Supernova-driven outflows and chemical evolution of dwarf spheroidal galaxies.

We present a general phenomenological model for the metallicity distribution (MD) in terms of [Fe/H] for dwarf spheroidal galaxies (dSphs). These galaxies appear to have stopped accreting gas from the intergalactic medium and are fossilized systems with their stars undergoing slow internal evolution. For a wide variety of infall histories of unprocessed baryonic matter to feed star formation, most of the observed MDs can be well described by our model. The key requirement is that the fraction of the gas mass lost by supernova-driven outflows is close to unity. This model also predicts a relationship between the total stellar mass and the mean metallicity for dSphs in accord with properties of their dark matter halos. The model further predicts as a natural consequence that the abundance ratios [E/Fe] for elements such as O, Mg, and Si decrease for stellar populations at the higher end of the [Fe/H] range in a dSph. We show that, for infall rates far below the net rate of gas loss to star formation and outflows, the MD in our model is very sharply peaked at one [Fe/H] value, similar to what is observed in most globular clusters. This result suggests that globular clusters may be end members of the same family as dSphs.

Sm-nd and rb-sr chronology of continental crust formation.

Samarium-neodymium and rubidium-strontium isotopic systematics together with plausible assumptions regarding the geochemical evlution of continental crust material, have been used to ascertain the times at which segments of continental crust were formed. Analyses of composites from the Canadian Shield representing portions of the Superior, Slave, and Churchill structural provinces indicate that these provinces were all formed within the period 2.5 to 2.7 aeons. It has been possible to determine the mean age of sediment provenances, as studies of sedimentary rocks suggest that the samarium-neodymium isotopic system is not substantially disturbed during sedimentation or diagenesis.

Isotopic composition of neodymium in waters from the drake passage.

The isotopic composition of neodymium has been determined in seawaters from the Drake Passage. The Antarctic Circumpolar Current, which controls interocean mixing, flows through this passage. The parameter epsilon(Nd)(0) which is a function of the ratio of neodymium-143 to neodymium-144, is found to be uniform with depth at two stations with a value which is intermediate between the values for the Atlantic and the Pacific and indicates that the Antarctic Circumpolar current consists of about 70 percent Atlantic water. Cold bottom water from a site in the south central Pacific has the neodymium isotopic signature of the waters in the Drake Passage. By using a box model to describe the exchange of water between the Southern Ocean and the ocean basins to the north together with the isotopic results, an upper limit of approximately 33 million cubic meters per second is calculated for the rate of exchange between the Pacific and the Southern Ocean. Concentrations of samarium and neodymium were also determined and found to increase approximately linearly with depth. These results suggest that neodymium may be a valuable tracer in oceanography and may be useful in paleo-oceanographic studies.

Potassium-feldspar phenocrysts in the surface of colomera, and iron meteorite.

Silicate aggregates, including large single crystals of potassium feldspar as long as 11 centimeters and sodium feldspar, are embeded in the surface of the medium octahedrite Colomera. Silicate nodules in the interior appear to be much smaller (about 0.3 centimeter). Glass nodules are abundant both on the external surface and in the interior. These observations are evidence that some iron meteorites formed as segregations within a silicate matrix and did not originate in a metallic core.

Gas-retention and cosmic-ray exposure ages of lunar rock 15555.

The last lava flow in the Hadley Rille area of Mare Imbrium, as inferred from an argon-40-argon-39 experiment on a plagioclase separate from the lunar basalt 15555, occurred 3.31+/-0.03x10(9) years ago. An argon-40-argon-39 experiment on a whole rock sample shows significant loss of radiogenic argon-40 and yields a well-defined, high-temperature plateau indicating a lower age of 3.22+/-0.03x10(9) years. A cosmic-ray exposure age of 90+/-10x10(6) years is determined from the ratio of spallogenic argon-38 to calcium.

Thorium-uranium fractionation by garnet: evidence for a deep source and rapid rise of oceanic basalts.

Mid-ocean ridge basalts (MORBs) and ocean island basalts (QIBs) are derived by partial melting of the upper mantle and are marked by systematic excesses of thorium-230 activity relative to the activity of its parent, uranium-238. Experimental measurements of the distribution of thorium and uranium between the melt and solid residue show that, of the major phases in the upper mantle, only garnet will retain uranium over thorium. This sense of fractionation, which is opposite to that caused by clinopyroxene-melt partitioning, is consistent with the thorium-230 excesses observed in young oceanic basalts. Thus, both MORBs and QIBs must begin partial melting in the garnet stability field or below about 70 kilometers. A calculation shows that the thorium-230-uranium-238 disequilibrium in MORBs can be attributed to dynamic partial melting beginning at 80 kilometers with a melt porosity of 0.2 percent or more. This result requires that melting beneath ridges occurs in a wide region and that the magma rises to the surface at a velocity of at least 0.9 meter per year.

