Noble gases in E-chondrites

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.     

On the siting of noble gases in E-chondrites

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).     

Revised values for the Gibbs free energy of formation of [Al(OH)4 aq−], diaspore,boehmite and bayerite at 298.15 K and 1 bar,the thermodynamic properties of kaolinite to 800 K and 1 bar,and the heats of solution of several gibbsite samples

Solution calorimetric measurements compared with solubility determinations from the literature for the same samples of gibbsite have provided a direct thermochemical cycle through which the Gibbs free energy of formation of [Al(OH)_{4 aq}^?] can be determined. The Gibbs free energy of formation of [Al(OH)_{4 aq}^?] at 298.15 K is ?1305 ± 1 kJ/mol. These heat-of-solution results show no significant difference in the thermodynamic properties of gibbsite particles in the range from 50 to 0.05 μm.The Gibbs free energies of formation at 298.15 K and 1 bar pressure of diaspore, boehmite and bayerite are ?9210 ± 5.0, ?918.4 ± 2.1 and ?1153 ± 2 kJ/mol based upon the Gibbs free energy of [A1(OH)_{4 aq}^?] calculated in this paper and the acceptance of ?1582.2 ± 1.3 and ?1154.9 ± 1.2 kJ/mol for the Gibbs free energy of formation of corundum and gibbsite, respectively.Values for the Gibbs free energy formation of [Al(OH)_{2 aq}⁺] and [AlO_{2 aq}^?] were also calculated as ?914.2 ± 2.1 and ?830.9 ± 2.1 kJ/mol, respectively. The use of [AlC_{2 aq}^?] as a chemical species is discouraged.A revised Gibbs free energy of formation for [H₄SiO_4aq⁰] was recalculated from calorimetric data yielding a value of ?1307.5 ± 1.7 kJ/mol which is in good agreement with the results obtained from several solubility studies.Smoothed values for the thermodynamic functions C_P⁰, ($\text{H}{}_{\mathrm{T}}{}^0\text{- H}{}_{298}{}^0\text{)}\text{T}$, $\text{(}\text{G}{}_{\mathrm{T}}{}^0\text{- H}{}_{298}{}^0\text{)}\text{T}$, S_T⁰ - S₀⁰, $\text{ΔH}{}_{\mathrm{?,298}}{}^0$ kaolinite are listed at integral temperatures between 298.15 and 800 K. The heat capacity of kaolinite at temperatures between 250 and 800 K may be calculated from the following equation: C_P⁰ = 1430.26 ? 0.78850 T + 3.0340 × 10^?4T² ?1.85158 × 10^?4T²$\text{1}\text{2}\text{+ 8.3341 × 10}{}^6\text{T}{}^{\mathrm{?2}}$.The thermodynamic properties of most of the geologically important Al-bearing phases have been referenced to the same reference state for Al, namely gibbsite.     

