E4's mostly below 16 Myr and E6's above 30 Myr. This may mean that the E-chondrite parent body contains predominantly a single petrologic type on the (~ 1 km) scale of individual impacts, in contrast to the more thoroughly mixed parent bodies of the ordinary chondrites.The heavy noble gases consist of at least two primordial components: the usual planetary component (${}^{36}\text{Ar}{}^{132}\text{Xe}\text{~ 80}$) and a less fractionated, ‘subsolar’ component ($\text{2700 ≤}{}^{36}\text{Ar}{}^{132}\text{Xe}\text{≤ 3800}$). The latter is found in highest concentration in the E4 chondrite South Oman (³⁶Ar = 760 × 10^?8cc/g, ${}^{36}\text{Ar}{}^{132}\text{Xe}\text{= 2700}$). The isotopic compositions of both components are similar to typical planetary values, indicating that some factor other than mass controlled the noble gas elemental ratios. The heavy Xe isotopes occasionally show some of the lowest ${}^{134}\text{Xe}{}^{132}\text{Xe}$ and ${}^{136}\text{Xe}{}^{132}\text{Xe}$ ratios measured in bulk chondrites, suggestive of nearly fission-free Xe (e.g. ${}^{136}\text{Xe}{}^{132}\text{Xe}\text{= 0.3095 ± 0.0020}$). Amounts of planetary gas in E4 E6 chondrites fall in the range for ordinary chondrites of types 4–6, but, in contrast to the ordinary chondrites. fail to correlate with petrologic type or volatile trace element contents. Another unusual feature of E-chondrites is that primordial Ne is present even in most 4's and 5's (²⁰Ne_p ~ 1 to 7 × 10^?8cc/g). with an isotopic composition consistent with planetary Ne.Analyses of mineral separates show that the planetary gases are concentrated in an HF- and HCl-insoluble mineral similar to phase Q, the poorly characterized, HNO₃-soluble carrier of primordial gases in carbonaceous and ordinary chondrites. The subsolar gases, on the other hand, are located in an HCl- and HNO₃-resistant phase, possibly enstatite or a minor phase included in enstatite. Much of the ¹²⁹Xe_r (50% for E4's, > 70% for E6's) is in HCl-resistant but HF-soluble sites, suggestive of a silicate.A similar subsolar component may be responsible for the high ${}^{36}\text{Ar}{}^{132}\text{Xe}$ ratios of some C3's, unequilibrated ordinary chondrites, and the unique aubrite Shallowater. The planet Venus also has a high $\text{Ar}\text{Kr}$ ratio, well above the planetary range, and hence may have acquired its noble gases from an E-chondrite-like material, similar to South Oman.  相似文献   

Isotopic anomalies of noble gases in meteorites and their origins—VII. C3V carbonaceous chondrites     

Jun-Ichi Matsuda  Roy S. Lewis  Hiroshi Takahashi  Edward Anders 《Geochimica et cosmochimica acta》1980,44(11):1861-1874

Noble gases were measured in bulk samples of the C3V chondrites Grosnaja, Vigarano, and Leoville, and in HF,HCl-insoluble residues before and after etching with HNO₃. The residues were characterized by INAA and SEM. Gas components were determined, directly or by subtraction, for the following fractions: HF,HCl-solubles (?98% of the meteorite), ‘sphase Q’, a poorly characterized trace mineral that is insoluble in HCl-HF but soluble in HNO₃, and an insoluble residue, consisting of ferrichromite, carbonaceous matter, and spinel.Bulk meteorites show some correlation of the noble-gas pattern with McSween's subclasses: two ‘oxidized’ C3V's—Allende (LEWIS et al, 1975) and Grosnaja— have lower Ar/Xe but higher Ne/Xe ratios than the ‘reduced’ C3V's—Vigarano and Leoville—which are transitional to LL3's and C3O chondrites in both respects. An HCl-soluble mineral of high Ar/Xr ratio seems to be responsible. In other respects, the 3 C3V's of this study resemble Allende, with only moderate differences. Phase Q contains most of the Ar, Kr, Xe, but only small amounts of Ne; the etched residues contain planetary Ne ($\text{Ne}{}^{20}\text{Ne}{}^{22}\text{? 8.5}$) and the controversial CCFXe component, enriched in the heavy Xe isotopes ($\text{Xe136}\text{Xe132 ? 0.4–0.5}$). The CCFXe is accompanied by an ‘L-Xe’ component that is enriched in the light Xe isotopes. The proportion of the two is virtually constant in C3V's. as in all other C-chondrites. in contrast to the ~ 2-fold variation in ordinary chondrites.C3V's have systematically higher $\text{Xe}{}^{136}\text{Xe}{}^{132}$ ratios, and hence higher ratios of CCFXe to planetary Xe, than do other chondrite classes. This may reflect some peculiarity in their formation conditions, favoring uptake of CCFXe.  相似文献   

