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

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

The extent of oxygen isotope exchange between clay minerals and sea water

The extent of oxygen isotopic exchange between detrital clay minerals and sea water was investigated by analyzing $\text{O}{}^{18}\text{O}{}^{16}$ ratios of separated fine-grained size fractions of deep-sea sediments from three North Pacific ocean cores. Isotopic results were interpreted according to models based on the assumption that the extent of isotopic exchange should increase with decreasing particle size and increasing time of exchange between the sediment and sea water. The data indicate that information concerning the provenance and mode of formation of detrital clay minerals can be obtained from the $\text{O}{}^{18}\text{O}{}^{16}$ ratios of the coarser-than-0.1 μm fraction of deep-sea sediments younger than several million years and the finer-than-0.1 μm fraction of deep-sea sediments younger than several tens of thousands of years. Furthermore, if the extent of chemical reaction between detrital clays and sea water is similar to the extent of oxygen isotopic exchange, such reaction may be important in regulating the chemistry of sea water.     

Columbia River volcanism: the question of mantle heterogeneity or crustal contamination

Basalts from the Columbia River flood basalt province of the northwestern U.S.A. show a large diversity in chemical and Nd and Sr isotopic compositions. ${}^{143}\text{Nd}{}^{144}\text{Nd}$ ranges from 0.51303 to 0.51208 and is strongly correlated with variations in ${}^{87}\text{Sr}{}^{86}\text{Sr}$. This correlation suggests mixing between two end member compositions, one characterized by ${}^{143}\text{Nd}{}^{144}\text{Nd}\text{> 0.51303}$ and ${}^{87}\text{Sr}{}^{86}\text{Sr}\text{< 0.7035}$, and the other with ${}^{143}\text{Nd}{}^{144}\text{Nd}\text{< 0.5120}$ and ${}^{87}\text{Sr}{}^{86}\text{Sr}\text{> 0.715}$. The more radiogenic component could be mantle enriched in incompatible elements during the Precambrian, or Precambrian materials of the continental crust. A quartz-rich xenolith found in the Columbia lavas has Rb-Sr and Sm Nd model ages of ≈ 1.4Æ, implying the existence of old, isotopically evolved crustal basement which could serve as contaminant. Nevertheless, crustal contamination alone cannot explain the chemical variation of the samples studied, and other fractionation processes must have occurred simultaneously. A model involving combined assimilation and crystal fractionation reproduces the chemical and isotopic characteristics of the volumetrically dominant Grande Ronde unit for an assumed crystallizing component of plagioclase, low calcium pyroxene and minor olivine. The data are not consistent with the suggestion that a ‘primordial’ mantle is the source for this continental flood basalt province. Rather they suggest that the main volume of these lavas was originally derived from a mantle similar in isotopic composition to island arc and ocean island basalts of the north Pacific. The primary magma was modified chemically and isotopically by crystal fractionation and assimilation of sialic crustal materials during its transport through, or storage in the continental crust.     

Intensive sampling of noble gases in fluids at Yellowstone: I. Early overview of the data; regional patterns

