The isotopic composition and concentration of Ag in iron meteorites and the origin of exotic silver

The isotopic composition of Ag and the concentration of Ag and Pd have been determined in Canyon Diablo (IA), Grant (IIIB), Hoba, Santa Clara, Tlacotepec and Warburton Range (IVB), Piñon and Deep Springs (anom.). Troilite from Grant and Santa Clara have also been analyzed. All of these meteorites, with the exception of Canyon Diablo, give ${}^{107}\text{Ag}{}^{109}\text{Ag}$ in the metal phase that is greater than the terrestrial value with the enrichments of ¹⁰⁷Ag ranging from ~2% to 212%. These data show that Ag of anomalous isotopic composition is common to all IVB and anomalous meteorites. The results on Grant suggest that the anomalies may be widespread including more common meteorite groups. There is a general correlation of ${}^{107}\text{Ag}{}^{109}\text{Ag}$ with $\text{Pd}\text{Ag}$ except for the data from FeS of Santa Clara. It is concluded that the excess ¹⁰⁷Ag is the result of decay of ¹⁰⁷Pd, a nuclide that is extinct at present with an abundance of ${}^{107}\text{Pd}{}^{108}\text{Pd}$ of about 3 × 10^?5. The troilite in Grant exhibits normal ${}^{107}\text{Ag}{}^{109}\text{Ag}$ to within errors, a high Ag concentration and a low ratio of ${}^{108}\text{Pd}{}^{109}\text{Ag}$ ~0.17. Grant metal has ${}^{107}\text{Ag}{}^{109}\text{Ag}$ that is ~2% greater than normal and a high ratio of ${}^{108}\text{Pd}{}^{109}\text{Ag}$ ~ 10³. The data from Grant appear to represent a ¹⁰⁷Pd-¹⁰⁷Ag isochron and indicate that the cooling rate at elevated temperatures was sufficiently rapid to preserve substantial isotopic differences between metal and troilite. Troilite in Santa Clara was found to contain Ag with a very high ${}^{107}\text{Ag}{}^{109}\text{Ag}$ ratio (108% above normal), an Ag concentration only a factor of three above the metal and a high value of ${}^{108}\text{Pd}{}^{109}\text{Ag}$ ~1.3 × 10⁴. The troilite has a higher ${}^{107}\text{Ag}{}^{109}\text{Ag}$ than the metal. These data are not compatible with a simple model of in situ decay and subsequent local Ag redistribution between metal and troilite during cooling. These data suggest that Ag in Santa Clara and possibly other IVB meteorites is made up of almost pure ¹⁰⁷Ag produced from ¹⁰⁷Pd decay and ¹⁰⁹Ag produced by nuclear reactions with only a small amount of “normal” Ag. This indicates an intense energetic particle bombardment history in the early solar system (~10²⁰ p/m²) which occurred after the formation of small planetary bodies. We infer that a T-Tauri activity by the early sun contributed to some late stage “nucleosynthesis” and the heating of a dust cloud. In addition, implications on the early thermal evolution of iron meteorites are presented based on ¹⁰⁷Pd decay and models of the cooling history.     

