Chemical composition of HAL,an isotopically-unusual Allende inclusion

Thirty-seven major, minor and trace elements were determined by INAA and RNAA in samples of hibonite, black rim and portions of friable rim from an unusual Allende inclusion, HAL. The peculiar isotopic, mineralogical and textural properties of HAL are accompanied by very unusual trace element abundances. The most striking feature of the chemistry is the virtual absence of Ce from an inclusion otherwise highly enriched in REE compared to Cl chondrites. HAL is also depleted in Sr, Ba, U, V, Ru, Os and Ir, relative to other refractory elements. Of the lithophile elements determined which are normally considered to be refractory in a gas of solar composition, Sr, Ba, Ce, U and V are the most volatile in oxidizing gases. The distribution of REE between hibonite and rims seems to have been established when hibonite and other refractory minerals were removed at slightly different temperatures from a hot, oxidizing gas in which they previously coexisted as separate grains. On the basis of HAL's chemical and isotopic composition, possible locations for the chemical and mass dependent isotopic fractionation are in ejecta from the low temperature helium-burning zone of a supernova and in the locally oxidizing environment generated by evaporation of interstellar grains of near-chondritic chemical composition.     

A corundum-rich inclusion in the Murchison carbonaceous chondrite

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

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.     

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.     

I-Xe studies of individual Allende chondrules

Iodine-xenon studies have been performed on nine Allende chondrules and a sample of oxidized Allende matrix material. The chondrules are all very rich in radiogenic xenon relative to trapped xenon, making it possible to determine a relatively precise model initial iodine composition for each temperature extraction. These model compositions show a total range in variation of about 20 percent, spanning the compositions seen in Bjurbole chondrules. One of the chondrules (chondrule 6) gives a well-defined isochron, with an apparent age .53 ±. 15 m.y. later than Bjurbole whole rock. The rest of the chondrules show a pattern of increasing apparent antiquity with increasing extraction temperature, which could be interpreted as relatively slow cooling (100–200°C/m.y.). Alternatively, poorly-defined plateaus in composition can be seen, perhaps indicative of a few phases with distinct initial iodine compositions (but also temperature-ordered), as has been previously suggested for Allende inclusions. Possible consequences of these interpretations are discussed. Elemental abundances were determined for some elements several months after the irradiation by INAA, and suggest that all the chondrules except chondrule 6 might be pyroxene- or mesostasis-rich. The oxidized matrix sample gives a well-defined isochron with an initial ${}^{129}\text{I}{}^{127}$I ratio higher than any plateaus seen in the chondrules, suggesting that, if this sample is representative of matrix, the matrix pre-dates the chondrules. The initial ${}^{244}\text{Pu}{}^{238}\text{U}$ ratios of the Allende chondrules and 10 Bjurbole chondrules irradiated earlier appear to be consistent with. 004–.007 values quoted for unfractionated material in the early solar nebula.     

26Al, 244Pu, 50Ti,REE, and trace element abundances in hibonite grains from CM and CV meteorites