Precise age determinations and petrogenetic studies using the KCa method

High precision mass spectrometric determination of calcium isotope ratios allows the ⁴⁰K → ⁴⁰Ca radioactive decay to be used for dating a much broader range of geologic materials than is suggested by previous work. ${}^{40}\text{Ca}{}^{42}\text{Ca}$ is used to monitor enrichments in ⁴⁰Ca and can be measured to ±0.01% (2σ) using an exponential mass discrimination correction (Russell et al., 1978) and large ion currents. The earth's mantle has such a low $\text{K}\text{Ca}$ (～0.01) that it has retained “primordial” ${}^{40}\text{Ca}{}^{42}\text{Ca}\text{= 151.016}$ ± 0.011 (normalized to ${}^{42}\text{Ca}{}^{44}\text{Ca}\text{= 0.31221}$), as determined by measurements on two meteorites, pyroxene from an ultramafic nodule, metabasalt, and carbonatite. ${}^{40}\text{Ca}{}^{42}\text{Ca}$ ratios can be conveniently expressed relative to this value as ?_Ca in units of 10^?4. To test the method for age dating, a mineral isochron has been obtained on a sample of Pikes Peak granite, which has been shown to have concordant KAr, RbSr, and UPb ages. Plagioclase, K-feldspar, biotite, and whole rock yield an age of 1041 ± 32 m.y. (2σ) in agreement with previous age determinations (λ_K = 0.5543 b.y.^?1, $\text{λ}{}_{\mathrm{\beta ?}}\text{λ}{}_{\mathrm{<mtext>K</mtext>}}\text{= 0.8952}$, ⁴⁰K = 0.01167%). The initial ${}^{40}\text{Ca}{}^{42}\text{Ca}$ of 151.024 ± 0.016 (?_Ca = +0.5 ± 1.0), indicates that assimilation of high K/Ca crust was insufficient to affect calcium isotopes. Measurements on two-mica granite from eastern Nevada indicate that the magma sources had K/Ca ≈ 1, similar to intermediate-composition crustal rocks. These results show that the KCa system can be used as a precise geochromometer for common felsic igneous and metamorphic rocks, and may prove applicable to sedimentary rocks containing authigenic K minerals. The relatively short half-life of ⁴⁰K, the non-volatile daughter, and the fact that potassium and calcium are stoichiometric constituents of many minerals, make the KCa system complementary to other dating methods, and potentially applicable to a variety of geologic problems.     

Geochronologic investigations of the Sudbury Nickel Irruptive and the Superior Province granites north of Sudbury

RbSr ($\text{λ}\text{Rb}\text{= 1.39 × 10}{}^{\mathrm{?11}}\text{yr}{}^{\mathrm{?1}}\text{)}$ and U-Pb ($\text{λ 238 = 1.54 × 10}{}^{\mathrm{?10}}\text{yr}{}^{\mathrm{?1}}\text{, λ235 = 9.72 × 10}{}^{\mathrm{?10}}\text{yr}{}^{\mathrm{?1}}$) measurements were undertaken in the Sudbury area, Sudbury, Ontario to determine the ages of the Sudbury Nickel Irruptive, Superior Province granites north of Sudbury, Sudbury Breccia and subsequent metamorphism. The Sudbury Nickel Irruptive norite whole rock Rb-Sr data yield an age of $\text{1883 ± 136}\text{Myr}$ ($\text{I.R}\text{. = 0.7071 ± 0.0005}$; all results quoted at 2π level) while the Nickel Irruptive micropegmatite Rb-Sr system has been disturbed and does not yield an isochron. A plagioclase-whole rock pair from the norite near the norite-micropegmatite transition yields an age of 1866 Myr, which when taken in conjunction with field (Stevenson and Colgrove, 1968) and geochemical (Naldrettet al., 1970, 1972) data does not support the conclusion of gibbins and McNurr (1972) that the micropegmatite is a later intrusion rather than a differentiate of the magma which produced the norite. Rb-Sr studies of the Superior Province granites north of Sudbury yield an age of $\text{2698 ± 162}\text{Myr}$ ($\text{I.R.}\text{= 0.7019 ± 0.0012}$). U-Pb zircon studies of these granites and granitic clasts within the Sudbury Breccia yield an age of $\text{2.71 ± 0.05}$ Byr and suggest the breccia granitic clasts were derived from the Superior Province granites. The granitic rocks ~150 km north of Sudbury have been undisturbed for ~ 2.6 Byr based on Rb-Sr mineral studies, whereas the granites and Sudbury Breccia within ~ 15 km of the Nickel Irruptive, as well as the Sudbury norite at the perimeter of the Irruptive have been disturbed by the Penokean Orogeny 1.7–1.75 Byr ago. The Penokean event appears to have overprinted isotopic evidence of the Sudbury impact event at least in the area studied.     