Interstellar organic matter in meteorites

Hydrogen which is highly enriched in deuterium is present in organic matter in a variety of meteorites including non-carbonaceous chondrites. The concentrations of this hydrogen are quite large. For example Renazzo contains 140 μmoles/g of the 10,000‰ δD hydrogen. The $\text{D}\text{H}$ ratios of hydrogen in the organic matter vary from 8 × 10^?5 to 170 × 10^?5 (δD ranges from ? 500‰ to 10,000‰) as compared to 16 × 10^?5 for terrestrial hydrogen and 2 × 10^?5 for cosmic hydrogen. The majority of the unequilibrated primitive meteorites contain hydrogen whose $\text{D}\text{H}$ ratios are greater than 30 × 10^?5. If the $\text{D}\text{H}$ ratios in these compounds were due to enrichment relative to cosmic hydrogen by isotope exchange reactions, it would require that these reactions take place below 150 K. In addition the organic compounds having $\text{D}\text{H}$ ratios above 50 × 10^?5 would require temperatures of formation of < 120 K. These types of deuterium enrichments must take place by ion-molecule reactions in interstellar clouds where both ionization and low temperatures exist. Astronomically observed $\text{D}\text{H}$ ratios in organic compounds in interstellar clouds are typically 180 × 10^?5 and range between about 40 × 10^?5 and 5000 × 10^?5. The $\text{D}\text{H}$ values we have determined are the lower limits for the organic compounds derived from interstellar molecules because all processes subsequent to their formation, including terrestrial contamination, decrease their $\text{D}\text{H}$ ratios.In contrast, the $\text{D}\text{H}$ ratios of hydrogen associated with hydrated silicates are relatively uniform for the meteorites we have analyzed with an average value of 14 × 10^?5; very similar to the terrestrial value. These phyllosilicates values suggest equilibration of H₂O with H₂ in the solar nebula at temperatures of about 200 K and higher.The ${}^{13}\text{C}{}^{12}\text{C}$ ratios of organic matter, irrespective its $\text{D}\text{H}$ ratio, lie well within those observed for the earth. If organic matter originated in the interstellar medium, our data would indicate that the ${}^{13}\text{C}{}^{12}\text{C}$ ratio of interstellar carbon five billion years ago was similar to the present terrestrial value.Our findings suggest that other interstellar material, representing various inputs from various stars, in addition to the organic matter is preserved and is present in the meteorites which contain the high $\text{D}\text{H}$ ratios. We feel that some elements existing in trace quantities which possess isotopic anomalies in the meteorites may very well be such materials.     

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.     

3He4He ratio,noble gas abundance and K-Ar dating of diamonds—An attempt to search for the records of early terrestrial history

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.     

40Ar39Ar dating,Ar diffusion properties,and cooling rate determinations of severely shocked chondrites

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.     

The 21Ne production rate in stony meteorites estimated from 10Be and other radionuclides

The ¹⁰Be contents of 28 stony meteorites with known ²¹Ne contents range from 0.97 to 23 dpm/kg and give an average ²¹Ne production rate (P₂₁) of (0.28 ± 0.02) × 10⁸ cm³ STP/g-Myr for shielding conditions corresponding to ${}^{22}\text{Ne}{}^{21}\text{Ne}\text{= 1.114}$ in an H-chondrite. Our $\text{P}{}_{21}\text{(}{}^{10}\text{Be)}$ agrees with others' P₂₁ based on ²²Na, ⁸¹Kr and ⁵³Mn but not on ²⁶A1. Temporal variations in the cosmic ray flux do not explain the disagreement satisfactorily; major errors in the radionuclide half-lives are not indicated. The discrepancy seems rooted in the data selection and the difficulties of making accurate corrections for shielding, chemical composition and other sources of variability.     

A carbonaceous inclusion from the Krymka LL-chondrite: noble gases and trace elements

A black inclusion from the Krymka LL3 chondrite was analyzed for 20 trace elements and five noble gases, by radiochemical neutron activation and mass spectrometry. The trace element pattern somewhat resembles that of C1 or C2 chondrites, but with several unique features. Elements of nebular condensation T ? 1000 K (U, Re, Os, Ir, Ni, Pd, Au, Sb and Ge) are essentially undepleted, as in C1 chondrites, but $\text{Re}\text{Ir}$ is 1.49 × higher than the characteristic Cl value. Among elements condensing below 1000 K, Cs, Se, Te, and In are depleted to approximately C2 levels (~0.6 × C1), whereas Ag, Bi, Tl are enriched to ~ 1.6 × C1. Such enrichments are thought to be characteristic of late nebular condensates.The noble-gas pattern also is unique. Gas contents are higher than in C1s, by factors of 2.6 to 19 for Ne through Xe. The $\text{Ar}{}^{36}\text{Xe}{}^{132}$ ratio of 500 is higher than mean values for C1s or C2s (109 or 89) and exceeds even the highest value seen in C3Os, 420, whereas the $\text{He}{}^4\text{Ne}{}^{20}$ ratio of 62 is much lower than the values for C1s and C2s (200–370). The $\text{Xe}{}^{129}\text{Xe}{}^{132}$ and $\text{Xe}{}^{136}\text{Xe}{}^{\mathrm{l32}}$ ratios of 1.040 and 0.320 resemble those of C1 chondrites, and seem to imply typical proportions of radiogenic Xe¹²⁹ and ‘fissiogenic’ xenon.It appears that the inclusion represents a new primitive meteorite type, similar to C-chondrites, but probably a late condensate from a region of higher nebular pressure.     