Precise timing of the last interglacial period from mass spectrometric determination of thorium-230 in corals.

The development of mass spectrometric techniques for determination of (230)Th abundance has made it possible to reduce analytical errors in (238)U-(234)U-(230)Th dating of corals even with very small samples. Samples of 6 x 10(8) atoms of (230)Th can be measured to an accuracy of +/-3 percent (2sigma) and 3 x 10(10) atoms of (230)Th can be measured to an accuracy of +/-0.2 percent. The time range over which useful age data on corals can be obtained now ranges from about 50 to about 500,000 years. For young corals, this approach may be preferable to (14)C dating. The precision with which the age of a coral can now be determined should make it possible to critically test the Milankovitch hypothesis concerning Pleistocene climate fluctuations. Analyses of a number of corals that grew during the last interglacial period yield ages of 122,000 to 130,000 years. The ages coincide with, or slightly postdate, the summer solar insolation high at 65 degrees N latitude which occurred 128,000 years ago. This supports the idea that changes in Pleistocene climate can be the result of variations in the distribution of solar insolation caused by changes in the geometry of the earth's orbit and rotation axis.

Magnesium isotopic composition of interplanetary dust particles.

The magnesium isotopic composition of some extraterrestrial dust particles has been measured. The particles are believed to be samples of interplanetary dust, a significant fraction of which originated from the disaggregation of comets and may contain preserved isotopic anomalies. Improvements in mass spectrometric and sample preparation techniques have made it possible to measure the magnesium isotopic composition of the dust particles, which are typically 10 micrometers in size and contain on the order of 10(-10) gram of magnesium. Of the 13 samples analyzed, nine have the terrestrial magnesium isotopic composition within 2 parts per thousand, and one shows isotopic mass fractionation of 1.1 percent per mass unit. A subset of the particles, described as chondritic aggregates, are very close to normal isotopic composition, but their normalized isotopic ratios appear to show nonlinear effects of 3 to 4 parts per thousand, which is near the present limit of detection for samples of this size. The isotopic composition of calcium was also determined in one particle and found to be normal within 2 percent. It is clear that the isotopic composition of interplanetary dust particles can be determined with good precision. Collection of dust particles during the earth's passage through a comet tail or an intense meteor stream may permit laboratory analysis of material from a known comet.

Presolar corundum and spinel in ordinary chondrites: origins from AGB stars and a supernova.

On the basis of anomalous isotopic compositions of oxygen and magnesium, 14 oxide grains from two primitive meteorites (Bishunpur and Semarkona) have been identified as circumstellar condensates. One corundum grain has a high 18O/16O ratio and isotopic compositions of magnesium, calcium, and titanium that are compatible with a formation in ejecta of a type II supernova that was about 15 times the mass of the sun. The other grains have oxygen, magnesium, and titanium compositions that are consistent with a formation around asymptotic giant branch (AGB) stars with a range of mass and initial composition. The large range of aluminum/magnesium in circumstellar corundum and spinel is considered to reflect various stages of back-reaction between condensed corundum and gaseous magnesium in cooling stellar ejecta.

Ages, irradiation history, and chemical composition of lunar rocks from the sea of tranquillity.

The (87)Rb-(87)Sr internal isochrons for five rocks yield an age of 3.65 +/-0.05 x 10(9) years which presumably dates the formation of the Sea of Tranquillity. Potassium-argon ages are consistent with this result. The soil has a model age of 4.5 x10(9) years, which is best regarded as the time of initial differentiation of the lunar crust. A peculiar rock fragment from the soil gave a model age of 4.44 x 10(9) years. Relative abundances of alkalis do not suggest differential volatilization. The irradiation history of lunar rocks is inferred from isotopic measurements of gadolinium, vanadium, and cosmogenic rare gases. Spallation xenon spectra exhibit a high and variable (131)Xe/(126)Xe ratio. No evidence for (129)I was found. The isotopic composition of solar-wind xenon is distinct from that of the atmosphere and of the average for carbonaceous chondrites, but the krypton composition appears similar to average carbonaceous chondrite krypton.

A two-reservoir recycling model for mantle-crust evolution.

