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Calcium–aluminum-rich inclusions (CAIs) are primitive objects that formed within the protoplanetary disk surrounding the young Sun. Recent Pb–Pb chronologic studies have demonstrated that CAIs are the oldest solar system solids, crystallizing 4567 Ma ago ( Amelin et al., 2002 , Connelly et al., 2012 ). The isotope systematics of CAIs therefore provide critical insight into the earliest history of the Solar System. Although Sm–Nd and Rb–Sr geochronometers are highly effective tools for investigating cosmochemical evolution in the early Solar System, previous studies of CAIs have revealed evidence for isotopically disturbed systems. Here we report new age data for Allende CAI Al3S4 derived from both the long-lived (147Sm–143Nd) and short-lived (146Sm–142Nd) isotopic systems. The 147Sm–143Nd chronometer yields an age of 4560 ± 34 Ma that is concordant with 207Pb–206Pb ages for CAIs and indicates that the Sm–Nd system was not significantly disturbed by secondary alteration or nucleosynthetic processes. The slope of the 146Sm–142Nd isochron defines the Solar System initial 146Sm/144Sm of 0.00828 ± 0.00044 . This value is significantly different from the value of 0.0094 determined by Kinoshita et al. (2012) . Ages recalculated from all published 146Sm–142Nd isochron data using the traditional 103 Ma half-life and the initial 146Sm/144Sm value determined here closely match Pb–Pb and 147Sm–143Nd ages determined on the same samples. In contrast, ages recalculated using the 68 Ma half-life determined by Kinoshita et al. (2012) and either of the initial 146Sm/144Sm values are often anomalously old. This is particularly true for the youngest samples with 146Sm–142Nd isochron ages that are most sensitive to the choice of 146Sm half-life used in the age calculation. In contrast to the Sm–Nd isotope system, the Rb–Sr system is affected by alteration but yields an apparent isochron with a slope corresponding to a much younger age of 4247 ± 110 Ma . Although the Rb–Sr system in CAIs appears to be disturbed, the initial 87Sr/86Sr value determined from the isochron is 0.698942 ± 0.000008 , and closely approximates estimates of the initial Solar System value. Although this isochron may be a mixing line, it might also record alteration on the Allende parent body in which Rb was added to the Al3S4 CAI that was initially largely devoid of Rb.

Oxygen isotope and trace element data for 13 samples of the Kaidun chondritic breccia reaffirm the complex polymict nature of this unique meteorite. Bulk Kaidun samples most closely resemble CR chondrites, but the matrix is CI-like. Two separated clasts are CR-like but have some properties that resemble CM, two clasts are enstatite chondrites (one EL and one EH), one clast is an aubrite-like metal-rich impact melt, and one clast is a unique layered olivine-bearing pyroxenite with the isotopic composition of an aubrite. Yet, although each clast resembles a known meteorite group, all deviate in some respect from the norms for those groups. Collectively, Kaidun has sampled materials not yet represented in the world meteorite collections and which greatly extend the definitions of known meteorite groups. Phyllosilicates in Kaidun span a very wide range in composition and vary from clast to clast, suggesting that the aqueous alteration experienced by the clasts predated assembly of the Kaidun parent body.

Kalahari 008 and 009 are two lunar meteorites that were found close to each other in Botswana. Kalahari 008 is a typical lunar anorthositic breccia; Kalahari 009 a monomict breccia with basaltic composition and mineralogy. Based on minor and trace elements Kalahari 009 is classified as VLT (very-low-Ti) mare basalt with extremely low contents of incompatible elements, including the REE. The Lu–Hf data define an age of 4286 ± 95 Ma indicating that Kalahari 009 is one of the oldest known basalt samples from the Moon. It provides evidence for lunar basalt volcanism prior to 4.1 Ga (pre-Nectarian) and may represent the first sample from a cryptomare. The very radiogenic initial 176Hf/177Hf (eHf = +12.9 ± 4.6), the low REE, Th and Ti concentrations indicate that Kalahari 009 formed from re-melting of mantle material that had undergone strong incompatible trace element depletion early in lunar history. This unusually depleted composition points toward a hitherto unsampled basalt source region for the lunar interior that may represent a new depleted endmember source for low-Ti mare basalt volcanism. Apparently, the Moon became chemically very heterogeneous at an early stage in its history and different cumulate sources are responsible for the diverse mare basalt types. Evidence that Kalahari 008 and 009 may be paired includes the similar fayalite content of their olivine, the identical initial Hf isotope composition, the exceptionally low exposure ages of both rocks and the fact that they were found close to each other. Since cryptomaria are covered by highland ejecta, it is possible that these rocks are from the boundary area, where basalt deposits are covered by highland ejecta. The concentrations of cosmogenic radionuclides and trapped noble gases are unusually low in both rocks, although Kalahari 008 contains slightly higher concentrations. A likely reason for this difference is that Kalahari 008 is a polymict breccia containing a briefly exposed regolith, while Kalahari 009 is a monomict brecciated rock that may never have been at the surface of the Moon. Altogether, the compositions of Kalahari 008 and 009 permit new insight into early lunar evolution, as both meteorites sample lunar reservoirs hitherto unsampled by spacecraft missions. The very low Th and REE content of Kalahari 009 as well as the depletion in Sm and the lack of a KREEP-like signature in Kalahari 008 point to a possible source far from the influence of the Procellarum-KREEP Terrane, possibly the lunar farside.

Bulk chemical and O-, Mg- and Si-isotopic compositions were measured for each of 17 Types A and B refractory inclusions from CV3 chondrites. After bulk chemical compositions were corrected for non-representative sampling in the laboratory, the Mg- and Si-isotopic compositions of each inclusion were used to calculate its original chemical composition assuming that the heavy-isotope enrichments of these elements are due to Rayleigh fractionation that accompanied their evaporation from CMAS liquids. The resulting pre-evaporation chemical compositions are consistent with those predicted by equilibrium thermodynamic calculations for high-temperature nebular condensates, but only if different inclusions condensed from nebular regions that ranged in total pressure from 10−6 to 10−1 bar, regardless of whether they formed in a system of solar composition or in one enriched in dust of ordinary chondrite composition relative to gas by a factor of 10 compared to solar composition. This is similar to the range of total pressures predicted by dynamic models of the solar nebula for regions whose temperatures are in the range of silicate condensation temperatures. Alternatively, if departure from equilibrium condensation and/or non-representative sampling of condensates in the nebula occurred, the inferred range of total pressure could be smaller. Simple kinetic modeling of evaporation successfully reproduces observed chemical compositions of most inclusions from their inferred pre-evaporation compositions, suggesting that closed-system isotopic exchange processes did not have a significant effect on their isotopic compositions. Comparison of pre-evaporation compositions with observed ones indicates that 80% of the enrichment in refractory CaO + Al2O3 relative to more volatile MgO + SiO2 is due to initial condensation and 20% due to subsequent evaporation for both Types A and B inclusions.