He,Ne and Ar isotopes in inclusions of some iron meteorites

He³, He⁴, Ne²¹ and Ar³⁸ contents were determined in 18 metal, troilite, sehreibersite and graphite inclusions of 9 iron meteorites, by total outgassing and stepwise heating. The $\text{He}{}^4\text{He}{}^3$ ratio in metal phase ranges from 3.85 to 4.65, but in non-metallic samples, from 6.70 to 30.5. The results for cosmogenic isotopes of helium, neon and argon disagree appreciably with data on accelerator-irradiated targets. It should be noted, however, that some inclusions have lost considerable amounts of gas by diffusion.Uranium contents of 22 troilite and sehreibersite samples were determined by the fission track technique. The average uranium content of troilite is 0.4-0.7 ppb. Excess He⁴ of unknown origin was observed in troilite inclusions. If one assumes that the excess He⁴ was produced by uranium decay in situ, then the apparent U-He⁴ age is at least 5.9 × 10⁹ yr.     

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.     

Rare gases and 36Cl in stony-iron meteorites: cosmogenic elemental production rates,exposure ages,diffusion losses and thermal histories

Metal and silicate portions from 13 mesosiderites, one pallasite, Bencubbin (“unique”) and Udei Station (‘iron with silicate inclusions’) have been analysed for their content of He, Ne and Ar; in most cases ³⁶Cl could be determined as well. ³⁶Cl-³⁶Ar cosmic ray exposure ages fall between 10 and 160 Myr. Half of the metal samples show a deficit of spallogenic ³He (up to 30%) which we ascribe to a loss of tritium. The observed depletion of ³He in the silicates is correlated with their mineralogical composition: feldspar has lost its ³He in all cases, pyroxene definitely in one and possibly in five others, while olivine has been affected in only two meteorites. The thermal histories during their exposure to the cosmic radiation have been different for different meteoroids. Nevertheless, with the exception of Veramin, the data are compatible with the assumption of a continuous diffusion loss during a considerable fraction of the exposure era. For Veramin, however, an episodic event late in the exposure history is required. The exceptionally high ${}^{39}\text{Ar}{}^{36}\text{Cl}$ ratio in the metal, which is due to a high ³⁹Ar activity, indicates that the event occurred during the last 500,000 years or so and resulted in an extremely excentric orbit (large aphelion).Production rates of ^38,39Ar from Ca and ^21,22Ne from Mg are given. The ratio $\text{P}{}^{38}{}_{\mathrm{Ca}}\text{P}{}^{21}{}_{\mathrm{Mg}}$ is close to unity. The ratios $\text{P}{}^{38}{}_{\mathrm{Ca}}\text{P}{}^{38}{}_{\mathrm{Fe}}$ vary between 20 and 50, and are not correlated with the absolute production rate of ³⁸Ar from metal. The ${}^{22}\text{Ne}{}^{21}\text{Ne}$ production ratio from Mg is found to be close to but below unity.Of the mesosiderites only Veramin shows unambiguous evidence for primordial rare gases with larger amounts and a higher ${}^{20}\text{Ne}{}^{36}\text{Ar}$ ratio in the olivine, suggesting in situ fractionation to have at least been partly responsible for the abundance pattern found. Bencubbin contains large amounts of strongly fractionated primordial gases, but again part of the fractionation may have occurred in situ. Udei Station shows an excess of (3.5 ± 0.6) × 10^?10 cm³ STP ¹²⁹Xe/g in the non-magnetic portion.     

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.     

Half-life of 92Nb

The long-lived nuclide ⁹²Nb together with ⁹¹Nb and ⁹⁴Nb were produced from Mo by neutron irradiation. The activities of the nuclides were determined by γ spectroscopy and the atomic abundances were determined by mass spectrometry. Intercomparison of ⁹²Nb and ⁹⁴Nb activities and abundances yielded a value for half-life $\text{(}{}^{92}\text{Nb) = (3.3 ± 0.5) × 10}{}^7$ yr based on a value for half-life $\text{(}{}^{94}\text{Nb) = 2.0 × 10}{}^4$ yr. The same value was obtained within errors from absolute counting data and dilution analysis.     