The exact solutions for the isotopic compositions and the concentrations of the two-reservoir model for mantle-crust evolution are given for arbitrary rates of crustal growth and of back flow to the mantle. The critical parameters are the chemical fractionation factors for crustal growth and refluxing and the integrated fractional mass-removal rates from the crust and the mantle. For the case where refluxing is proportional to crustal growth, all the solutions reduce to simple analytic expressions. The expression for the mean age of the mass of the crust with refluxing is given. If refluxing is significant, the model shows that highly incompatible elements have short residence times in the mantle. With plausible concentration values, material balance implies that the continents were derived from only a small fraction of the mantle.

Neodymium isotopes in flood basalts from the Siberian Platform and inferences about their mantle sources.

The initial isotopic compositions of Nd and Sr in basalts from the Central Siberian Plateau and other major continental flood basalts are reported. The continental flood basalts appear to be the product of partial melting of mantle sources that consist of relatively primitive undifferentiated material and are clearly distinct from midocean ridge basalts, which sample mantle reservoirs that have been modified by extraction of continental crust earlier in earth history. These observations provide fundamental constraints on models of mantle structure and dynamics. Isotopic effects of crustal contamination are clearly recognizable in some continental flood basalts, but these effects can be distinguished from isotopic patterns inherited from the mantle magma sources.

Models of earth structure inferred from neodymium and strontium isotopic abundances.

A simplified model of earth structure based on the Nd and Sr isotopic characteristics of oceanic and continental tholeiitic flood basalts is presented, taking into account the motion of crustal plates and a chemical balance for trace elements. The resulting structure that is inferred consists of a lower mantle that is still essentially undifferentiated, overlain by an upper mantle that is the residue of the original source from which the continents were derived.

Determination of iridium in natural waters by clean chemical extraction and negative thermal ionization mass spectrometry.

Methods for the precise, routine measurement of Ir in seawater, riverwater, and estuarine water using isotope dilution negative thermal ionization mass spectrometry (ID-NTIMS) have been developed. After equilibration with a (191)Ir-enriched spike, Ir is separated from solution by coprecipitation with ferric hydroxide, followed by anion exchange chromatography using a reductive elution technique. UV irradiation is employed for the decomposition of trace organics, which interfere with negative ion production. IrO(2)(-) ions are produced in the mass spectrometer by heating the sample on a Ni-wire filament in the presence of Ba(OH)(2). Detection efficiencies ranged from 0.1% to 0.3%. We have used these procedures to determine the concentrations of Ir in 4 kg samples from the Pacific Ocean, the Atlantic Ocean, the Baltic Sea, and the rivers supplying the Baltic. Our chemical procedures introduce a total blank of ∼2 × 10(8) atoms per sample. The distribution of Ir in the oceans is fairly uniform, averaging ∼4 × 10(8) atoms kg(-)(1). The concentrations in the rivers supplying the Baltic Sea range from (17.4 ± 0.9) × 10(8) for a pristine river to (92.9 ± 2.2) × 10(8) atoms kg(-)(1) for a polluted river. The distribution, speciation, and transport of Ir in natural waters can now be subjected to intensive study.

Diffusion of water in rhyolitic glasses.

Water dehydration experiments on rhyolitic glasses have been carried out at 400-550 degrees C under a N2 atmosphere. Concentration profiles of both H2O molecules and OH groups were measured by Fourier transform infrared spectroscopy. As found in previous studies of water diffusion in rhyolitic melts, the measured total water concentration profiles do not match expectations based on a single constant diffusion coefficient for total water. The diffusion of total water is described by considering the diffusion of both H2O molecules and OH groups and the reaction between them. The concentration relationship between the two species has been obtained from direct infrared measurement on quenched experimental charges. The quench is inferred to be rapid enough to preserve concentrations of both species at experimental temperature based on experimental results designed to examine reaction kinetics. The measured species concentrations along diffusion profiles show that local equilibrium between H2O and OH is approximately reached at high temperatures and high water contents. However, at lower water content or lower temperature, local equilibrium is not reached. In treating the diffusion problem, this disequilibrium effect is partially compensated by using empirical relationships between H2O and OH concentrations based on measurements, instead of using an equilibrium relationship. It is thus possible to obtain diffusion coefficients for both species from their concentration profiles. The diffusion coefficient of OH is found to be negligible compared to that of H2O at 403-530 degrees C (DOH < 0.02 DH2O and could be much smaller); i.e., H2O is the dominant diffusing species even at total water concentration as low as 0.2 wt%. The variation of OH concentration along the diffusion profile is inferred to be due to the local interconversion between OH groups and H2O molecules; the reaction also provides the diffusing H2O species. DH20 values are found to vary by less than a factor of 2 over a total water concentration range of 0.2 to 1.7 wt%. This simple model, coupled with the assumption of local equilibrium between H2O and OH, yields a very good fit to the data from diffusion-couple experiments of LAPHAM et al. (1984) at 850 degrees C. When our data are combined with DH2O obtained from that fit, DH2O (in m2/s) is given by: ln DH2O = (-14.59 +/- 1.59) - (103000 +/- 5000) / RT; 673 K < or = T < or = 1123 K, where T is temperature in K and R is the gas constant in J K-1 mol-1. This equation also approximates well DH2O values calculated from previous measurements of concentration-dependent bulk water diffusion coefficients of KARSTEN et al. (1982). The diffusion of H2O is also compared to the diffusion of the noble gas elements. The activation energy for diffusion in rhyolitic glasses is well correlated with neutral species radii of He, Ne, H2O, and Ar. This supports the contention that the diffusing species for "water" is neutral molecular H2O. The role of speciation may also be important in understanding the diffusion of many other multi-species components, and the effect can be treated in a similar fashion as that during water diffusion.