The Roving Automated Rare Gas Analysis (RARGA) lab of Berkeley's Physics Department was deployed in Yellowstone National Park for a 19 week period commencing in June, 1983. During this time 66 gas and water samples representing 19 different regions of hydrothermal activity within and around the Yellowstone caldera were analyzed on site. Routinely, the abundances of five stable noble gases and the isotopic compositions of He, Ne, and Ar were determined for each sample. In a few cases the isotopes of Kr and Xe were also determined and found to be of normal atmospheric constitution.Correlated variations in the isotopic compositions of He and Ar can be explained within the precision of the measurements by mixing of only three distinct components. The first component is of magmatic origin and is enriched in the primordial isotope ³He with ${}^3\text{He}{}^4\text{He}\text{≥ 16}$ times the air value. This component also contains radiogenic ⁴⁰Ar and possible ³⁶Ar with ${}^{40}\text{Ar}{}^{36}\text{Ar}\text{≥ 500}$, resulting in a ${}^3\text{He}{}^{36}\text{Ar}$ ratio ≥ 41,000 times the air value. The second component is assumed to be purely radiogenic ⁴He and ⁴⁰Ar (${}^{41}\text{He}{}^{401}\text{Ar}\text{= 4.08 ± .33}$). This component is the probable carrier of observed excesses of ²¹¹Ne, attributed to the α,n reaction on ¹⁸O. Its radiogenic character implies a crustal origin in U. Th, and Krich aquifer rocks. The third component, except for possible mass fractionation, is isotopically indistinguishable from the noble gases in the atmosphere. This component originates largely from infiltrating run-off water saturated with atmospheric gases.In addition to exhibiting nucleogenic ²¹¹Ne, Ne data show anomalies in the ratio ${}^{20}\text{Ne}{}^{20}\text{Ne}$, which correlate roughly with the ${}^{21}\text{Ne}{}^{22}\text{Ne}$ anomalies for the most part, but not as would occur from simple mass fractionation. Some exaggerated instances of the ${}^{20}\text{Ne}{}^{22}\text{Ne}$ anomaly occur which could be explained by combined mass fractionation of Ne and Ar isotopes to a severe degree coupled with remixing with normally isotopic gases. Otherwise exotic processes have to be invoked to explain the ²⁰Ne data.Relative abundances of the non-radiogenic and non-nucleogenic noble gases (²²Ne, ³⁶Ar, ⁸⁴Kr, and ¹³²Xe) are highly variable but strongly correlated. High Xe/Ar ratios are always accompanied by low Ne/ Ar ratios and vice versa. Except for water from the few cold (T < 20°C) springs analyzed, none of the samples have relative abundances consistent with air saturated water and the observed variations are not readily explained by the distillation of air saturated water.In characterizing each area of hydrothermal activity by the highest ${}^3\text{He}{}^4\text{He}$ ratio found for that area, we find that within the caldera this parameter is somewhat uniform at ~7 ± 1 times the air value. There are exceptions, most notably at Mud Volcano, an area located along a crest of recent and rapid uplift. Here the maximum ${}^3\text{He}{}^4\text{He}$ ratio is ~ 16 times the air value. Also noteworthy is Gibbon Basin which is in the vicinity of the most recent rhyolitic volcanism and exhibits a ${}^3\text{He}{}^4\text{He}$ ratio ~ 13 times the air value. Immediately outside the caldera the maximum $\text{sol}{}^3\text{He}{}^4\text{He}$ ratio decreases rapidly to values < ~3 times the air value.     

Methane-producing bacteria: natural fractionations of the stable carbon isotopes

The ${}^{13}\text{C}{}^{12}\text{C}$ fractionation factors ($\text{CO}{}_2\text{CH}{}_4$) for the reduction of CO₂ to CH₄ by pure cultures of methane-producing bacteria are, for Methanosarcina barkeri at 40°C, 1.045 ± 0.002; for Methanobacterium strain M.o.H. at 40°C, 1.061 ± 0.002; and, for Methanobacterium thermoautotrophicum at 65°C, 1.025 ± 0.002. These observations suggest that the acetic acid used by acetate dissimilating bacteria, if they play an important role in natural methane production, must have an intramolecular isotopic fractionation ($\text{CO}{}_2\text{H}\text{CH}{}_3$) approximating the observed $\text{CO}{}_2\text{CH}{}_4$ fractionation.     

Annual periodicity of the 18O16O and 13C12C ratios in the coral Montastrea annularis

The isotopic ratios ${}^{18}\text{O}{}^{16}\text{O}$ and ${}^{13}\text{C}{}^{12}\text{C}$ show an annual periodicity in the coral Montastrea annularis from Bermuda, Jamaica and Barbados. The abundances of ¹⁸O and ¹³C are positively correlated in the Jamaica and Barbados samples, but inversely related in the Bermuda sample. Annual high density growth bands are formed during the season of warmest water temperature at all 3 sites and are enriched in ¹⁶O. M. Annularis has a constant displacement from oxygen isotopic equilibrium and accurately records seasonal temperature variations via the temperature-dependent aragonite-water fractionation factor. Light intensity, through the activity of the coral's endosymbiotic algae, regulates the depth-dependent and seasonal variations in the skeletal carbon isotopic composition.     