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

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.     

FUN with PANURGE: High mass resolution ion microprobe measurements of Mg in Allende inclusions

The performance characteristics of PANURGE, a modified CAMECA IMS3F ion microprobe, have been studied at a mass resolving power of 5000 for the purpose of determining isotopic ratios at a precision level approaching that of counting statistics using beam switching. The techniques used for this type of measurement are described. Using this approach, the isotopic composition of Mg and Si and the atomic ratio of $\text{Al}\text{Mg}$ in minerals from the Allende inclusion WA and the Allende FUN inclusion Cl have been measured with the ion microprobe at high mass resolving power. Enrichments in ²⁶Mg of up to 260%. have been found. Mg and $\text{Al}\text{Mg}$ measurements on cogenetic spinel inclusions and host plagioclase crystals yield Mg-Al isochrons in excellent agreement with precise mineral isochrons determined by thermal emission mass spectrometry. The measurements confirm the presence of substantial excess ²⁶Mg in WA (${}^{26}\text{Mg}{}^1{}^{27}\text{Al = 5 × 10}{}^{\mathrm{?5}}$) and its near absence in Cl (${}^{26}\text{Mg}{}^1{}^{27}\text{Al}\text{< 4 × 10}{}^{\mathrm{?6}}$). In WA plagioclase, data for which ${}^{27}\text{Al}{}^{24}\text{Mg}\text{= 300 to 1000}$ define a linear array with ${}^{26}\text{Mg}{}^1{}^{27}\text{Al}\text{= 3 × 10}{}^5$ and with initial ${}^{26}\text{Mg}{}^{24}\text{Mg}$ composition 30%. greater than in high Mg phases. This suggests a metamorphic reequilibration of Mg in Allende plagioclase at least 0.6 my after WA formation. There were no variations in detected ${}^{26}\text{Mg}{}^1{}^{27}\text{Al}$ in WA plagioclase associated with concentration of ²⁶Mg¹ into isolated clusters. We have confirmed by ion probe measurements that the Mg composition in Allende Cl is highly fractionated and is uniform among pyroxene, melilite, plagioclase, spinel crystals and spinel included in melilite and plagioclase crystals. Likewise, the Si composition is mass fractionated and is the same in pyroxene, melilite and plagioclase.     

Diffusivity of oxygen in jadeite and diopside melts at high pressures

The diffusivity of oxygen was determined in melts of Jadeite (NaAlSi₂O₆) and diopside (CaMgSi₂O₆) compositions using diffusion couples with ¹⁸O as a tracer. In the Jadeite melt, the diffusivity of oxygen increases from $\text{6.87}{}_{\mathrm{?0.25}}{}^{\mathrm{+0.28}}\text{× 10}{}^{\mathrm{?10}}\text{cm}{}^2\text{/}\text{sec}$ at 5 Kb to $\text{1.32 ± 0.08 × 10}{}^{\mathrm{?9}}\text{cm}{}^2\text{/}\text{sec}$ at 20 Kb at constant temperature (1400°C), whereas in the diopside melt at 1650°C, the diffusivity decreases from $\text{7.30}{}_{\mathrm{?0.18}}{}^{0.29}\text{× 10}{}^{\mathrm{?7}}\text{cm}{}^2\text{/}\text{sec}$ at 10 Kb to $\text{5.28}{}_{\mathrm{?0.55}}{}^{\mathrm{+0.60}}\text{× 10}{}^{\mathrm{?7}}\text{cm}{}^2\text{/}\text{sec}$ at 17 Kb. These results demonstrate that the diffusivity is inversely correlated with the viscosity of the melt. For the jadeite melt, in particular, the inverse correlation is very well approximated by the Eyring equation using the diameter of oxygen ions as a unit distance of translation, suggesting that the viscous flow is rate-limited by the diffusion of individual oxygen ions. In the diopside melt, the activation volume is slightly greater than the molar volume of oxygen ion, indicating that the individual oxygen ion is the diffusion unit. The negative activation volume obtained for the jadeite melt is interpreted as the volume decrease associated with a diffusive jump of an oxygen ion due to local collapse of the network structure.     