Isotopic anomalies of noble gases in meteorites and their origins—IV. C3 (Ornans) carbonaceous chondrites     

Leo Alaerts  Roy S Lewis  Edward Anders 《Geochimica et cosmochimica acta》1979,43(9):1421-1432

The C3O chondrites Kainsaz, Lancé and Ornans were studied by an acid dissolution technique, to characterize the noble-gas components in 3 mineral fractions: HF, HCl-solubles (99% of the meteorite), chromite and carbon (0.3–0.9%), and ‘phase Q’, a poorly characterized trace mineral (0.05–0.4%) containing most of the Ar, Kr, Xe. For all fractions, gas contents decline in the order Kainsaz > Lancé > Ornans; this trend parallels volatile contents but not heterogeneity of olivine composition or degree of metamorphism and seems to reflect progressively higher condensation temperatures from the solar nebula.Solubles contain nearly unfractionated Xe, and show ${}^{136}\text{Ar}{}^{132}\text{Xe}$ ratios up to 850. Hence the high $\text{Ar}\text{Xe}$ ratios (200–400) of bulk C3O chondrites must be due to an HF-soluble mineral (possibly magnetite). Phase Q contains ordinary planetary gases and a Ne component of ${}^{20}\text{Ne}{}^{22}\text{Ne}\text{= 10.3 ± 0.4.}$Chromite and carbon contain Ne of ${}^{20}\text{Ne}{}^{22}\text{Ne}\text{= 8.6 ± 0.1}$ and ‘CCF’ xenon (a peculiar component of possibly fissiogenic origin, enriched in the heavy isotopes but accompanied by a component enriched in the light isotopes).In all primitive chondrites, both the amount and the chemical separability of CCFXe parallel the abundance of promordial noble gases and other volatiles, such as C, N, Tl, Bi and In. The close correlation of CCFXe with various properties of undoubtedly local origin (volatile content, petrologic type, presence of ferrichromite and carbon, etc.) is more consistent with a local than with an extrasolar origin of this component. A volatile superheavy element seems to be the most plausible source, but the evidence is not conclusive.  相似文献   

Extinct I129 in C3 chondrites     

Jane Crabb  Roy S. Lewis  Edward Anders 《Geochimica et cosmochimica acta》1982,46(12):2511-2525

Eight C3 chondrites were examined by the I¹²⁹Xe¹²⁹ dating method, to see whether their IXe “ages” (better, initial $\text{I}{}^{129}\text{I}{}^{127}$ratios ≡ R₀) correlate with any other properties. The R₀'s range from 1.60 × 10^?4 to 1.09 × 10^?4, corresponding to IXe ages from 2.0 Myr before to 6.7 Myr after Murchison magnetite. Three C3O's (Lancé, Felix, Ornans) have essentially indistinguishable R₀'s of (1.41 ± 0.13) to (1.17 ± 0.10) × 10^?4; the fourth C3O, Warrenton, is undatable owing to homogenization of radiogenic and trapped Xe.Four C3V's show a distinct spread: Vigarano and Grosnaja are highest [R₀ = (1.60 ± 0.07) and (1.57 ± 0.14) × 10^?4], Mokoia is intermediate, and Kaba is lowest [R₀ = (1.38 ± 0.06) and (1.09 ± 0.10) × 10^?4]. Literature values for Allende place it near Kaba. These R₀'s correlate inversely with 4 other properties: I-, Br-, and Cd-content, and olivine composition, both percent mean deviation (PMD) and proportion of iron-poor olivine grains (≤2% fayalite).It is difficult to accept the ～9 Myr spread in R₀ as a true age, reflecting either nebular or parent-body processes. This time span is more than an order of magnitude longer than the lifetime of the solar nebula inferred from astronomical evidence. Nor does the degree of thermal metamorphism, which is slight for C3's anyway, correlate with R₀. A more plausible interpretation is that the variations in R₀ reflect mainly isotopic heterogeneity of iodine. The simplest model that accounts for the correlations with R₀ involves mixing of two iodine components in the solar nebula, associated with gas and grains, respectively. The second, of lower $\text{I}{}^{129}\text{I}{}^{127}$ ratio, predominated at later times and thus became enriched in late-formed meteorites, along with other volatiles such as Cd and Br. The low Fe content and large PMD of olivine may reflect either less metamorphism owing to shallow location in the parent body, or greater reduction of Fe²⁺ during chondrule formation.  相似文献   