We have critically reevaluated equilibrium iron isotope fractionation factors for oxide and sulfide minerals using recently acquired data obtained by Mossbauer spectroscopy and inelastic nuclear resonant X-ray scattering (INRXS) synchrotron radiation. Good agreement was observed in the iron b-factors of metallic iron (a-Fe) and hematite calculated using both Mossbauer- and INRXS-derived data, which supports the validity and reliability of the calculations. Based on this excellent agreement, we suggest the use of the present data on the iron b-factors of hematite as a reference. The previous Mossbauer-derived iron b-factor for magnetite has been modified significantly based on the Fe-sublattice density of states obtained from the INRXS experiments. This resolves the disagreement between naturally observed iron iso- tope fractionation factors for mineral pairs involving magnetite and those obtained from the calculated b-factors. The cor- rectness of iron b-factor for pyrite has been corroborated by the good agreement with experimental data of sulfur isotope geothermometers of pyrite-galena and pyrite-sphalerite. A good correlation between the potential energy of the cation site, the oxidation state of iron and the iron b-factor value has been established. Specifically, ferric compounds, which have a high- er potential energy of iron than ferrous compounds, have higher b-factors. A similar dependence of b-factors on the oxidation state and potential energy could be extended to other transition metals. Extremely low values of INRXS-derived iron b-fac- tors for troilite and Fe3S significantly widen the range of iron b-factors for covalently bonded compounds. � 2007 Elsevier Ltd. All rights reserved.

Experimental and theoretical aspects of oxygen isotope fractionation in the system calcite–water at low temperatures were critically examined. Contrary to the claim made by Zhou and Zheng [Zhou G.-T., and Zheng Y.-F. (2003) An experimental study of oxygen isotope fractionation between inorganically precipitated aragonite and water at low temperatures. Geochim. Cosmochim. Acta 67 , 387–399], there is excellent agreement between fractionation factors that were experimentally determined by means of slow, inorganic precipitation of calcite from solutions and those obtained largely from theoretical, statistical–mechanical calculations of the reduced partition function ratios. This agreement strongly suggests that calcite was precipitated from a solution very close to isotopic equilibrium. However, recently Zhou and Zheng [Zhou G.-T., and Zheng Y.-F. (2005) Effect of polymorphic transition on oxygen isotope fractionation between aragonite, calcite and water: a low-temperature experimental study. Am. Miner. 90 , 1121–1130] presented, without any explanation, conclusions on these major aspects that contradict the previous statements of Zhou and Zheng (2003). The apparent discrepancy in calcite–water oxygen isotope fractionation between experimental and theoretical studies discussed by Zhou and Zheng (2003) originates from the “mineral–water interaction” term in the modified increment method, which was developed by one of the authors (Y.-F. Zheng). We call for evidence for the theoretical nature of the modified increment method, which has never been presented in any of Zheng’s papers. Without such evidence, great caution must be exercised in using fractionation factors derived from the modified increment method.

Isotopic compositions of up to three elements (Mo, Zr, Ba) were measured on 55 presolar SiC grains from the Murchison meteorite, allowing identification of grains potentially contaminated with solar system material. The range of compositions of uncontaminated grains may constrain the amount of 13C produced in parent AGB stars to a narrow range around the amount required to explain solar system s-process abundances.

Direct oxygen isotope fractionation between cassiterite and calcite has been investigated experimentally at 15 kbar with temperature ranging from 800 to 1000°C. Combined with the quartz-calcite fractionation measured with the same technique ( Clayton et al., 1989 ), the calcite-cassiterite and quartz-cassiterite oxygen isotope fractionations can be expressed as: Δ CaCO 3 − SnO 2 = 4.14 × 10 6 T − 2 Δ SiO 2 − SnO 2 = 4.52 × 10 6 T − 2 at temperatures higher than 600°C. These calibrations are in good agreement with those obtained from heat capacity and X-ray resonant data. The theory of using X-ray resonant data to calculate the reduced partition function ratios of transition elements that have at least one Mossbauer-sensitive isotope is evaluated with the current experimental result.

Oxygen isotope equilibrium fractionation constants (β18O-factors) of cassiterite were evaluated on the basis of heat capacity and X-ray resonant (Mossbauer spectroscopy and X-ray inelastic scattering) data. The low-temperature heat capacity of cassiterite was measured in the range from 13 to 340 K using an adiabatic calorimeter. Results of measurements of two samples agree very closely but deviate more than 5% from previous heat capacity data used for calculation of thermodynamic functions. The temperature dependence of heat capacity was treated using the modern version of the Thirring expansion, and the appropriate temperature dependence of the vibrational kinetic energy was found. Measurements of temperature-dependent Mossbauer parameters of cassiterite were conducted in the range from 300 to 900 K. The attempt to describe Mossbauer fraction and the second order Doppler (SOD) shift on the basis of the Debye model failed. The first term of the Thirring expansion of the Mossbauer SOD shift agrees with that calculated from the Sn sublattice vibration density of states (VDOS) obtained via synchrotron X-ray scattering. Based on this agreement we calculated the kinetic energy of the cassiterite Sn sublattice from VDOS. From the kinetic energy of the total cassiterite crystalline lattice and its Sn sublattice, β18O-factors of cassiterite were computed in the temperature range 300–1500 K by the method of Polyakov and Mineev (2000). Appropriate polynomials, which are valid at temperatures above 400 K, are the following: 103ln⁡βSnO2=(7.176±0.252)x − (0.07369±0.00089)x2 +(0.0008026±0.0001022)x3, x = 106/T2;103ln⁡αCaCO3−SnO2=4.607x − 0.3463x2 + 0.01500x3, x = 106/T2;103ln⁡αSiO2−SnO2=4.942x − 0.2963x2 + 0.01150x3, x = 106/T2. The evaluated cassiterite isotope fractionation factors are significantly different from those obtained by synthesis, increment and empirical methods. To resolve the differences, laboratory direct exchange experiments are needed.

The heat capacity of tin dioxide was measured at low temperatures by the adiabatic calorimeter technique. The measurements were conducted for two samples of tin dioxide. The discrepancy between two sets of the measurements does not exceed experimental error. However, a large disagreement (more than 5%) was observed between this study and data previously used for thermodynamic calculations. Using non-linear least-square method (LSM), the equation approximating and smoothing experimental data was derived. Thermodynamic functions at 298.15 K (heat capacity, entropy and enthalpy increment) values calculated from experimental data are as follows: C p, m 0 =55.24±0.03 J mol −1 K −1 , Δ 0 298 S m 0 =51.82±0.07 J mol −1 K −1 , Δ 0 298 H m 0 =8.806±0.005 kJ mol −1 . These values of the thermodynamic functions are about 5% larger than those used in reference books elsewhere.