Diffusion of a multi-species component and its role in oxygen and water transport in silicates.

An important but poorly understood factor that affects diffusion rates is the role of speciation during diffusion of a multi-species component. The diffusion of such a component is complicated by the different diffusion coefficient of each species and the interconversion reactions among the species. These complexities can be treated by a diffusion equation that incorporates the diffusive fluxes of all species contributing to the concentration of the component. The effects of speciation on the diffusion of the component can be investigated experimentally in some simple cases by measuring concentration profiles of all species developed during diffusion experiments or by studying some of their other consequences. Experimental data on water diffusion in rhyolitic glasses indicate that although dissolved water is present as two species, H2O molecules and OH groups, molecular H2O is the dominant diffusing species at very low to high water concentrations. This explains the apparently complex behavior of water diffusion. Experimental data on oxygen diffusion in some silicates using 18O tracers in the form of H2(18O) are consistent with the idea that 18O transport is dominated by diffusion of H2O molecules even at lower water contents (ppm or less). This explains why oxygen transport depends on the presence of water and generally depends on water fugacity linearly. For this mode of oxygen transport, there is a simple theoretical relationship between the effective total oxygen diffusion coefficient and the total water diffusion coefficient that is a function of only the water concentration of the silicate at low water content. This relationship appears to describe quantitatively the existing data over a wide range in water contents and diffusion coefficients in several phases.

Correlated Si isotope anomalies and large 13C enrichments in a family of exotic SiC grains.

A suite of morphologically distinctive silicon carbide (SiC) grains from the Orgueil and Murchison carbonaceous chondrite meteorites contains Si and C of highly anomalous isotopic composition. All of the SiC grains in this suite are characterized by a distinctive platy morphology and roughly developed hexagonal crystal forms that allow them to be distinguished from other types of SiC found in the host meteorites. The delta 29Si and delta 30Si values of individual SiC crystals deviate from those of normal solar material by more than 100%, while the delta 13C values range from 150 to 5200%. Isotopically normal C and Si are not found in any of these SiC crystals. The SiC grains belonging to this morphological suite are isotopically distinct from fine-grained SiC aggregates and other morphological types of SiC in unequilibrated meteorites. The 29Si/28Si and 30Si/28Si ratios of these platy grains are well correlated and define a linear array that does not pass through the composition of normal, solar Si. This behavior contrasts sharply with the diverse and poorly correlated Si isotopic compositions shown by the total SiC population. We suggest that the distinctive morphological characteristics and comparatively simple Si isotope systematics identify the platy SiC crystals as a genetically related family, formed around a single, isotopically heterogeneous presolar star or an association of related stars. The enrichments in 13C and the Si isotope systematics of the platy SiC are broadly consistent with theoretical models of nucleosynthesis in low-mass, carbon stars on the asymptotic giant branch. The Si isotope array most plausibly reflects mixing between 28Si-rich material, inherited from a previous generation of stars, and material enriched in 29Si and 30Si, produced in intershell regions by neutron capture during He-burning. 13C is also produced in intershell regions by proton reactions on 12C seed nuclei and is carried with s-process nuclei to the stellar envelope by convection which penetrates down to the He shell. The absence of a correlation between the Si and C isotopic compositions of the SiC suggests either episodic condensation of SiC, extending over several thermal pulses, in the atmosphere of a single star, or derivation of the SiC from several stars characterized by different rates of 13C production. In the multiple star scenario, the linear correlation of the 29Si/28Si and 30Si/28Si ratios among the platy SiC indicates that these stars evolved from a common Si seed composition under similar conditions of neutron-capture nucleosynthesis. The 29Si/30Si ratio of the SiC, inferred by us to be produced by neutron capture in the stellar interior, is distinct from values calculated from models of nucleosynthesis in AGB stars.