Isotopic anomalies of noble gases in meteorites and their origins—III. LL-chondrites     

Leo Alaerts  Roy S Lewis  Edward Anders 《Geochimica et cosmochimica acta》1979,43(9):1399-1415

Nine LL-chondrites were studied by a selective etching technique, to characterize the noblegas components in three mineral fractions: HF-HCl-solubles (silicates, metal, troilite, etc.; comprising ～ 99% of the meteorite), chromite and carbon (～ 0.3–0.7%) and Q (a poorly characterized mineral defined by its solubility in HNO₃, comprising ～ 0.05% of the meteorite but containing most of the Ar, Kr, Xe and a neon component of ${}^{20}\text{Ne}{}^{22}\text{Ne}\text{= 10.9 ± 0.8}$). The ${}^{20}\text{Ne}{}^{36}\text{Ar}$ ratio in Q falls wi petrologic type and rising ³⁶Ar content, as expected for condensation from a cooling solar nebula, but contrary to the trend expected for metamorphic losses. Chondrites of different petrologic types therefore cannot all be derived from the same volatile-rich ancestor, but must have formed over a range of temperatures, with correspondingly different intrinsic volatile contents.The CCFXe (carbonaceous chondrite fission) component varies systematically with petrologic type. The most primitive LL3s (Krymka, Bishunpur, Chainpur) contain substantial amounts of CCFXe in chromite-carbon, enriched relative to primordial Xe as shown by high ${}^{136}\text{Xe}{}^{132}\text{Xe}$ (0.359–0.459, vs 0.310 for primordial Xe). These are accompanied by He and by Ne with ${}^{20}\text{Ne}{}^{22}\text{Ne}\text{≈ 8.0}$ and by variable amounts of a xenon component enriched in the light isotopes. The chromite in these meteorites is compositionally peculiar, containing substantial amounts of Fe(III). These meteorites, as well as Parnallee (LL3) and Hamlet (LL4) also contain CCFXe in phase Q, heavily diluted by primordial $\text{Xe}\text{(}{}^{136}\text{Xe}{}^{132}\text{Xe}\text{= 0.317–0.329)}$. On the other hand, LL5s and 6s (Olivenza, St. Séverin, Manbhoom and Dhurmsala) contain no CCFXe in either mineral. This deficiency must be intrinsic rather than caused by metamorphic loss, because Q in these meteorites still contains substantial amounts of primordial Ne.If CCFXe comes from a supernova, then its distribution in LL-chondrites requires three presolar carrier minerals of the right solubility properties, containing three different xenon components in certain combinations. These minerals must be appropriately distributed over the petrologic types, together with locally produced Q containing primordial gases, and they must be isotopically normal, in contrast to the gases they contain. On the other hand, if CCFXe comes from fission of a volatile superheavy element, then its decrease from LL3 to LL6 can be attributed to progressively less complete condensation from the solar nebula. Ad hoc assumptions must of the host phase Q, its association with ferrichromite and the origin of the associated xenon component enriched in the light isotopes.Soluble minerals in LL3s and LL4s contain a previously unobserved, solar xenon component, which, however, is not derived from the solar wind. Three types of ‘primordial’ xenon thus occur side-by-side in different minerals of the same meteorite: strongly fractionated Xe in ferrichromite and carbon, lightly fractionated Xe in phase Q, and ‘solar’ Xe in solubles. Because the first two can apparently be derived from the third by mass fractionation, it seems likely that all were trapped from the same solar nebula reservoir, but with different degrees of mass fractionation.  相似文献   