Oxygen isotopic exchangeability of diatom valve silica; interpretation and consequences for paleoclimatic studies

Problems of analytical reproducibility have impeded the application of ${}^{18}\text{O}{}^{16}\text{O}$ ratio measurements of biogenic opal to paleoclimatology. Lack of reproducibility has been attributed to the labile nature of part of the oxygen of the silica. This has been studied using oxygen isotopic exchange between diatom silica and water vapor. This reaction involves the reversible hydrolysis of weak Si-O bonds. Using controlled exchange with waters of different oxygen isotopic composition, the isotopic ratio of both the exchanged and the unexchanged silica-bound oxygen were estimated. Optimum conditions for reproducible measurement of the oxygen isotopic composition of diatom silica are defined.     

Importance of the Lu-Hf isotopic system in studies of planetary chronology and chemical evolution

The ¹⁷⁶Lu-¹⁷⁶Hf isotope method and its applications in earth sciences are discussed. Greater fractionation of Lu/Hf than Sm/Nd in planetary magmatic processes makes ${}^{176}\text{Hf}{}^{177}\text{Hf}$ a powerful geochemical tracer. In general, proportional variations of ${}^{176}\text{Hf}{}^{177}\text{Hf}$ exceed those of ${}^{143}\text{Nd}{}^{\mathrm{l44}}\text{Nd}$ by factors of 1.5–3 in terrestrial and lunar materials. Lu-Hf studies therefore have a major contribution to make in understanding of terrestrial and other planetary evolution through time, and this is the principal importance of Lu-Hf. New data on basalts from oceanic islands show unequivocally that whereas considerable divergences occur in ${}^{176}\text{Hf}{}^{177}\text{Hf}\text{-}{}^{87}\text{Sr}{}^{86}\text{Sr}$ and ${}^{143}\text{Nd}{}^{\mathrm{l44}}\text{Nd}\text{-}{}^{87}\text{Sr}{}^{86}\text{Sr}$ diagrams, ${}^{176}\text{Hf}{}^{177}\text{Hf}$ and ${}^{143}\text{Nd}{}^{144}\text{Nd}$ display a single, linear isotopic variation in the suboceanic mantle. These discordant ${}^{87}\text{Sr}{}^{86}\text{Sr}$ relationships may allow, with the acquisition of further Hf-Nd-Sr isotopic data, a distinction between processes such as mantle metasomatism, influence of seawater-altered material in the magma source, or recycling of sediments into the mantle. In order to evaluate the Hf-Nd isotopic correlation in terms of mantle fractionation history, there is a need for measurements of Hf distribution coefficients between silicate minerals and liquids, and specifically for a knowledge of Hf behavior in relation to rareearth elements. For studying ancient terrestrial Hf isotopic variations, the best quality Hf isotope data are obtained from granitoid rocks or zircons. New data show that very U-Pb discordant zircons may have upwardly-biased ${}^{176}\text{Hf}{}^{177}\text{Hf}$, but that at least concordant to slightly discordant zircons appear to be reliable carriers of initial ${}^{176}\text{Hf}{}^{177}\text{Hf}$. Until the controls on addition of radiogenic Hf to zircon are understood, combined zircon-whole rock studies are recommended. Lu-Hf has been demonstrated as a viable tool for dating of ancient terrestrial and extraterrestrial samples, but because it offers little advantage over existing methods, is unlikely to find wide application in pure chronological studies.     