I-Xe and 40Ar-39Ar dating of silicate from Weekeroo Station and Netschaëvo IIE iron meteorites

Silicate inclusions from two IIE iron meteorites were dated by the I-Xe and ⁴⁰Ar-³⁹Ar techniques. Weekeroo Station, a ‘normal’ IIE iron, shows no loss of radiogenic ⁴⁰Ar at low temperature, and the well-defined ⁴⁰Ar-³⁹Ar plateau yields an age of 4.54 ± 0.03 Byr. The xenon data define a good I-Xe correlation with an age of +10.9 ± 0.5 Myr relative to Bjurböle [the monitor error (±2.5 Myr) is not included].^Despite its relatively young age, Weekeroo Station's $\text{(}{}^{129}\text{Xe}{}^{132}\text{Xe)}{}_{\mathrm{trappad}}$ ratio (= 0.84 ± 0.05) lies significantly below the solar value. Netschaëvo silicate has a chondritic composition, unlike ‘normal’ IIE silicate which is more differentiated. Nevertheless Netschaëvo gives a ⁴⁰Ar-³⁹Ar plateau-age of only 3.79 ± 0.03 Byr, with the xenon data failing to define an I-Xe isochron.Only irons from the IAB and IIE groups contain silicate inclusions, but these two groups differ in many other respects, mostly suggesting that IAB meteorites are more primitive. The I-Xe chronology supports this suggestion inasmuch as Weekeroo Station formed well after (8–15 Myr) IAB silicates. In terms of Scott and Wasson's (1976) model, ages for Weekeroo Station date the shock event which formed ‘normal’ IIE irons by mixing the low-melting fraction of the parent silicate with shock-liquefied metal. Scott and Wasson's suggestion that Netschaëvo represents IIE parent material, however, is contradicted by Netschaëvo's 3.8 Byr age.The four silicate-bearing IIE irons which have now been dated can be subdivided into distinct pairs: Weekeroo Station and Colomera formed near the beginning of the solar system, while Netschaëvo and Kodaikanal both formed only 3.8 Byr ago. A review of other properties of these meteorites generally support this subdivision.This work underscores the complexity of the history of IIE meteorites; in particular, an adequate model must account for the formation of two IIE irons at 3.8 Byr without disturbing rare gases in Weekeroo Station. All formation models are quite speculative, but the one which seems best to fit the available evidence postulates two parent bodies: the 3.8 Byr old silicate formed on one parent body, all other IIE material resided in a separate body, and subsequent collision(s) mixed the young silicate with IIE metal.     

Thermochemical redox equilibria of ZoBell's solution

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.     

Oxygen diffusion in amphiboles

The kinetics of oxygen isotope self-diffusion in natural samples of hornblende, tremolite, and richterite have been measured. Samples were run under hydrothermal conditions using ¹⁸O enriched water. Profiles of ${}^{18}\text{O}\text{(}{}^{16}\text{O +}{}^{18}\text{O)}$vs depth into the crystal were obtained using an ion microprobe; the depths of sputtered holes were measured using an optical interferometer. At 1000 bars (100 MPa) water pressure, the activation energies (Q) and pre-exponential factors (D₀) for diffusion parallel to c are: D₀(cm²/sec) Q (kcal/gm-atom) T (°C) Hornblende 1⁺²⁰_?1 × 10^?741 ± 6 650–800 Tremolite 2⁺³⁰_?2× 10^?8 39 ± 5 650–800 Richterite 3⁺⁵_?2 × 10^?4 57 ± 2 650–800The diffusion coefficient (D) for hornblende at 800°C and 1000 bars water pressure measured parallel to the c crystallographic direction is at least ten times greater than that parallel to the a or b directions. An increase in water pressure from 200 to 2000 bars increases D by a factor of 2.7 for diffusion parallel to c at 800°C. The D value for hornblende at 800°C is about 0.01 that for quartz and 0.001 that for anorthite. As a result, closure temperatures for oxygen exchange in natural primary amphiboles are significantly higher than for quartz or feldspars. It is unlikely that amphiboles will exchange oxygen isotopes by diffusion under most crustal conditions.     