Stability of ethylxanthate ion in neutral and weakly acidic media. Part 1: Influence of pH

Xanthates are used in the flotation of sulfide ores although their aqueous solutions are not stable under certain conditions. Their stability in acidic and weakly acidic aqueous solutions was therefore investigated, as these media are required for some processes.The peak absorbances of ethylxanthate ion and carbon disulfide were first determined in aqueous solution. The decomposition of ethylxanthate ion was analyzed by measuring variations in absorbance (at 301 nm) and pH with respect to time. A pH regulation system was then used while measuring variations in absorbance and productions of protons caused by xanthate decomposition.The results concerning xanthate half-lives show good agreement with the literature, but the kinetic results deviate substantially. The following relation was obtained for half-life:

$\text{T}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{=9.67×10}{}^{\mathrm{?6}}\text{(pH)}{}^{11}\text{;4?7;T}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{in seconds}$

We established that ethylxanthate decomposition at pH 4 is a first order reaction with respect to ethylxanthate concentration, and postulating this order to the other pH values, the following kinetic relation was found:

$\text{v= ?(1.22×10}{}^4\text{[H}{}^{\mathrm{+}}\text{]?1.36×10}{}^{\mathrm{?2}}\text{)([}\text{EtX}{}^{\mathrm{?}}\text{]}{}_{\mathrm{\infty }}\text{) (4?pH?7)}$

where v is the rate of decomposition (mol l^?1 min^?1), and [EtX^?]_∞ is the ethylxanthate concentration when the decomposition equilibria are reached (mol l^?1). The better concentration was found to obey the law:

$\text{[}\text{EtX}{}^{\mathrm{?}}\text{]}{}_{\mathrm{\infty }}\text{=3.142×10}{}^{\mathrm{?5}}\text{pH ? 1.255 × 10}{}^{\mathrm{?4}}\text{(4?pH?6)}$

     

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

The geochemical evolution of the Pleistocene Lake Lisan-Dead Sea system

The geochemical history of Lake Lisan, the Pleistocene precursor of the Dead Sea, has been studied by geological, chemical and isotopic methods.Aragonite laminae from the Lisan Formation yielded (equivalent) Sr/Ca ratios in the range 0.5 × 10^?2?1 × 10^?2, Na/Ca ratios from 3.6 × 10^?3 to 9.2 × 10^?3, $\text{δ}{}^{18}\text{O}{}_{\mathrm{PDB}}$ values between 1.5 and 7%. and $\text{δ}{}^{13}\text{C}{}_{\mathrm{PDB}}$ from ?7.7 to 3.4%..The distribution coefficient of Na⁺ between aragonite and aqueous solutions, $\text{λ}{}^{\mathrm{A}}{}_{\mathrm{Na}}$, is experimentally shown to be very sensitive to salinity and nearly temperature independent. Thus, Na/Ca in aragonite serves as a paleosalinity indicator.Sr/Ca ratios and $\text{δ}{}^{18}\text{O}$ values in aragonite provide good long-term monitors of a lake's evolution. They show Lake Lisan to be well mixed, highly evaporated and saline. Except for a diluted surface layer, the salinity of the lake was half that of the present Dead Sea (15 vs 31%).Lake Lisan evolved from a small, yet deep, hypersaline Dead Sea-like, water body. This initial lake was rapidly filled-up to its highest stand by fresh waters and existed for about 40,000 yr before shrinking back to the present Dead Sea. The chemistry of Lake Lisan at its stable stand represented a material balance between a Jordan-like input, an original large mass of salts and a chemical removal of aragonite. The weighted average depth of Lake Lisan is calculated, on a geochemical basis, to have been at least 400, preferably 600 m.The oxygen isotopic composition of Lake Lisan water, which was higher by at least 3%. than that of the Dead Sea, was probably dictated by a higher rate of evaporation.Na/Ca ratios in aragonite, which correlate well with $\text{δ}{}^{13}\text{C}$ values, but change frequently in time, reflect the existence of a short lived upper water layer of varying salinity in Lake Lisan.     

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

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.