D'Orbigny is the sixth and by far the largest angrite known. Its bulk chemical and mineral chemical compositions, rare gas abundances and oxygen and rare gas isotope compositions fit the composi- tional ranges known from other angrites. It is, however, peculiar with respect to three features: the abundance of hollow shells, the presence of abundant open druses and the abundant presence of glasses. The shape, structure and texture of D'Orbigny and its mineral and bulk chemical compositions indicate an unusual genesis under changing redox conditions. In our view, data and observations are incompatible with an igneous origin of this rock but are suggestive of a complex growth and metasomatism scenario. The sequence of events apparently began with the formation of spheres of a phase which later vanished and therefore is unknown but could have been CaS. On top of these spheres (sizes from 1-30 mm) olivine-anorthite intergrowths precipitated forming compact shells and fluffy protrusions. Aggregation of these objects plus occasional large plates made of the same intergrowths led to formation of a highly porous object with abundant large open space between the olivine-anorthite intergrowths. The aggregate also included previously formed olivines, olivinite rocks and Al-spinels. The latter carry highly porous decomposition rims of Cr-enriched Al-spinel and record mildly oxidizing conditions prevailing very early in D'Orbigny's history. Conditions changed (with falling T?) and became oxidizing causing the phase(s) that constituted the spheres to become unstable. Their breakdown liberated large amounts of Ca and trace elements which at least in part re-precipitated by reacting with Si and Mg from the vapor to form augites that grew into the open space thus forming augite druses. Also, some of the preexisting olivine was converted into augite, which is very rich in refractory lithophile trace elements (abundances 10 CI). Augites grew mainly under oxidizing conditions leading to atomic Fe/(FeMg) ratios of about 0.44. Finally, conditions became highly oxidizing and strongly mobilized Ca from a source that apparently became unstable. The high partial pressures of Ca and Fe (and also Ti) led to precipitation of Ca-olivine and kirschsteinite (Fo1La20 and Fo1La33, respectively) and of titaniferous aluminous hedenbergite—atomic Fe/(FeMg) 0.97. Ulvospinel and sulfides were also precip- itated. Because the original phase(s) forming the early spheres vanished during these oxidizing events, the shells remained empty. In this scenario, D'Orbigny provides us with a record of changing conditions ranging from extremely reducing to highly oxidizing and with a record of the formation of an achondritic rock from a chondritic source. Angrites bear many similarities with CAIs, texturally, mineralogically and chemically. Possibly, they can be seen as CAIs, which grew larger than the ones we know from carbonaceous chondrites. Thus, angrites may bear a record of rare and special conditions in some part of the early solar nebula. They reproduce most of the textures and structures of CAIs: crystallized liquids (Asuka 881371, LEW 87051), metasomatic granoblastic rocks (LEW 86010, Angra dos Reis?) and aggregates (D'Orbigny). In addition, all angrites record metasomatic alterations, subsolidus processing after formation, also similar to what is recorded by most CAIs. Obviously, they missed the alkali metasomatic event recorded by many CAIs but they record a siderophile— lithophile element separation event that is not recorded by CAIs. Copyright © 2004 Elsevier Ltd

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

Gujba is a coarse-grained meteorite fall composed of 41 vol% large kamacite globules, 20 vol% large light-colored silicate globules with cryptocrystalline, barred pyroxene and barred olivine textures, 39 vol% dark-colored, silicate-rich matrix, and rare refractory inclusions. Gujba resembles Bencubbin and Weatherford in texture, oxygen-isotopic composition and in having high bulk delta N-15 values (approximately +685%0). The He-3 cosmic-ray exposure age of Gujba (26 +/- 7 Ma) is essentially identical to that of Bencubbin, suggesting that they were both reduced to meter-size fragments in the same parent-body collision. The Gujba metal globules exhibit metal-troilite quench textures and vary in their abundances of troilite and volatile siderophile elements. We suggest that the metal globules formed as liquid droplets either via condensation in an impact-generated vapor plume or by evaporation of preexisting metal particles in a plume. The lower the abundance of volatile elements in the metal globules, the higher the globule quench temperature. We infer that the large silicate globules also formed from completely molten droplets; their low volatile-element abundances indicate that they also formed at high temperatures, probably by processes analogous to those that formed the metal globules. The coarse-grained Bencubbin-Weatherford-Gujba meteorites may represent a depositional component from the vapor cloud enriched in coarse and dense particles. A second class of Bencubbin-like meteorites (represented by Hammadah a1 Hamra 237 and QUE 94411) may be a finer fraction derived from the same vapor cloud

Barium isotopic compositions of single 2.3–5.3 μm presolar SiC grains from the Murchison meteorite were measured by resonant ionization mass spectrometry. Mainstream SiC grains are enriched in s-process barium and show a spread in isotopic composition from solar to dominantly s-process. In the relatively coarse grain size fraction analyzed, there are large grain-to-grain variations of barium isotopic composition. Comparison of single grain data with models of nucleosynthesis in asymptotic giant branch (AGB) stars indicates that the grains most likely come from low mass carbon-rich AGB stars (1.5 to 3 solar masses) of about solar metallicity and with approximately solar initial proportions of r- and s-process isotopes. Measurements of single grains imply a wide variety of neutron-to-seed ratios, in agreement with previous measurements of strontium, zirconium and molybdenum isotopic compositions of single presolar SiC grains.

A synthetic material with solar elemental proportions of iron, magnesium, silicon, titanium, calcium, and aluminum oxides and doped with rare earth elements was evaporated in a vacuum furnace at 1800 and 2000°C for different durations to study its chemical and isotopic evolution during the evaporation process. It is demonstrated that kinetic evaporation of solar composition material can produce residues of calcium-, aluminum-rich inclusion bulk chemistry. The evaporation sequence of the main constituents in this solar composition material is iron > silicon ≈ magnesium > titanium. Calcium and aluminum remain unevaporated after evaporation of 95% of the solar composition material. The chemical fractionation between the gas and condensed phase is a function not only of temperature and pressure, but also of the bulk chemical composition of the condensed phase. During the evaporation process, cerium is almost as volatile as iron. The 2,000-fold cerium depletion found in some refractory inclusions in carbonaceous chondrites was reproduced in the evaporation experiment and can be readily explained as a result of evaporation of preexisting meteoritic material. Kinetic isotopic fractionation of magnesium, oxygen, and silicon follows the Rayleigh distillation law during the laboratory evaporation of synthetic solar composition material. This implies that the residue is well mixed during the evaporation process and that the evaporation kinetic processes (both chemical and isotopic) are surface reaction-controlled. The isotopic mass fractionation factors are lower than those predicted from theoretical calculations by using the square root of mass ratios of likely evaporating species. Thus, the surface reaction is more complicated than decomposition into single gas species of each element.