On the siting of noble gases in E-chondrites     

Jane Crabb  Edward Anders 《Geochimica et cosmochimica acta》1982,46(11):2351-2361

We have investigated the siting of noble gases in 6 E-chondrites, by analyzing fractions separated by density, grain size, and chemical resistance from Qingzhen (E3), Indarch (E4), Abee and Saint Sauveur (E4-5) and Yilmia and North West Forrest (E6).The new “subsolar” (i.e. Ar-rich) component in E6's is concentrated in the main, ensatite-rich fraction of the meteorites, with density 3.06–3.3 g/cm³. It is unaffected by HCl and HNO₃ treatments of such fractions and remains in unchanged concentration when the samples are partially dissolved by HF. These properties suggest that the subsolar component is located in enstatite, or less likely, in a phase closely associated with it. E4-5's have at least half of their subsolar gases in HCl- and HNO₃-resistant sites (enstatite?), but fail to show the increasing gas concentration with decreasing grain size that is characteristic of most other primordial gas carriers. This may mean that the subsolar gases originally were in some other phase, but were then transferred to enstatite by metamorphism.Most of the ¹²⁹Xe_r of E6's is concentrated in the same fractions as the subsolar gases, again suggesting enstatite or an associated phase as the host. Only a few percent of the ¹²⁹Xe_r is contained in fractions enriched in other major and minor minerals. In E4's, on the other hand, ¹²⁹Xe_r is enhanced in finegrained, low density fractions and is also partly associated with chondrules. Perhaps ¹²⁹I was originally contained in fine-grained matrix, but was transferred to enstatite during metamorphism.A carbon-rich fraction of Indarch (E4) is enhanced in Ne-A, CCF-Xe, and L-Xe. Interestingly, both the isotopic composition of Xe and the Ne/CCF-Xe ratios resemble those of C-chondrites, yet these two meteorite classes probably formed rather far apart. Thus, if these components were mixed at a late stage, it must have been in fairly constant ratio over a large scale. Alternatively, they may have been mixed at an earlier stage, into a common carrier that was spread through a significant portion of the solar nebula.The primordial gases of Qingzhen (E3) resemble those of Indarch: they are present in moderate amounts (${}^{20}\text{Ne}{}_{\mathrm{p}}\text{= 1.2 × 10}{}^{\mathrm{?8}}\text{cc/g,}{}^{132}\text{Xe = 10 × 10}{}^{\mathrm{?10}}\text{cc/g)}$, with little or no contribution from the subsolar component. Thus Qingzhen reinforces our earlier finding that E-chondrites show no regular increase in noble gas content with decreasing petrologic type. One notable feature of Qingzhen is its very low ${}^3\text{He}{}^{21}\text{Ne}$ ratio of 1.07, which indicates that ³He has been lost by solar heating. Solar heating may also account for its low, discordant gas retention ages (U,Th-He age = 1.1 AE, KAr age = 3.2AE).  相似文献   

Isotopic anomalies of noble gases in meteorites and their origins—VI. Presolar components in the Murchison C2 chondrite     

Leo Alaerts  Roy S. Lewis  Jun-ichi Matsuda  Edward Anders 《Geochimica et cosmochimica acta》1980,44(2):189-209

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On neutron-induced and other noble gases in Allende inclusions     

R. Göbel  F. Begemann  U. Ott 《Geochimica et cosmochimica acta》1982,46(10):1777-1792

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${}^{40}\text{Ar}{}^{39}\text{Ar}$ dating,Ar diffusion properties,and cooling rate determinations of severely shocked chondrites     

D.D. Bogard  W.C. Hirsch 《Geochimica et cosmochimica acta》1980,44(11):1667-1682

Determinations of ${}^{40}\text{Ar}{}^{39}\text{Ar}$ ages are reported for seven severely shock-heated chondrites. Shaw gives a plateau age of 4.29 Gyr. Louisville, Farmington, and Wickenburg give well-defined intercept ages of 0.5–0.6 Gyr. Orvinio, Arapahoe, and Lubbock show complex ${}^{40}\text{Ar}{}^{39}\text{Ar}$ release curves, with age minima of 0.7–1.0 Gyr. Degassing times of 0.5–1.0 Gyr are suggested for these meteorites. Most severely shocked chondrites were apparently not totally degassed of ⁴⁰Ar by the event, but retained from ~ 2 to ~45% of their ⁴⁰Ar. When calculated values of the diffusion parameter, $\text{D}\text{a}{}^2$, for Ar are examined in Arrhenius plots, they show two distinct linear relationships, which apparently correspond to the degassing of different mineral phases with distinct $\text{K}\text{Ca}$ ratios and different average temperatures for Ar release. The experimentally determined values of $\text{D}\text{a}{}^2$ for the high temperature phase of several severely shocked chondrites are ~10^?7 to 10^?5sec^?1 for their determined shock-heating temperatures of ~950°C to ~ 1200°C. The inferred reheating temperatures, $\text{D}\text{a}{}^2$ values, and fraction of ⁴⁰Ar loss during the reheating event for these seven chondrites suggest post-shock cooling rates and burial depth of ~ 10^?2 10^?4°C/sec and ~0.5–2m, respectively. For three chondrites these cooling rates agree with those determined from Ni diffusion in metal grains: for five chondrites the cooling rates derived from ⁴⁰Ar and Ni disagree by a factor of ~10⁵. It is suggested that five of these severely shocked chondrites were part of large ejecta blankets containing hot material and cold clasts with a distribution of sizes and that the cooling rate of this ejecta appreciably decreased as a function of time.  相似文献   

Noble gas contents of shergottites and implications for the Martian origin of SNC meteorites     