Atmospheric and juvenile noble gases in the Skaergaard layered igneous intrusion

Gabbro and diorite from the Skaergaard layered igneous intrusion contain noble gases which are mixtures of atmospheric and juvenile components. Atmospheric noble gases predominate in samples that have undergone extensive oxygen isotope exchange with meteoric-hydrothermal water. The source of the atmospheric noble gas component is inferred to be the hydrothermal circulation system. A juvenile component with ${}^{40}\text{Ar}{}^{36}\text{Ar}\text{≥ 6100}$ and containing fission xenon is also present This component predominates in samples showing unaltered magmatic oxygen isotope compositions. Neon of atmospheric isotopic composition is associated with the juvenile radiogenic ⁴⁰Ar and fission xenon. The source of this second noble gas component may be either the crustal country rock or the upper mantle. If the neon is juvenile primordial neon from a mantle source region, terrestrial primordial ${}^{20}\text{Ne}{}^{22}\text{Ne}$ is the same as atmospheric to within 4%. However, subduction of atmospheric noble gases into the upper mantle may provide an alternate source of neon and other noble gases in the mantle.     

Experimental observations on carbon isotope exchange in carbonate-water systems

This study presents data from experiments investigating carbon isotope exchange between carbonate solution and solid calcite using carbon-13 as a tracer. All experiments were done with calcite saturated solutions and results show that a two-step adsorption-recrystallization reaction takes place. Isotope effects are caused by exchange by carbonate on the solid surface with carbon in the aqueous phase. Adsorption reactions are characterized by a maximum isotopic exchange capacity (IEC) on crystal surfaces of about 10¹¹ reaction sites per cm², following a second order rate law with respect to ¹³C concentration in solution ($\text{constant}\text{kex ? 10}{}^6\text{cm}{}^5\text{mole}{}^{\mathrm{?1}}\text{s}{}^{\mathrm{?1}}$ and $\text{half-life}\text{t}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{= 700}\text{s}$). The adsorption reaction was followed by a first order recrystallization which is characterized by a rate constant of the order of 10^?8 s^?1 and a $\text{t}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ of 10⁷ s. Negative isotopic gradient experiments and runs with calcite crystals in Mg²⁺ spiked solutions provided the preliminary basis for the characterization of the mechanisms of both proposed reactions.     

Isotopic composition of strontium in Indian kimberlites

Strontium isotopic studies on twenty three whole rock kimberlites from two petrographic provinces in India show variation of initial ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios from 0.7027 to 0.7102. The variation is unrelated to the degree of alteration. Between the micaceous and basaltic varieties there is some overlap in the Sr isotopic ratios. Leaching experiments on whole rock samples showed more highly radiogenic Sr in leaches compared to the bulk samples.In two diatremes, the initial ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios show a positive correlation with $\text{Rb}\text{Sr}$ which is believed to reflect a source event earlier than the formation of the kimberlites. The observed Sr isotopic data can be caused by (i) melting of a heterogeneous source or (ii) disequilibrium partial melting in the source region. In the former case, variable isotopic composition would be a necessary consequence of melting in small subsystems.     

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.     

Hydrogen and carbon isotopic ratios of the cellulose nitrate and saponifiable lipid fractions prepared from annual growth rings of a California redwood

The $\text{D}\text{H}$ and ${}^{13}\text{C}{}^{12}$C ratios of the cellulose nitrate and saponifiable lipid fractions prepared from eleven annual growth rings of a California redwood were determined. The $\text{D}\text{H}$ ratios of the two fractions are related to one another for the annual rings in the sapwood portion of the tree, but not for those in the heartwood or in the wood undergoing the transition from sapwood to heartwood. No relationship was observed between the ${}^{13}\text{C}{}^{12}$ ratios of the two fractions. These results suggest that analysis of the hydrogen isotopic composition of the saponifiable lipid fractions in plants will provide information useful for climatic reconstruction provided the initial isotopic record has not been changed by subsequent physiological or diagenetic processes.     