Single crystals of forsterite were evaporated in a vacuum furnace at temperatures of 1500–1800°C to study evaporation kinetics, magnesium isotopic fractionation, and magnesium diffusion in forsterite. The evaporation of single crystal forsterite revealed that the evaporation process is kinetically hindered, in agreement with the results of Hashimoto (1990) on polycrystalline forsterite. The activation energy of forsterite evaporation obtained from this study is 628 kJ/mole. Forsterite can thus be much more refractory at low temperatures than expected from thermodynamic predictions. The evaporation of solid forsterite supports a model of isotopic fractionation under diffusion-controlled conditions such that isotopic fractionation during the evaporation process is restricted to the vicinity of the evaporating surface. The measured solid-gas fractionation factor of 26Mg/24Mg is smaller than the theoretical prediction, suggesting more complicated gas speciation than a monatomic Mg gas. Diffusion coefficients of forsterite at high temperature (1500–1800°C) were obtained based on measurement of isotopic profiles in the evaporation residues. Mg diffusion in forsterite along its crystallographic a-axis has a very high activation energy (608 kJ/mole).

The carbonaceous chondrites display the widest range of oxygen isotopic composition of any meteorite group, as a consequence of the interaction of primordial isotopic reservoirs in the solar nebula. These isotopic variations can be used to identify the reservoirs and to determine conditions and loci of their interactions. We present a comprehensive set of whole-rock analyses of CV, CO, CK, CM, CR, CH, and CI chondrites, as well as selected components of some of these meteorites. A simple model is developed which describes the isotopic behavior during parent-body aqueous alteration processes. The process of thermal dehydration also produces a recognizable effect in the oxygen isotopic composition.

Oxygen isotope analyses have been obtained for magnetite and diopside from mafic alkaline volcanic rocks of kamafugitic affinities from Brazil. These rocks are part of the Alto do Paranaiba and Santo Antonio volcanic provinces of Cretaceous age. Based on the clinopyroxene–magnetite pair, the isotopic temperatures obtained for the rocks of the two provinces are: mafitites −1140–920°C; leucitites −920–830°C; kalsilitites −820°C; analcimites (originally leucitites) −1060–1050°C; cumulate pyroxenites 750–690°C. The Mata da Corda (Alto Paranaiba Province) and Santo Antonio da Barra range in δ 18 O coincides with typical values for mantle-derived magmas.

We report the isotopic composition of molybdenum in twenty-three presolar SiC grains from the Murchison meteorite which have been measured by resonant ionization mass spectrometry (RIMS). Relative to terrestrial abundance (and normalized to s-process-only 96Mo), the majority of the analyzed grains show strong depletions in the p-process isotopes 92Mo and 94Mo and the r-process isotope 100Mo. Sixteen of these grains have δ-values

We have characterized the most phyllosilicate-rich members of the CM chondrite group. Based upon petrographic and compositional factors, we conclude that these particular meteorites have experienced pervasive aqueous alteration far beyond that witnessed by typical CMs. The lack of anhydrous silicates, CAI and (except as relicts) chondrules merits the classification of type CMI for three meteorites (EET 83334, ALH 88045, and one Kaidun lithology). Still other CMs, notably ALH 83100, EET 90047, and Yamato 82042, are clearly intermediate between types 1 and 2. Brecciated CM chondrites like Cold Bokkeveld contain all of these varied lithologies. The CM chondrites thus exhibit the complete petrologic range from 2 through 1. Our results show that progressive aqueous alteration on the parent CM asteroid(s) was, locally, accompanied by significant increases in temperature (to a peak of ∼450°C for the Kaidun lithology), fO2, and (locally) degree of chemical leaching, all well beyond the conditions recorded by typical CM2s. The most altered CMs also are commonly deformed, displaying a distinct lineation probably due to static rather than dynamic forces.

We have conducted petrologic, chemical, and isotopic studies of lodranites in an attempt to constrain their genesis. Lodran, Gibson, Y-791491, Y-791493, Y-74357, Y-8002, Y-75274, MAC 88177, LEW 88280, EET 84302, FRO 90011, and QUE 93148 are classified as lodranites. Lodranites and acapulcoites are indistinguishable on the basis of oxygen isotopic compositions but are distinct in average grain sizes of their mafic silicates, with lodranites being significantly coarser-grained. Lodranites exhibit a diverse range of petrologic and mineralogic features: they range widely in mafic silicate compositions (Fa3–13), plagioclase (0–11.4 vol%), Fe,Ni metal (0.5–20 vol%), and troilite (0.2–5.3 vol%) contents; and shock levels (S1–S4) . They appear to have experienced high peak temperatures and rapid cooling in the temperature range recorded by metallographic cooling rates (i.e., 700-350°C). The only dated lodranite, Gibson, cooled to Ar closure temperatures at 4.49 ± 0.01 Ga. Lodranites formed from chemically and isotopically heterogeneous precursors in which the mineral and oxygen isotopic compositions were correlated. Heating of their parent body to temperatures between ∼ 1050–1200°C resulted in formation of Fe,NiFeS and basaltic partial melts. Depletions of troilite and/ or plagioclase in most lodranites testify to the removal of some of these partial melts, although melt migration was complex. Lodranites appear to have experienced a complex cooling history of slow cooling at high temperatures, followed by rapid cooling at intermediate temperatures, possibly related to breakup of the parent body. Lodranites were liberated from their parent body during 1–3 impact events, with most having cosmic ray exposure ages of 5.5–7 Ma. The acapulcoites are samples from the same parent body but were heated to lower temperatures and, thus, experienced lower degrees of partial melting.

The Kakangari, LEW 87232, and Lea Co. 002 chondrites have a similar set of petrologic and oxygen isotopic characteristics that distinguishes them from other chondrite groups. They are here established to constitute a single chondrite grouplet—the K (after Kakangari) chondrites. The K chondrites have (1) high matrix abundances (33–77 vol%) as do carbonaceous chondrites, (2) metal abundances (6–10 vol%) that are similar to the H group ordinary chondrites, (3) average mafic silicate compositions (average Kakangari olivine = Fa2.2; enstatite Fs4.4) that indicate an oxidation state intermediate between H and E chondrites, (4) matrix that differs from that in other chondrite groups in being enstatite-rich with compositions more Mg-rich (average = Fs3) than those in the chondrules, (5) refractory lithophile element abundances (