The ion microprobe was used to measure Ti and Mg isotopes as well as rare earth and other trace elements in ten hibonites from the CM carbonaceous chondrites Murchison, Murray, and Cold Bokkeveld and in two hibonites and Ti-rich pyroxene from the CV chondrite Allende. In hibonites from Murchison and Murray fission track densities were also measured, as were Th and U concentrations. Eight of the hibonites, from all four meteorites, exhibit large Ti isotopic anomalies, particularly in ⁵⁰Ti. Two grains from Murray have ⁵⁰Ti excesses of ~ 10%. At least four nucleosynthetic components are required to account for all the Ti isotopic data. Neutron-rich nuclear statistical equilibrium nucleosynthesis is the most likely process to account for a ⁵⁰Ti-rich component (with ${}^{50}\text{Ti}{}^{49}\text{Ti}\text{\$}\text{̆}\text{20}$). The ion probe Ti isotopic measurements confirm that the solar nebula was isotopically heterogeneous on a small spatial scale and argue for a chemical memory origin of the Ti isotopic anomalies which were probably carried into the solar system in the form of refractory dust grains. However, there is no experimental evidence that such interstellar grains survived the formation of the hibonites. The REE and trace element patterns of the hibonites are similar to those seen in CAIs and can be interpreted in terms of fractionation effects during condensation from a gas of solar composition, thus arguing for a solar system origin of the hibonites. Additional evidence for such an origin is provided by the $\text{Pu}\text{Th}$ ratios, which are ~ 10⁻⁴, and by the Mg isotopic compositions which are normal except for ²⁶Mg1 due to ²⁶Al.Only three out of ten hibonites exhibit ²⁶Mg1, consistent with previous studies which demonstrated the paucity of ²⁶Mg1 in hibonites. Because of the refractory nature of hibonite and the presence of large Ti isotopic effects, we conclude that a heterogeneous distribution of ²⁶Al in the early solar system is the most likely reason. In particular, our observations of δ⁵⁰Ti = 15%. and of an isochron with (${}^{26}\text{Al}{}^{27}\text{Al}\text{)}{}_0\text{= 5 × 10}{}^{\mathrm{-8}}$ in the FUN inclusion HAL are evidence against both late formation and Mg redistribution to explain the lack of ²⁶Al in hibonites.There are no obvious correlations between the Ti isotopic compositions, the presence of ²⁶Mg1, the presence of ²⁴⁴Pu, and the REE and trace element patterns in individual hibonites. This indicates that the anomalous ⁵⁰Ti, as well as ²⁶A1 and ²⁴⁴Pu, were not co-produced in a single astrophysical source, and/or that these nuclides were introduced into the solar nebula by different carriers before being incorporated into the hibonites.     

Rb-Sr dating of the Lackner Lake Complex,northern Ontario,Canada

The Lackner Lake Complex of northern Ontario consists of nepheline syenite and ijolite with associated bodies of apatite—magnetite rock and carbonatite. A whole-rock Rb-Sr isochron indicates that these rocks crystallized 1078 ± 7 Ma ago ($\text{λ}{}^{87}\text{Rb = 1.39·10}{}^{\mathrm{?11}}\text{a}{}^{\mathrm{?1}}$) and had an initial ⁸⁷Sr/⁸⁶Sr ratio of 0.070282 ± 0.00011. This date is slightly lower than a K-Ar date of 1090 Ma for biotite reported previously, but is in agreement with K-Ar dates of several nearby syenite-carbonatite complexes.     

The isotopic composition of titanium in the Allende and Leoville meteorites

We describe the analytical techniques developed for the precise measurement of the titanium isotope abundances using a TiO⁺ ion beam. Terrestrial, lunar, and bulk meteorite samples yield identical results. Using a normalization to ${}^{46}\text{Ti}{}^{48}\text{Ti}$ for mass dependent isotope fractionation, we obtain the normal Ti composition: ${}^{46}\text{Ti}{}^{48}\text{Ti}\text{= 0.108548}$; ${}^{47}\text{Ti}{}^{48}\text{Ti}\text{= 0.099315 ± 0.000005}$; ${}^{49}\text{Ti}{}^{48}\text{Ti}\text{= 0.074463 ± 0.000004}$; ${}^{50}\text{Ti}{}^{48}\text{Ti}\text{= 0.072418 ± 0.000004}$ (2σ grand mean), taking ${}^{18}\text{O}{}^{16}\text{O}\text{= 0.002045}$ and ${}^{17}\text{O}{}^{16}\text{O}\text{= 0.00037}$. Measurements on thirteen coarse-grained and fine-grained Ca-Al-Ti-rich inclusions from the Allende and Leoville meteorites show the presence of widespread, significant, nonlinear isotope anomalies in the Ti isotopes which were not used for normalization. The data require the addition of at least three exotic components. The distinct correlation of non-linear effects for the most neutron-rich isotopes of Ca and Ti and the absence of substantial effects at ⁴⁶Ca in the FUN samples EK-1-4-1 and C-1 indicate that the effects reflect neutron-rich equilibrium or quasi-equilibrium nucleosynthetic processes in the outer layers of a supernova core. The results on Ca and Ti in conjunction with the isotopic effects on other elements (Mg, Sr, Ba, Nd, Sm) show that the samples represent mixtures of different nucleosynthetic components from distinctive processes (‘e’, ‘r’, ‘p’) which do not appear to be related to processes in the same stellar sites.     