D.D. Bogard  L.E. Nyquist  P. Johnson 《Geochimica et cosmochimica acta》1984,48(9):1723-1739

Isotopic concentrations of the noble gases have been measured in several different phases of Elephant Moraine A79001 and in whole rock samples of Zagami and Allan Hills A77005, three meteorites which belong to the rare group of SNC achondrites that may have originated from the planet Mars. Shocked phases of EETA79001 contain a trapped Ar, Kr, and Xe component characterized by ${}^{84}\text{Kr}{}^{132}\text{Xe}$ ～15, ${}^{40}\text{Ar}{}^{36}\text{Ar}\text{> 2000}$, ${}^{129}\text{Xe}{}^{132}\text{Xe ≥ 2}$, and ${}^4\text{He}{}^{40}\text{Ar}\text{≤ 0.1}$. These elemental and isotopic ratios are unlike those for any other noble gas component except analyses of the Martian atmosphere made by Viking spacecraft. The isotopic composition of the trapped Kr shows an approximate 1% per mass unit enrichment of lighter isotopes compared to terrestrial Kr, and the traped Xe may show either a fission component or a fractionated enrichment of heavier isotopes compared to terrestrial Xe. It is hypothesized that these gases represent a portion of the Martian atmosphere which was shock-implanted into EETA79001, and that they constitute direct evidence of a Martian origin for the shergottite meteorites. Cosmic ray-produced gases in the eight known SNC meteorites form three distinct groups with exposure ages of ～11 MY (Chassigny and the nakhlites), ～2.6 MY (Shergotty, Zagami, and ALHA77005), and ～0.5 MY (EETA79001). These ages suggest three distinct events and cannot have been produced by irradiation for a common time under greatly different shielding. Comparison of cosmogenic ${}^3\text{He}{}^{21}\text{Ne}$ measured in EETA79001 with two independent models for the production of this ratio as a function of shielding indicates that this meteorite was irradiated in space as a relatively small object. If the SNC meteorites were ejected from Mars ～ 180 My ago, the shock age of the shergottites, they must have been relatively large objects (>6 meters diameter) which experienced at least three space collisions to initiate cosmic ray exposure. Ejection from Mars by three events at the times of initiation of cosmic ray exposure would permit the ejected objects to have been much smaller (<1 meter diameter), but would require three such events on 1.3 Gy Martian terraine in the past ～10 MY and would not explain the common 180 MY shock age seen in all four shergottites.  相似文献   

Inert gases in a terra sample: measurements in six grain-size fractions and two single particles from Luna 20     

D Heymann  S Lakatos  J.R Walton 《Geochimica et cosmochimica acta》1973,37(4):875-885

The inert gases have been measured in six size fractions covering the range below 500 μm, in a single feldspathic fragment weighing 523 μg, and in an agglutinate particle weighing 465 μg. The two size fractions between 125 and 250 μm as well as 250 and 500 μm were separated into magnetic and non-magnetic portions, which were measured separately. Like the Apollo and Luna 16 fines, the terra fines represented by Luna 20 are very rich in trapped solar-wind gases, but they contain relatively less He⁴ and Ne²⁰, which is revealed by their average $\text{He}{}^4\text{Ne}{}^{20}$ ratio of 35 and $\text{Ne}{}^{20}\text{Ar}{}^{36}$ ratio of 2.9. Obviously the terra materials are less retentive for solar-wind He and Ne than typical mare fines such as 10084. Whether this is due to the relatively small TiO₂ or the relatively large plagioclase content of the former is not resolved. ($\text{Ar}{}^{36}\text{Kr}{}^{84}\text{)}{}_{\mathrm{trapped}}$ and ($\text{Ar}{}^{36}\text{Xe}{}^{132}\text{)}{}_{\mathrm{trapped}}$ ratios are relatively large; the average values are 2800 and 14400, respectively. The apparent Ne²¹ radiation ages of all the size fractions are in the range 209–286 × 10⁶ yr; the average is 260 × 10⁶ yr. This is in the range of values known for the Apollo and Luna 16 fines. The feldspathic fragment has a much greater apparent Ne_c²¹ age of 780 × 10⁶ yr. The Ar⁴⁰-Ar³⁶ systematic reveals the presence of two Ar⁴⁰ components, because Ar⁴⁰ = (1.41 ± 0.076)Ar³⁶ + (0.490 ± 0.130) × 10^?4 (cm³ STP/g). The $\text{Ar}{}^{40}\text{Ar}{}^{36}$ slope of 1.41 is not inconsistent with an origin of the sample from a relatively old terra region.  相似文献   

Prediction of Gibbs free energies of calcite-type carbonates and the equilibrium distribution of trace elements between carbonates and aqueous solutions     