We have conducted petrologic, chemical, and isotopic studies of acapulcoites (Acapulco, Monument Draw, Yamato 74063, ALH A77081, ALH A81261, ALH A81315, ALH 78230, ALH A81187 and ALH 84190) in an attempt to constrain their genesis. Acapulcoites have distinctly different oxygen isotopic compositions than silicate inclusions in IAB and IIICD irons, winonaites and ureilites and, thus, formed on a different parent body. Oxygen isotopic compositions, which are slightly heterogeneous within the group, overlap with lodranites, indicating a likely origin on a common parent body. These groups can be distinguished on the basis of mafic silicate grain size. All acapulcoites have mafic silicate compositions intermediate between E and H chondrites, roughly chondritic mineralogies, achondritic, equigranular textures, micrometer to centimeter sized veins of Fe,NiFeS which cross-cut silicate phases, rapid metallographic cooling rates at ∼600−400°C (103–105°C/Myr) and trapped noble gas abundances comparable to type 3–4 ordinary chondrites. They exhibit variable mafic silicate zoning, abundance of Fe,NiFeS veins, REE abundances and patterns and, possibly, cosmic ray exposure ages (∼5–7 Ma). Momument Draw and Yamato 74063 retain rare relict chondrules. Phosphates are associated with Fe,NiFeS veins or form separate veins in Monument Draw and Acapulco. Heating and cooling of acapulcoites occurred very early in the history of the Solar System, as evidenced by the 39Ar40Ar ages of ∼4.51 Ga. These ages appear distinctly younger than the likely formation time for Acapulco of 4.557 Ga, but are older than analogous 39Ar40Ar ages for most chondrites. Acapulcoites formed from a precursor chondrite which differs from known chondrites in mineral and oxygen isotopic compositions. Heating to ∼950–1000°C resulted in melting at the Fe,NiFeS cotectic, but silicates did not melt. Silicate textures resulted from extensive solid-state recrystallization. Heating was by noncollisional sources (e.g., 26Al, electromagnetic induction). Despite uncertainties owing to a lack of data, acapulcoites may have experienced a three-stage thermal history of slow cooling at high temperature, rapid cooling at intermediate temperatures, and slow cooling at low temperatures, possibly resulting from breakup and gravitational reassembly of the parent body. The complex thermal history is also reflected in disequilibrium REE abundances. One or at most two impact events (∼7 Ma and possibly ∼5 Ma ago) are consistent with the cosmic ray exposure ages of all four acapulcoites for which cosmogenic noble gas data exist.

Oxygen isotope fractionations in laboratory systems have been determined for each of the following minerals relative to calcite: muscovite, phlogopite, fluorophlogopite, and rutile. Statistical mechanical calculations following the method of Kieffer (1982) were fit to the experimental data and then used to extrapolate the experimental results to higher and lower temperatures. The calculations are represented by a series of equations which allow the reduced partition function ratios (β factors) for each of these minerals to be calculated at T > 400 K. These equations can be combined with corresponding equations for calcite, quartz, albite, anorthite, diopside, forsterite, and magnetite (Clayton and Kieffer, 1991) to give a large number of mineral-pair fractionations for use as isotopic thermometers. It was found that the high-frequency vibrations of OH bonds contribute such a small amount of the fractionation factors that they do not introduce significant nonlinearity to plots of Δ vs. T−2. The commonly used calibrations of quartz-muscovite and quartz-biotite fractionations are not in good agreement with the present experimental measurements. This probably reflects disturbance of the rock assemblages on which those calibrations were based, as a consequence of the high diffusivity of oxygen in micas. The experimental quartz-rutile fractionations are in good agreement with some earlier hydrothermal experiments and with an empirically determined calibration. The calculated rutile partition functions of Kieffer (1982) are not consistent with the experimental results, probably due in part to the neglect of the effect of cation mass on the vibrational energies. The large number of mineral systems with measured fractionation factors allows a test of various empirical relationships based on oxygen bond strengths. In general, these relationships are successful for anhydrous silicates, but do not adequately account for the behavior of hydrous minerals or metal oxides.

Oxygen isotope abundances provide a powerful tool for recognizing genetic relationships among meteorites. Among the differentiated achondrites, three isotopic groups are recognized: (l ) SNC (Mars), (2) Earth and Moon, and (3) HED (howardites, eucrites, diogenites). The HED group also contains the mesosiderites, main-group pallasites, and silicates from IIIAB irons. The angrites may be marginally resolvable from the HED group. Within each of these groups, internal geologic processes give rise to isotopic variations along a slope- 1 2 fractionation line, as is well known for terrestrial materials. Variations of Δ17O from one planet to another are inherited from the inhomogeneities in the solar nebula, as illustrated by the isotopic compositions of chondrites and their constituents. Among the undifferentiated achondrites, five isotopic groups are found: (1) aubrites, (2) winonaites and IAB-IIICD irons, (3) brachinites, (4) acapulcoites and lodranites, and (5) ureilites. The isotopic compositions of aubrites coincide with the Earth and Moon, and also with the enstatite chondrites. These bodies apparently were derived from a. common reservoir, the isotopic composition of which was established at the chondrule scale by nebular processes. Isotopic similarities between chondrites and achondrites are seen only for the following instances: (1) enstatite chondrites and aubrites, (2) H chondrites and HE irons, and (3) L or LL chondrites and IVA irons. The isotopic data also support the following genetic associations: (1) winonaites and IAB-IIICD irons, (2) acapulcoites and lodranites, and (3) ureilites and dark inclusions of C3 chondrites. An attempt to reconcile the whole-planet isotopic compositions of Earth, Mars, and the eucrite parent body with mixing models of their chemical compositions failed. It is not possible to satisfy both the chemical and isotopic compositions of the terrestrial planets using known primitive Solar System components.

Laboratory experiments have been conducted to determine rates and other details of the oxygen isotopic exchange process between meteoritic material and water vapor. The meteoritic samples were totally or partially melted, or completely unmelted. The furnace atmosphere consisted of water vapor and hydrogen, and was diluted with helium for some of the experiments. Both isothermal and flash heating experiments were performed. Extensive oxygen isotope exchange has been observed between chondrule analogue melt and surrounding dilute water vapor, such that 50% equilibration occurs in charges near their liquidus in five minutes or less. The principal rate-limiting mechanism of the exchange is diffusion within the melt. The initial exchange rate also depends on the partial pressure of water, which points to the effect of the surface exchange process. The kinetics of the surface reaction have not been determined due to the restrictions of our experimental configuration. The extent of exchange observed in short time isothermal runs and in flash heating runs suggests that much of the isotopic variability of natural chondrules can be produced during chondrule-forming events by the gas/melt isotopic exchange processes. However, due to the very low gas densities in the nebula, multiple melting events might be needed to produce the chondrules with highly exchanged isotopic compositions. For a partially melted sample, as is often the case in natural chondrules, the rate of isotopic change of the bulk sample is determined by the exchange rates of both the melt and unmelted relict minerals. If the melt and relict minerals have a large difference in isotopic compositions, the exchange trajectory becomes markedly nonlinear. These observations are consistent with the observed dependence of extent of exchange in natural chondrules on the degree of melting, and imply that for each of the linear trends on the three-isotope diagram observed for natural chondrules, only two initial isotopic reservoirs might have existed.