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

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

Single-grain 207Pb206Pb and U/Pb age determinations with a 10-μm spatial resolution using the ion microprobe mass analyzer (IMMA)

Analytical techniques have been developed for using a secondary ion mass spectrometer, the ion microprobe mass analyzer (IMMA), to determine, in situ, ${}^{207}\text{Pb}{}^{206}\text{Pb}$ and U/Pb ages on approximately 10-μm areas of individual mineral phases containing relatively abundant radiogenic Pb isotopes. Standard samples of known age and U, Th and Pb contents, together with the Andersen-Hinthorne local thermal equilibrium (LTE) model for predicting ionization parameters are used to establish a semi-empirical relationship for correcting observed U/Pb intensities to atom ratios. Measurements of isotope standards show that mass fractionation corrections are not required and that the accuracy and precision of analysis are generally limited by Poisson counting statistics.Many U-rich accessory minerals yield spectra which consist only of Pb at masses 204, 206, 207 and 208; thus the measurement of ${}^{207}\text{Pb}{}^{206}\text{Pb}$ ages is accomplished by simply measuring the intensities of these peaks and the background. An excellent correspondence of the ages determined using the IMMA with those from more conventional techniques is demonstrated for terrestrial, lunar and meteoritic phases. For example, the following ${}^{207}\text{Pb}{}^{206}\text{Pb}$ ages were obtained from polished thin sections of crystalline lunar samples: 10047, 3.75 ± 0.05 (2σ) Ga; 14310, 3.96 ± 0.03 Ga; and 15555, 3.36 ± 0.06 Ga. From small U-rich phases in CaAl-rich inclusions in the Allende carbonaceous chondrite, seven ${}^{207}\text{Pb}{}^{206}\text{Pb}$ ages were obtained, averaging 4.60 ± 0.09 (2σ) Ga.A method of correcting low-resolution Pb-isotope data for molecular ion interferences in zircon and baddeleyite is presented and shown to be practical through the analysis of terrestrial and lunar samples.     

Medium pressure crystallization of a monchiquitic magma — evidence from megacrysts of Drever''s block, Ubekendt Ejland, West Greenland

Megacrysts and polymineralic fragments of extraordinary diversity from a Tertiary monchiquitic dyke of Ubekendt Ejland comprise three groups: (1) Cr-diopside-fassaitic diopside + olivine, Fo_90.5?81.5 + CrAl spinels. (II) Fassaitic salite-ferrisalite + KTi-pargasite-ferropargasite + apatite + AlTi-magnetite, (III) Scapolite + hyalophane + potassium feldspar + nepheline + analcime. By comparison with mineralogy and phase relations in the host rock and experimental data from alkaline rocks the megacrysts are related to a sequence of crystallization from primitive monchiquitic to potassic phonolitic magmas rich in H₂O and CO₂ at 5–11 kb. Group I megacrysts formed at temperatures of 1300-1150°C and group II between ? bar at the latter temperature. High P_co2 may have stabilized the scapolite in the more evolved liquid and K-feldspar and nepheline began to crystallize at ca. 800°C possibly together with the ferrisalite.     

U234U238 Ratios in limestone cave seepage waters and speleothem from West Virginia

Speleothem from West Virginia, ranging in age from 2000 to 200,000 yr B.P. contains uranium with $\text{U}{}^{234}\text{U}{}^{238}$ ratios significantly greater than unity. This ratio varies from one speleothem to another, as does average U content. Initial ratios, corrected for age, are remarkably constant for a given speleothem. By contrast, $\text{U}{}^{234}\text{U}{}^{238}$ ratios in seepage waters vary significantly from month to month at a given drip site, and their average values differ from that of the speleothem which they are depositing. This discrepancy is attributed either to long-term averaging-out of fluctuations, or fractional precipitation on the speleothem of a chemical species of uranium with a more constant ratio. Constancy of initial $\text{U}{}^{234}\text{U}{}^{238}$ ratios from $\text{Th}{}^{230}\text{U}{}^{234}$. datable portions of speleothems should permit $\text{U}{}^{234}\text{U}{}^{238}$-dating of older portions of the same speleothem, back to about 10⁶ yr B.P., with estimated precision of ±5 per cent.     