Gibbsite solubility and thermodynamic properties of hydroxy-aluminum ions in aqueous solution at 25°C

Solubility curves were determined for a synthetic gibbsite and a natural gibbsite (Minas Gerais, Brazil) from pH 4 to 9, in 0.2% gibbsite suspensions in 0.01 M NaNO₃ that were buffered by low concentrations of non-complexing buffer agents. Equilibrium solubility was approached from oversaturation (in suspensions spiked with Al(NO₃)₃ solution), and also from undersaturation in some synthetic gibbsite suspensions. Mononuclear Al ion concentrations and pH values were periodically determined. Within 1 month or less, data from over-and undersaturated suspensions of synthetic gibbsite converged to describe an equilibrium solubility curve. A downward shift of the solubility curve, beginning at pH 6.7, indicates that a phase more stable than gibbsite controls Al solubility in alkaline systems. Extrapolation of the initial portion of the high-pH side of the synthetic gibbsite solubility curve provides the first unified equilibrium experimental model of Al ion speciation in waters from pH 4 to 9.The significant mononuclear ion species at equilibrium with gibbsite are Al³⁺, AlOH²⁺, Al(OH)⁺₂ and Al(OH)^?₄, and their ion activity products are $\text{1K}{}_{50}\text{= 1.29 × 10}{}^8$, $\text{1K}{}_{\mathrm{s1}}\text{= 1.33 × 10}{}^3$, $\text{1K}{}_{\mathrm{s2}}\text{= 9.49 × 10}{}^{\mathrm{?3}}$ and $\text{1K}{}_{\mathrm{s4}}\text{= 8.94 × 10}{}^{\mathrm{?15}}$. The calculated standard Gibbs free energies of formation (ΔG°_f) for the synthetic gibbsite and the A1OH²⁺, Al(OH)⁺₂ and Al(OH)^?₄ ions are ?276.0, ?166.9, ?216.5 and ?313.5 kcal mol^?1, respectively. These ΔG°_f values are based on the recently revised ΔG°_f value for Al³⁺ (?117.0 ± 0.3 kcal mol_?1) and carry the same uncertainty. The ΔG°_f of the natural gibbsite is ?275.1 ± 0.4 kcal mol^?, which suggests that a range of ΔG°_f values can exist even for relatively simple natural minerals.     

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

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.     

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

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.     

An electrochemical study of Ni2+, Co2+, and Zn2+ ions in melts of composition CaMgSi2O6

Cyclic voltammetry has been done for Ni²⁺, Co²⁺, and Zn²⁺ in melts of diopside composition in the temperature range 1425 to 1575°C. Voltammetric curves for all three ions excellently match theoretical curves for uncomplicated, reversible charge transfer at the Pt electrode. This implies that the neutral metal atoms remain dissolved in the melt. The reference electrode is a form of oxygen electrode. Relative to that reference assigned a reduction potential of 0.00 volt, the values of standard reduction potential for the ions are $\text{E}{}^1\text{(}\text{Ni}{}^{\mathrm{2+}}\text{Ni}{}^0\text{,}\text{diopside}\text{, 1500°C) = ?0.32 ± .01}\text{V}$, $\text{E}{}^1\text{(}\text{Co}{}^{\mathrm{2+}}\text{Co}{}^0\text{,}\text{diopside}\text{, 1500°C) = ?0.45 ± .02}\text{V}$, and $\text{E}{}^1\text{(}\text{Zn}{}^{\mathrm{2+}}\text{Zn}{}^0\text{,}\text{diopside}\text{, 1500°C) = ?0.53 ± .01}\text{V}$. The electrode reactions are rapid, with first order rate constants of the order of 10^?2 cm/sec. Diffusion coefficients were found to be 2.6 × 10^?6 cm²/sec for Ni²⁺, 3.4 × 10^?6 cm²/sec for Co²⁺, and 3.8 × 10^?6 cm²/sec for Zn²⁺ at 1500°C. The value of $\text{E1}$ ($\text{Ni}{}^{\mathrm{2+}}\text{Ni}{}^0$, diopside) is a linear function of temperature over the range studied, with values of ?0.35 V at 1425°C and ?0.29 V at 1575°C. At constant temperature the value of $\text{E}{}^1\text{(}\text{Ni}{}^{\mathrm{2+}}\text{Ni}{}^0\text{, 1525°C}$) was not observed to vary with composition over the range CaO · MgO · 2SiO₂ to CaO·MgO·3SiO₂ or from 1.67 CaO·0.33MgO·2SiO₂ to 0.5 CaO·1.5MgO·2SiO₂. The value for the diffusion coefficient for Ni²⁺ decreased by an order of magnitude at 1525°C over the compositional range CaO · MgO · 1.25SiO₂ to CaO · MgO · 3SiO₂. This is consistent with a mechanism by which Ni²⁺ ions diffuse by moving from one octahedral coordination site to another in the melt, with the same Ni²⁺ species discharging at the cathode regardless of the SiO₂ concentration in the melt.     