Oxygen isotopic compositions have been determined for whole-rock and separated components from the CI chondrites Alais, Ivuna, and Orgueil, and from the atypical CM chondrites Bells and Essebi. The composition of CI matrix is in agreement with previous measurements and is systematically different from that of CM matrix, probably due to warmer and wetter conditions of aqueous alteration for CI matrix. Although Bells matrix is like that of other CM chondrites, the matrix of Essebi falls in the CI field. Essebi also contains abundant magnetite, like CIs and unlike other CMs. The isotopic compositions of magnetite in Alais, Ivuna, Orgueil and Essebi define a trend with Δ17O of +1.3 to +1.8, distinctly out of isotopic equilibrium with the phyllosilicates in each meteorite. The magnetite serves as an isotopic tracer for the fluid which brought about aqueous alteration and oxidation, and thus provides additional evidence for a gaseous reservoir in the solar nebula which was more 16O-depleted than the earth.

Iron meteorites analyzed in this study have nitrogen concentrations 70 microg/g or less and delta N-15 from -90 to +150 percent. Although the iron meteorites have a large range of delta N-15, most have values more negative than -50 percent. The nitrogen isotopic compositions were established by cosmochemical processes and were little modified by fractional crystallization or other chemical processes within the parent bodies. The data do not suggest the existence of a well-mixed solar nebular reservoir for nitrogen, as was already inferred from data from stony meteorites. The range of greater than 1100 percent observed for delta N-15 in bulk meteorites is probably too large to be accounted for by physical and chemical mass-dependent fractionation processes in the solar nebula, and thus reflects nebular inhomogeneities of nucleosynthetic origin.

A petrologic, geochemical, and oxygen isotropic study of the CR chondrites including Renazzo, Al Rais, El Djouf 001 and the paired Acfer meteorites, EET87770 and the paired samples, MAC87320, Y790112, Y793495, and Y791498 is presented. It is concluded that the CR group is characterized by abundant large multilayered, Fe, Ni metal-rich, type I chondrules; abundant matrix and dark inclusions; unique assemblages of serpentine and chlorite-rich phyllosilicates and Ca-carbonates; Ca-carbonate rims on chondrules; abundant Fe, Ni metal with a positive Ni vs. Co trend and a solar Ni:Co ratio; and amoeboid olivine aggregates with Mn-rich and Mn-poor forsterite.

Ten chondrites with chemical and mineralogical similarities to the carbonaceous chondrite Renazzo were recovered at two locations of the Sahara: Acfer 059, 087, 097, 114, 139, 186, 187, 209, 270 and El Djouf 001. Although the El Djouf location is more than 500 km away from the Acfer location, all samples appear to result from a single fall based on chemical and petrographic similarities and supported by light element stable isotope geochemistry, noble gas record, and similar 26Al contents. The Acfer-El Djouf meteorite is classified as a CR (Renazzo-type) carbonaceous chondrite. This group presently comprises three non-Antarctic members (Al Rais, Renazzo, Acfer-El Djouf) and five Antarctic meteorites. The major lithological components of the Acfer-El Djouf meteorite are large chondrules (up to 1 cm in size; mean diameter: 1.0 ± 0.6 mm), chondrule and mineral fragments, Ca,Al-rich inclusions, FeNi-metal (about 8–10 vol%) and dark inclusions embedded in a fine-grained fragment-bearing groundmass. Mineral compositions of the ten Acfer-El Djouf samples are similar to those of other CR chondrites. Most of the Ca,Al-rich inclusions are below 300 μm in size and rich in melilite and spinel. In some CAIs the rare phase CaAl4O7 is dominant. Fo-rich, Cr-bearing olivine (Fa0–4) and enstatite (Fs0–4) are the major phases of the chondrite. The meteorite is mildly shocked with a shock stage of S2 indicating a peak shock pressure of 5–10 GPa for the bulk meteorite. The oxygen isotopic compositions and carbon and nitrogen stable isotope geochemistry of the Acfer-El Djouf samples are very similar to those of the other CR-type chondrites. The major element composition of the Acfer-El Djouf meteorite is indistinguishable from CR chondrites. When compared to Renazzo the Acfer-El Djouf samples, however, have systematically lower contents of the moderately volatile elements Zn, Ga, As, Au, Sb, and Se and the highly volatile elements Br, C, and N. This is thought to reflect primary differences between Renazzo and the Acfer-El Djouf meteorite.

A study of mineralogy, chemistry, and isotopic composition of the Coronation Supergroup (about 1.9 Ga, NWT), Canada, and the McArthur Group (about 1.65 NT), Australia, is reported in order to obtain better constrained data for the first- and second-order variations in the isotopic composition of late Paleoproterozoic (1.9 +/- 0.2 Ga) seawater. Petrologically, both carbonate sequences are mostly dolostones. The McArthur population contains more abundant textural features that attest to the former presence of sulfates and halite, and the facies investigated represent ancient equivalents of modern evaporitic sabkhas and lacustrine playa lakes. It is suggested that dolomitization was an early diagenetic event and that the O-18 depletion of the Archean to late Paleoproterozoic carbonates is not an artifact of postdepositional alteration.

The mineralogy, chemistry, and isotopic composition of the Malmani Dolomite, Duck Creek Dolomite, and Bruce 'Limestone' Member of the Espanola Formation are studied in an effort to restrict the first- and second-order variations in isotopic composition of Early Paleoproterozoic seawater. The diagenetic rank is found to increase in the order Duck Creek less than Bruce less than Malmani. The interpolation of alteration trends to 'best' value yields an estimate of 0.70550 for Sr-87/Sr-86. For delta C-13, the measured range of 0 +/- 1.5 percent PDB is similar to that observed for Phanerozoic marine carbonates, while the 'best' delta O-18 value for dolostones is -5 percent PDB, depleted in O-18 relative to Phanerozoic counterparts but comparable to estimates obtained for Archean facies. The isotope geochemistry and mineralogy of Bruce 'Limestone' Member is consistent with the proposition that the sequence was deposited in a lacustrine environment.

Oxygen and carbon isotopic fractionation factors have been measured by direct exchange between carbon dioxide and calcite over the temperature range 400–950°C at pressures of 1–13 kilobars. Equilibrium constants for oxygen exchange are well determined from 400 to 800°C, and differ substantially from previous experimental and theoretical estimates. Carbon isotopic fractionations have larger uncertainties at all temperatures. Both oxygen and carbon isotopic fractionations are well reproduced by statistical mechanical calculations with simple treatment of the calcite lattice vibrations. A recalculated calcite-graphite fractionation curve based on new calculations of partition functions ratios for calcite suggests that this system is well suited for high-temperature isotopic thermometry of graphitic marbles as first proposed by Valley and O'Neil (1981). The rate of exchange of both oxygen and carbon between carbon dioxide and calcite is rapid, and proceeds by a combination of diffusion and minor recrystallization.