Sedimentary iron monosulfides: Kinetics and mechanism of formation

The reaction between hydrous iron oxides and aqueous sulfide species was studied at estuarine conditions of pH, total sulfide, and ionic strength to determine the kinetics and formation mechanism of the initial iron sulfide. Total, dissolved and acid extractable sulfide, thiosulfate, sulfate, and elemental sulfur were determined by spectrophotometric methods. Polysulfides, S₄^2? and S₅^2?, were determined from ultraviolet absorbance measurements and equilibrium calculations, while product hydroxyl ion was determined from pH measurements and solution buffer capacity.Elemental sulfur, as free and polysulfide sulfur, was 86% of the sulfide oxidation products; the remainder was thiosulfate. Rate expressions for the reduction and precipitation reactions were determined from analysis of electron balance and acid extractable iron monosulfide vs time, respectively, by the initial rate method. The rate of iron reduction in moles/liter/minute was given by $\text{d(}\text{reduction}\text{Fe)}\text{dt}\text{= kS}{}_{\mathrm{t}}{}^{0.5}\text{(J}{}^{\mathrm{+}}\text{)}{}^{0.5}\text{A}{}_{\mathrm{FeOOH}}{}^1$ where S_t was the total dissolved sulfide concentration, (H⁺) the hydrogen ion activity, both in moles/ liter; and A_FeOOH the goethite specific surface area in square meters/liter. The rate constant, k, was 0.017 ± 0.002m^?2 min^?1. The rate of reduction was apparently determined by the rate of dissolution of the surface layer of ferrous hydroxide. The rate expression for the precipitation reaction was $\text{d(FeS)}\text{dt}\text{= kS}{}_{\mathrm{t}}{}^1\text{(H}{}^{\mathrm{+}}\text{)}{}^1\text{A}{}_{\mathrm{FeOOH}}{}^1$ where $\text{d(FeS)}\text{dt}$ was the rate of precipitation of acid extractable iron monosulfide in moles/liter/minute, and k = 82 ± 18 mol^?1l²m^?2 min^?1.A model is proposed with the following steps: protonation of goethite surface layer; exchange of bisulfide for hydroxide in the mobile layer; reduction of surface ferric ions of goethite by dissolved bisulfide species which produces ferrous hydroxide surface layer elemental sulfur and thiosulfate; dissolution of surface layer of ferrous hydroxide; and precipitation of dissolved ferrous specie and aqueous bisulfide ion.     

Delivery of transuranic elements by rain to the Mediterranean Sea

The concentrations of ²³⁸Pu, ^{239 + 240}Pu, ²⁴¹Am and ¹³⁷Cs were determined in rain samples collected at Monaco in the course of 1978–1979. Based on these data, the annual deliveries of these radionuclides to the Mediterranean by rain are computed to be 0.18 ± 0.01 pCim^?2 for ²³⁸Pu, 8.1 ± 0.1 pCim^?2 for ^{239 + 240}Pu, 0.58 ± 0.02 pCim^?2 for ²⁴¹Am and 351 ± 4 pCim^?2 for ¹³⁷Cs.Comparing the delivery data with the mixed layer inventories of ^{239 + 240}Pu and ²⁴¹Am in the Mediterranean, the upper limits of the mean residence time of these radionuclides in the mixed layer were estimated to be 12.3 yr for ^{239 + 240}pu and 2.9 yr for ²⁴¹Am. These values are consistent with the conclusion deduced from the vertical distribution pattern of these transuranic elements in the Mediterranean.Based on delivery values, the annual activity ratios for ${}^{238}\text{pu}{}^{\mathrm{239\; +\; 240}}\text{Pu}$, ${}^{241}\text{Am}{}^{\mathrm{239\; +\; 240}}\text{Pu}$ and ${}^{\mathrm{239\; +\; 240}}\text{pu}{}^{137}\text{Cs}$ are found to be 0,022, 0.072 and 0.023 respectively. The ${}^{238}\text{pu}{}^{\mathrm{239\; +\; 240}}\text{pu}$ and ${}^{\mathrm{239\; +\; 240}}\text{Pu}{}^{137}\text{Cs}$ activity ratios vary within relatively narrow ranges with time, while a much wider variation was observed for the ${}^{241}\text{Am}{}^{\mathrm{239\; +\; 240}}\text{Pu}$ activity ratio. The cause of the wider variation of the ${}^{241}\text{Am}{}^{\mathrm{239\; +\; 240}}\text{Pu}$ ratio may be related to the difference in the mean age of fallout brought down in different seasons.