Dimitri A Sverjensky 《Geochimica et cosmochimica acta》1984,48(5):1127-1134

A linear correlation exists between the standard Gibbs free energies of formation of calcite-type carbonates (MCO3) and the corresponding conventional standard Gibbs free energies of formation of the aqueous divalent cations (M2+) at 25 °C and 1 bar ΔGMCO30 = m(ΔGf,M2+0) ? 141,200 cal · mole?1 where m is equal to 0.9715. This relationship enables prediction of the standard free energies of formation of numerous hypothetical carbonates with the calcite structure. Associated uncertainties typically range from about ± 250 to 600 cal · mole?1. An important consequence of the above correlation is that the thermodynamic equilibrium constant for the distribution of two trace elements M and N between carbonate mineral and aqueous solution at 25 °C and 1 bar is proportional to the free energy difference between the corresponding two aqueous ions: In Combination of predicted standard free energies, entropies and volumes of carbonate minerals at 25°C and 1 bar with standard free energies of aqueous ions and the equation of state in Helgesonet al. (1981) enables prediction of the thermodynamic equilibrium constant for trace element distribution between carbonates and aqueous solutions at elevated temperatures and pressures. Interpretation of the thermodynamic equilibrium constant in terms of concentration ratios in the aqueous phase is considerably simplified if pairs of divalent trace elements are considered that have very similar ionic radii (e.g., $\text{Sr}{}^{\mathrm{2+}}\text{Pb}{}^{\mathrm{2+}}$, $\text{Mg}{}^{\mathrm{2+}}\text{Zn}{}^{\mathrm{2+}}$). In combination with data for the stabilities of complex ions in aqueous solutions, the above calculations enable useful limits to be placed on the concentrations of trace elements in hydrothermal solutions.  相似文献   

Thermochemical redox equilibria of ZoBell's solution     

Darrell Kirk Nordstrom 《Geochimica et cosmochimica acta》1977,41(12):1835-1841

The redox potential of ZoBell's solution, consisting of $\text{3.33 × 10}{}^{\mathrm{?3}}$ molar K₄Fe(CN)₆, $\text{3.33 × 10}{}^{\mathrm{?3}}$ molar K₃Fe(CN)₆ and 0.10 molar KCl, has been measured by a polished platinum electrode vs a saturated KCl, Ag/AgCl reference electrode. Measurements in the temperature range 8–85°C fit the equation $\text{E(}\text{volts}\text{) = 0.23145 ? 1.5220 × 10}{}^{\mathrm{?3}}\text{(t ? 25) ? 2.2449 × 10}{}^{\mathrm{?6}}\text{(t ? 25)}{}^2$ where $\text{t}$ is in degrees Celsius. Evaluation of literature data was necessary to obtain a reliable value for the Ag/AgCl half-cell reference potential as a function of temperature. Combining the measurements from this study with the literature evaluation of the Ag/AgCl reference potential yields the temperature dependent potential for ZoBell's solution: $\text{E(}\text{volts}\text{) = 0.43028 ? 2.5157 × 10}{}^{\mathrm{?3}}\text{(t ? 25) ? 3.7979 × 10}{}^{\mathrm{?6}}\text{(t ? 25)}{}^2$ relative to the standard hydrogen potential. From these data the enthalpy, entropy, free energy and heat capacity for the ferro-ferricyanide redox couple have been calculated. The temperature equation for the potential of ZoBell's solution may be used for checking potentiometric equipment in the determination of the redox potential of natural waters.  相似文献   

Noble gas evidence for two fluids in the Baca (Valles Caldera) geothermal reservoir     

S.P. Smith  B.M. Kennedy 《Geochimica et cosmochimica acta》1985,49(4):893-902

Noble gas elemental and isotopic abundances were measured in steam from four wells in the Baca geothermal reservoir located in the Valles Caldera, New Mexico. The ${}^{40}\text{Ar}{}^{36}\text{Ar}$ ratio and noble gas elemental abundances relative to ³⁶Ar are all strongly correlated with 1/³⁶Ar, the inverse of the argon content. Ratios of (α,n)-produced ²¹Ne1 and radiogenic ⁴⁰Ar1 to total ⁴He (dominantly radiogenic) are nearly constant at 2.1 × 10?8 and 0.20, respectively. The ${}^3\text{He}{}^4\text{He}$ ratio covers a restricted range of 3.9 to 4.8 times atmospheric. The high ³He content of the gas indicates the presence of a helium component ultimately derived from the mantle. Kr and Xe isotopic compositions are close to atmospheric; excess ¹²⁹Xe1 is <0.25% of the total ¹²⁹Xe.The high degree of linear correlation among the various noble gas results strongly suggests that the Baca reservoir contains two distinct fluids that are produced in varying proportions from individual wells. The noble gases in fluid A (~2900 mg/1 C1) are air-like, but with lighter gases and isotopes preferentially enriched. The fluid A ³⁶Ar content is low, only 13% that of 10°C air-saturated water (ASW). The second fluid, B (~ 1700 mg/1 C1), is the dominant carrier of the radiogenic and mantle-derived gases. The heavier non-radiogenic gases are preferentially enriched in fluid B, and its ³⁶Ar content is very low, only 5–7% ASW. The source of the noble gases in fluid A is tentatively ascribed to leaching of the relatively young (<1.4 m.y.) volcanic Bandelier Tuff. The radiogenic gases and mantle-derived helium in fluid B suggest a deeper source, possibly including gases escaping from a magma.  相似文献   