The petrogenesis of the Carlisle Lakes-type chondrites and their relationship to other chondrites are studied using new petrologic data, especially on mineralogical zoning patterns, and oxygen isotopic analyses of the whole chondrites and some of chondrules. Detailed zoning profiles of mafic silicates are measured in order to determine the environment(s) in which their oxidation states are established. It is concluded that the zoning did not form during crystallization from a melt droplet chondrule but post-dated chondrule formation. Parent-body thermal metamorphism and nebular gas-solid exchange reactions accompanied by condensation of new FeO-rich olivine, utilizing existing olivine surfaces as nucleation sites are considered as hypotheses explaining the zoning. The occurrence of zoned grains in a host that is mainly equilibrated suggests that the equilibration of the Carlisle Lakes-type chondrites occurred prior to final lithification.

Several stages in the evolution of ordinary chondritic meteorites are recorded in the oxygen isotopic composition of the meteorites and their separable components (chondrules, fragments, clasts, and matrix). The whole-rock isotopic compositions reflect the iron-group of the meteorite (H, L, or LL). Isotopic uniformity of H3 to H6 and L3 to L6 are consistent with closed-system metamorphism within each parent body. LL3 chondrites differ slightly from LL4 to LL6, implying a small degree of open-system aqueous alteration and carbon reduction. On the scale of individual chondrules, the meteorites are isotopically heterogeneous, allowing recognition of the solar-nebular processes of chondrule formation. Chondrules for all classes of ordinary chondrites are derived from a common population, which was separate from the population of chondrules in carbonaceous or enstatite chondrites. Chondrules define an isotopic mixing line dominated by exchange between (O - 16)-rich and (O - 16)-poor reservoirs. The oxygen isotopic compositions of chondrites serve as 'fingerprints' for identification of genetic association with other meteorite types (achondrites and iron) and for recognition of source materials in meteoritic breccias.

Resonance ionization of sputtered species has emerged as an exceedingly powerful technique for surface-compositional analysis and as a means to study a variety of fundamental aspects of the sputtering process. To deal with the problem of non- or near-resonant ionization, one needs to achieve the highest selectivity for photoionization of the species of interest relative to isobarically overlapping species by choosing a specific photoionization scheme tailored to that purpose. The present paper illustrates this point with several examples and helps point the way to still further improvements in detection sensitivity by minimizing non- or near-resonant ionization through detailed exploration of alternative photoionization schemes.

Results are presented on a detailed petrologic, chemical, and isotopic study of the so-called FUN inclusion (1623-5) from the Vigarano C3V chondrite. It is shown that the precursor material from which the Vigarano 1623-5 has formed contained some nuclear isotopic anomalies; this precursor was composed of melted and crystallized spinel, olivine, fassaite, and melilite. The results on the petrologic and isotopic properties of 1623-5 indicate unambiguously the action of volatilization in the evolution of this inclusion.

Samples from the Pangola and Ventersdorp Supergroups (Kaapvaal Craton, South Africa) and from the Fortescue and Hamersley Groups (Pilbara Block, Australia) were analyzed, using XRF, AAS, and isotope-analysis techniques to investigate the mineralogical, chemical, and isotopic features of these representatives of contemporary shelf carbonates (Pangola and Hamersley samples) and nonmarine carbonates (the Ventersdorp and Fortescue samples). Results show that, mineralogically, the shelf carbonates are almost exclusively dolostones, while the lacustrine facies are predominantly limestones. Geological, trace-element, and oxygen-isotope results of the shelf carbonates suggest that their original mineralogy may have been aragonite, and that the Pangola dolostones may represent a direct dolomitization product of this precursor. By contrast, the stabilization of the Hamersley carbonates may have involved an additional step of transformation of a metastable precursor into limestone.

The Sr, Nd, and O isotopic compositions of garnet and clinopyroxene mineral separates from nine eclogite xenoliths from the Bellsbank kimberlite (erupted at 120 Ma) define three groups. Group A eclogites, considered to be mantle cumulates, are characterized by 6180, and 87Sr/Srsr values typical of mantle-derived materials (+5.1 to +5.6%o and 0.7042-0.7046, respectively), and very low Sm/Nd ratios, (apparent) Rb/Sr ratios and ~NaLlZ01 values (0.057-0.078, 0.00005-0.00136 and - 14 to - 16 respectively). The REE and isotopic data for these eclogites can be modelled in terms of crystallization from a Group II kimberlite magma at - 1-1.5 Ga. Group B and C eclogites, believed to be the metamorphosed products of ancient subducted oceanic crust, are characterized by low 3180 (+2.9 to +4.7), extremely high ~Nd[a20] (-- +40 to +219), and radiogenic 87Sr/S6Sr ratios (0.708-0.710). The Sm/Nd ratios of the Group B eclogites are very high (up to 1.6). The data for Group B and C eclogites define a linear correlation on Sm/Nd and 1/Nd vs. ~Nal~201 diagrams. These relationships are consistent with mixing of the Bellsbank kimberlite (CNO [1201 = --10; Sm/Nd = 0.10) with a depleted eclogite end-member (eNd[120 ] + 219; Sm/Nd = 1.6) during a cryptic metasomatic event. The Sr isotopic variations in Group B and C eclogites cannot be generated by simple two-component mixing. The St, Nd, and O isotope data for Group B and C eclogites probably reflect a complex sequence of depletion and enrichment events, in both crust and mantle settings. Enrichments which possibly affected the Group B and C eclogites include seawater-alteration of a MORB-like protolith, which lowered the 6180 and raised the SVSr/86Sr ratio, but left the Nd isotopic compositions unchanged, and cryptic metasomatism by the magmatism that produced the Bellsbank kimberlite. The high Sm/Nd ratio of the depleted eclogite end-member cannot be generated by extraction of a melt from a modern MORB composition. Rather, it is argued that such high Sm/Nd ratios are produced as a result of partitioning during the recrystallization of a MORB-like component to eclogite during subduction. Nd model ages suggest that this process occurred - 2.3-2.4 Ga.

Oxygen and hydrogen isotope ratios for natural samples of the zeolites analcime, chabazite, clinoptilolite, laumontite, mordenite, and natrolite have been obtained. The zeolite samples were classified into sedimentary, hydrothermal, and igneous groups. The ratios for each species of zeolite are reported. The results are used to discuss the origin of channel water, the role of zeolites in water-rock interaction, and the possibility that a calibrated zeolite could be used as a low-temperature geothermometer.

The oxygen isotope fractionation between analcime and water is studied to test the feasibility of using zeolites as low-temperature thermometers. The fractionation of oxygen isotopes between natural analcime and water is determined at 300, 350, and 400 C, and at fluid pressures ranging from 1.5 to 5.0 kbar. Also, isotope ratios for the analcime framework, the channel water, and bulk water are obtained. The results suggest that the channel water is depleted in O-18 relative to bulk water by a constant value of about 5 percent, nearly independent of temperature. The analcime-water fractionation curve is presented, showing that the exchange has little effect on grain morphology and does not involve recrystallization. The exchange is faster than any other observed for a silicate. The exchange rates suggest that zeolites in active high-temperature geothermal areas are in oxygen isotopic equilibrium with ambient fluids. It is concluded that calibrated zeolites may be excellent low-temperature oxygen isotope geothermometers.