Complexing of silica by iron(III) in natural waters

Determination of amorphous silica solubility in acidified ferric nitrate solutions confirms the presence of ferric silicate complexing. A dissociation constant for the reaction:

$\text{FeH}{}_3\text{SiO}{}_4{}^{\mathrm{2+}}\text{→}\text{Fe}{}^{\mathrm{3+}}\text{+}\text{H}{}_3\text{SiO}{}_4{}^{\mathrm{?}}$

of 10^?9.8 ± 0.3 pK units at room temperature (22 ± 3°C) is obtained, in close agreement with reported values at 25°C corrected to zero ionic strength of 10^?9.9 by Weber and Stumm and 10^?9.5 by Olson and O'Melia. Iron-silicate complexing may be of significance to the mobilization of silica in acid waters associated with oxidizing sulphide deposits and coal strip mining and the precipitation of secondary silicate mineral phases.     

Use of Pitzer's equations to determine the media effect on the formation of lead chloro complexes

The spectrophotometric measurements of chloro complexes of lead in aqueous HCl, NaCl, MgCl₂ and CaCl₂ solutions at 25°C have been analyzed using Pitzer's specific interaction equations. Parameters for activity coefficients of the complexes PbCl⁺, PbCl₂⁰ and PbCl₃^? have been determined for the various media. Values of $\text{K}{}_1\text{= 30.0 ± 0.6}$, $\text{K}{}_2\text{= 106.7 ± 2.1}$ and $\text{K}{}_3\text{= 73.0 ± 1.5}$ were obtained for the cumulative formation constants. [$\text{Pb}{}^{\mathrm{2+}}\text{+ nCl}{}^{\mathrm{?}}\text{→ PbCl}{}_{\mathrm{n}}{}^{\mathrm{2?n}}\text{)}$]. These values are in reasonable agreement with literature data. The Pitzer parameters for the PbCl ion pairs in various media were used to calculate the speciation of Pb²⁺ in an artificial seawater solution.     

A corundum-rich inclusion in the Murchison carbonaceous chondrite

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.     

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

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.     

Determination of the 87Rb decay constant

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 $\text{1.419(±0.012) × 10}{}^{\mathrm{?11}}\text{yr}{}^{\mathrm{?1}}\text{(2σ)}$. [$\text{τ}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{= 4.89(±0.04) × 10}{}^{10}\text{yr}$.]     

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

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.     

On the observation of 92Nb and 94Nb in nature

Radioactivity measurements have shown evidence for long-lived ⁹²Nb and $\text{2.03 × 10}{}^4\text{yr}{}^{94}\text{Nb}$ in natural niobium. The specific activity of ⁹⁴Nb was observed to be 0.32 ± 0.03 dis/min. kg Nb and that of ⁹²Nb to be 0.058 ± 0.035 dis/min. kg Nb. With $\text{t}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ taken as ≈ 1.7 × 10⁸yr, the isotopic abundance of ⁹⁸Nb is 1.2 × 10^?10 per cent.