A corundum-rich inclusion in the Murchison carbonaceous chondrite     

Miryam Bar-Matthews  Ian D Hutcheon  Glenn J MacPherson  Lawrence Grossman 《Geochimica et cosmochimica acta》1982,46(1):31-41

A corundum-hibonite inclusion, BB-5, has been found in the Murchison carbonaceous chondrite. This is the first reported occurrence of corundum as a major phase in any refractory inclusion, even though this mineral is predicted by thermodynamic calculations to be the first condensate from a cooling gas of solar composition. Ion microprobe measurements of Mg isotopic compositions yield the unexpected result for such an early condensate that ²⁶Mg excesses are small: δ_N²⁶Mg = 7.0 ± 1.6%. for hibonite and 5.0 ± 4.8%. for corundum, despite very large ${}^{27}\text{Al}{}^{24}\text{Mg}$ ratios, 130 and 2.74 × 10⁴, respectively. Within the errors, δ_N²⁶Mg does not vary over this exceedingly large range of ${}^{27}\text{Al}{}^{24}\text{Mg}$ ratios. The extreme temperature required to melt this inclusion makes a liquid origin unlikely, except possibly by hypervelocity impact involving refractory bodies. If, instead, BB-5 is a direct gas-solid condensate, textural evidence implies that corundum formed first and later reacted to produce hibonite. In this model, BB-5's uniform enrichment in ²⁶Mg must be a characteristic of the reservoir from which it condensed. Because severe difficulties are encountered in making such a reservoir by prior decay of ²⁶Al, nebular heterogeneity in magnesium isotopic composition is a preferred explanation.  相似文献   

The effect of pressure on the solubility of minerals in water and seawater     

Frank J Millero 《Geochimica et cosmochimica acta》1982,46(1):11-22

The effect of presure on the solubility of minerals in water and seawater can be estimated from In where the volume (ΔV) and compressibility (ΔK) changes at atmospheric pressure (P = 0) are given by Values of the partial molal volume ($\text{V}\text{?}$) and compressibilty ($\text{K}\text{?}$) in water and seawater have been tabulated for some ions from 0 to 50°C. The compressibility change is quite large (~10 × 10^?3 cm³ bar^?1 mol^?1) for the solubility of most minerals. This large compressibility change accounts for the large differences observed between values of ΔV obtained from linear plots of In K_sp versus P and molal volume data (Macdonald and North, 1974; North, 1974). Calculated values of $\text{K}{}^{\mathrm{P}}{}_{\mathrm{sp}}\text{K}{}^{\mathrm{o}}{}_{\mathrm{sp}}$ for the solubility of CaCO₃, SrSO₄ and CaF₂ in water were found to be in good agreement with direct measurements (Macdonald and North, 1974). Similar calculations for the solubility of minerals in seawater are also in good agreement with direct measurements (Ingle, 1975) providing that the surface of the solid phase is not appreciably altered.  相似文献   

${}^3\text{He}{}^4\text{He}$ ratio,noble gas abundance and K-Ar dating of diamonds—An attempt to search for the records of early terrestrial history     

M. Ozima  S. Zashu  O. Nitoh 《Geochimica et cosmochimica acta》1983,47(12):2217-2224

The ${}^3\text{He}{}^4\text{He}$ ratios measured in 27 Southern Africa diamond stones, four from Premier Mine and the rest of unidentified origin, range from 4.2 × 10^?8 to 3.2 × 10^?4, with three stones above 1 × 10^?4. We conclude that the initial helium isotopic ratio (${}^3\text{He}{}^4\text{He)}{}_0$ in the earth was significantly higher than that of the planetary helium-A (${}^3\text{He}{}^4\text{He = 1.42 × 10}{}^{\mathrm{?4}}$), but close to the solar helium (${}^3\text{He}{}^4\text{He ? 4 × 10}{}^{\mathrm{?4}}$).The apparent K-Ar ages for the twelve diamonds of unidentified origin show enormously old age, indicating excess argon-40. ${}^3\text{He}{}^4\text{He}$ evolution in diamonds suggests that the diamonds with the high ${}^3\text{He}{}^4\text{He}$ ratio (>2 × 10^?4) may be as old as the earth.Noble gas elemental abundance in the diamonds relative to the air noble gas abundance shows monotonie decrease with a decreasing mass number.This paper discusses the implications of these observations on the early solar system and the origin of diamonds.  相似文献   