The origin and the history of dark inclusions (DIs) are investigated using petrologic, chemical, and oxygen isotopic data on ten DI samples from Allende, Leoville, and Vigarano. These data indicate that the DIs of the Leoville and Vigarano are closely similar to those of Allende. The inclusions appear to be fragments of CV3 parent bodies which were processed to different degrees prior to their incorporation as clasts into the Allende, Leoville, and Vigarano chondrites. The processing homogenized the olivine compositions, presumably through heating, and also involved oxygen exchange with O-16-poorer surroundings.

The relationship between the porphyritic chondrules and coase-grained chondrule rims of the Allende CV chondrite are examined. The oxygen isotopic compositions of seven chondrule-rim pairs and a large rimless refractory chondrule from Allende are determined. The results suggest that, to account for the O-isotopic compositions of the CV chondrules and rims, three solid precursor components are required: a high-temperature, refractory-, alkali, and (O-16)-rich component; a low-temperature, FeO-rich, refractory, and (O-16)-poor component, and an additional component to explain the composition of BO chondrules.

Oxygen isotope fractionations between wollastonite, diopside, jadeite, hedenbergite and water have been experimentally studied at high pressures (1 18 O 16 O fractionations were made close to equilibrium and initial 17 O 16 O ratios were well removed from equilibrium, allowing accurate determinations of the equilibrium 18 O 16 O fractionations and of the extent of isotopic exchange. Scanning electron microscope and rate studies show that the wollastonite-water and diopside-water exchange reactions occur largely by solution-precipitation (Ostwald Ripening) mechanisms. Equilibrium 18 O 16 O fractionations between water and the minerals wollastonite, diopside, and hedenbergite are in close agreement with one another, whereas significantly more positive fractionations are found for jadeite-water. These isotopic substitution effects can be ascribed to replacement of SiOM bonds (M is a divalent metal cation in octahedral coordination) by higher frequency SiOAl bonds. The fractionations determined in this study can be combined with quartz- and feldspar-water data of Matsuhisa et al. (1979) and revised magnetite-water data of O'NEIL (1963), to provide a coherent set of mineral-pair fractionations satisfactorily represented by straight lines through the origin on a conventional graph of In /ga versus T−2. Mineral-water data, on the other hand, cannot readily be fitted to the simple relationship suggested by Bottinga and Javoy (1973). Coefficients “A” for the mineral-pair fractionations 1000 ln α = A × 106T−2 are: Ab Jd An Di Wo Mt Q 0.50 1.09 1.59 2.08 2.20 6.11 Ab 0.59 1.09 1.58 1.70 5.61 Jd 0.50 0.99 1.11 5.02 An 0.49 0.61 4.52 Di 0.12 4.03 Wo 3.91 Geologically reasonable temperatures are found for appropriate natural assemblages.

Systematic change of voltage on the components of the secondary ion (SI) extraction system of our AEI-IM20 ion microprobe produced major changes of relative intensities of secondary ions passing through the mass spectrometer. The repeller, which bends the SI beam through about 60°, has the greatest effect, and can be used to plot the energy distribution. The extractor and the deflecting and focusing components have smaller but significant effects. Because low-energy secondary ions have a near-symmetrical distribution, whereas high-energy ones have an assymetric distribution favoring high energies, tuning of the acceptance band to higher energy reduces interference from low-energy ions, which tend to be unwanted molecular ions, at the expense of reduced transmission. Tuning to lower energy increases interference but gives higher transmission. The former condition is desirable for instruments restricted to low mass resolution, whereas both conditions are valuable for instruments adjustable for both high and low mass resolution. Other important factors are (a) sensitivity to surface irregularities which perturb SI energy collection, and (b) change in derived “temperatures” from thermodynamic sputtering models merely from tuning the energy acceptance band. Careful attention to the above factors yielded reproducible SI ratios for the binary series of plagioclase feldspars.

Nitrogen in the Allende meteorite consists of at least two components, partially resolvable in a stepwise heating experiment. L-nitrogen, released below 1000 C, has a low delta N-15 (-60 to -90 per mil), and is associated with neon-A and CCF-xenon and may reside in a carbonaceous carrier. H-nitrogen, released above 1000 C, is associated with normal xenon, and may reside in silicate minerals. It is very difficult to account for the entire range of N-15/N-14 ratios in solar system materials by mass-dependent chemical and physical processes alone. In particular, an N-14 enriched component of nuclear origin appears necessary to account for the L-nitrogen in Allende.

Foreign inclusions in stony meteorites. II - Rare gases and oxygen isotopes in a carbonaceous chondritic xenolith in the Plainview gas-rich chondrite

Nitrogen contents range from a few parts per million in ordinary chondrites and achondrites to several hundred parts per million in enstatite chondrites and carbonaceous chondrites. Four major isotopic groups are recognized: (1) C1 and C2 carbonaceous chondrites, (2) enstatite chondrites, (3) C3 chondrites, and (4) ordinary chondrites. The major variations are primary, representing isotopic abundances established at the time of condensation and accretion. Secondary processes, such as spallation reactions, solar wind implantation and metamorphic loss may cause small but observable isotopic variations in particular cases. The large isotopic difference between enstatite chondrites and carbonaceous chondrites cannot be accounted for by equilibrium condensation from a homogeneous nebular gas, and requires either unusually large kinetic effects, or a temporal or spatial variation of isotopic composition of the nebula. Nitrogen isotopic heterogeneity in the nebula due to nuclear processes has not been firmly established, but may be required to account for the large variations found within the Allende and Leoville meteorites. The unique carbonaceous chondrite, Renazzo, also requires a special source. It is not yet possible, from the meteoritic data, to establish the mode of accretion of nitrogen onto the primitive earth.

Oxygen isotopic fractionations have been determined between quartz and water, albite and water, and anorthite and water at temperatures from 300 to 825°C, and pressures from 1.5. to 25 kbar. The equilibrium quartz-feldspar fractionation curves can be approximated by the following equations: 1000ln αQ−PI = (0.46 + 0.55β)106T−2 + (0.02 + 0.85β) between 500 and 800°C 1000ln αQ−PI = (0.79 + 0.90β)106T−2 — (0.43 − 0.30β) between 400 and 500°C where β is the mole-fraction of anorthite in plagioclase. Application of these isotopic thermometer calibrations to literature data on quartz and feldspar gives temperatures for some metamorphic rocks which are concordant with quartz-magnetite temperatures. Plutonic igneous rocks typically have quartz-feldspar fractionations which are substantially larger than the equilibrium values at solidus temperatures, indicating substantial retrograde exchange effects.