Rare earth element geochemistry of the Betts Cove ophiolite,Newfoundland: complexities in ophiolite formation     

R.A. Coish  R. Hickey  F.A. Frey 《Geochimica et cosmochimica acta》1982,46(11):2117-2134

The Betts Cove ophiolite includes the components of typical ocean crust: pillow lavas, sheeted dikes, gabbros and ultramafics. However, the trace element geochemistry of basaltic rocks is unusual. Three geochemical units are recognized within the lava and dike members. Within the pillow lavas, the geochemical units correspond to stratigraphic units. Upper lavas have ‘normal’ (i.e., typical for ocean floor basalts) TiO₂ contents (0.75 to 2.0 wt%), heavy rare earth elements (HREE) values in the range 6–20× chondrites and chondrite-normalized REE patterns with relative LREE depletion. Intermediate lavas have TiO₂ contents between 0.30 and 0.50 wt%, HREE contents from 4–7× chondrites and extreme relative LREE depletion. Lower lavas have anomalously low TiO₂ contents (<0.30 wt%) and unusual convex-downwards REE patterns with REE abundances around 2–5 × chondrite. These geochemical differences can be explained if the three groups were derived from different mantle sources. Independent mantle sources for the three units are consistent with their different ${}^{143}\text{Nd}{}^{144}\text{Nd}$ ratios varying at 480 m.y.B.P. from 0.51222 in a lower lava to 0.51238 in an upper lava. The upper lavas may be partial melts of a source similar in composition to that of modern MORB, the intermediate lavas may be from a very depleted oceanic mantle (second stage melt), and the lower lavas may have formed by melting an extremely depleted mantle that had been invaded by a LREE-enriched fluid. A possible tectonic environment where these different sources could be juxtaposed is a back-arc or inter-arc basin.  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   

The isotopic composition of silver and lead in two iron meteorites: Cape York and Grant     

J.H. Chen  G.J. Wasserburg 《Geochimica et cosmochimica acta》1983,47(10):1725-1737

Silver in the metal phases of Cape York (IIIA) and Grant (IIIB) has been determined after an extensive surface cleaning process. The ${}^{107}\text{Ag}{}^{109}\text{Ag}$ was found to be enriched over that found in terrestrial Ag by ~7%. to 19%., demonstrating the presence of excess ¹⁰⁷Ag (¹⁰⁷Ag¹) in this class of meteorites. An effort was made to find schreibersite with a distinctive ¹⁰⁸Pd/¹⁰⁹Ag ratio in order to establish a three-point isochron, but the results are not markedly different from those obtained for the bulk metal. The Ag isotopic ratio of sulfides from the same meteorites were nearly normal in composition. These results demonstrate correlations of ${}^{107}\text{Ag}{}^{109}\text{Ag}$ with ${}^{108}\text{Pd}{}^{109}\text{Ag}$ between coexisting phases of two iron meteorites that are associated with planetary differentiation processes. The ratios ${}^{107}\text{Ag}{}^1{}^{108}\text{Pd}$ were found to be 1.7 × 10^?5 and 1.2 × 10^?5 for Cape York and Grant, respectively. These observations are in support of the widespread presence of ¹⁰⁷Pd in the early solar system. The difference in isotopic composition between metal and sulfide phases demonstrates that silver diffusion was small (over 6.5 × 10⁶ y) indicating a cooling rate much greater than 150°C/my for meteorites which have been attributed to small planetary cores. Uranium determinations were carried out on the metal phases and concentrations of ~ $\text{1 × 10}{}^{12}$ g U/g and 2 × 10^?10g U/g were found for Cape York and Grant, respectively. The Pb in these meteorites was determined using the improved cleaning procedures and chemical separations with low blank levels. The results confirm the presence of variable proportions of radiogenic Pb in both the metal and sulfide phases of iron meteorites. No simple explanation for the presence of radiogenic lead is apparent; while terrestrial contamination may appear to be the obvious explanation, it is possible that this effect could result from relatively recent metamorphism in the meteorite parent body.  相似文献