A detailed Pb isotopic study of crustal contamination/assimilation: The Edgecumbe volcanic field,SE Alaska

To better understand the process of crustal contamination/assimilation, 23 Pb isotopic compositions and 12 concentrations have been measured on lavas and basement rocks from the Edgecumbe volcanic field, SE Alaska. Measured isotopic ratios have the following ranges: ${}^{206}\text{Pb}{}^{204}\text{Pb}\text{= 18.477–19.161}$; ${}^{207}\text{Pb}{}^{204}\text{Pb}\text{= 15.562–15.679}$; ${}^{208}\text{Pb}{}^{204}\text{Pb}\text{= 38.17–38.85}$. While the data form well-constrained linear arrays on Pb-Pb diagrams, no simple correlation exists with major element composition. Basaltic lavas (≤ 51 wt% SiO₂) are characterized by two isotopic groups. The olivine basalt (≤ 48% SiO₂) is more radiogenic than the plagioclase basalt (48–51%) which also shows more heterogeneity. In the silica range 52–55%, Pb isotopic ratios increase significantly but remain fairly constant in the range 55–70% SiO₂. Lead concentrations vary from 1 ppm in the basalts to 7 ppm in the rhyodacites. Analyzed basement rocks are more radiogenic than any of the lavas $\text{(}{}^{206}\text{Pb}{}^{204}\text{Pb}\text{= 19.20}$; ${}^{207}\text{Pb}{}^{204}\text{Pb}\text{= 15.65}$; ${}^{208}\text{Pb}{}^{204}\text{Pb}\text{= 38.86}$. The Pb isotopic data are qualitatively consistent with the contamination process described by Myerset al. (1984). However, because of fundamental differences in the mixing relations between the Sr system studied earlier and the Pb system, the new Pb data have revealed details of the process not apparent from the Sr data alone. In particular, it has been shown that the parent magma was more primitive than originally assumed, and that two contamination events are recorded in the lavas. The first event, involving a mafic parent and different crustal contaminants, produced the intermediate and siliceous hybrids in cupolas located above the main basaltic chamber. The types of country rock intruded as well as the degree of partial fusion achieved in individual cupolas controlled the range of hybrid compositions produced while the eruption sequence was determined by the order in which the cupolas were tapped. The second contamination event produced the plagioclase basalt, the most voluminous basaltic unit, by mixing the mafic parent with the olivine basalt, an independent, primary magma. Our results suggest crustal contamination models that assume bulk assimilation of crustal end members may be too simplistic.     

Pb isotope geochemistry of a massif-type anorthositic-charnockitic body: The Hidra Massif (Rogaland,S.W. Norway).

The Hidra Massif (Rogaland complex, S.W. Norway) is a massif-type anorthositic-charnockitic body. It consists of undeformed anorthosites and leuconorites, grading into fine-grained jotunites at the contact with the granulite facies gneisses of the metamorphic envelope. A stockwork of charnockitic dykes cross-cuts the massif. The Pb isotopic compositions of the anorthosites and leuconorites are comparable or slightly less radiogenic than those of the jotunites (${}^{206}\text{Pb}{}^{204}\text{Pb}$ from 18.079 to 19.307,(${}^{207}\text{Pb}{}^{204}\text{Pb}$ from 15.568 to 15.657 and ${}^{208}\text{Pb}{}^{204}\text{Pb}$ from 37.617 to 38.493). These values are compatible with an upper mantle origin for the parental magma of jotunitic composition and for the plagioclasic cumulates, but show the incorporation of lower crustal material (U-depleted and thus less radiogenic). The charnockitic dykes have significantly less radiogenic Pb isotopic compositions (${}^{206}\text{Pb}{}^{204}\text{Pb}$ from 17.472 to 19.171, ${}^{207}\text{Pb}{}^{204}\text{Pb}$ from 15.489 to 15.620and ${}^{208}\text{Pb}{}^{204}\text{Pb}$ from 36.991 to 40.922) which can be explained by a larger proportion of lower crustal contamination material. The contaminant could be the granulite facies gneisses of the metamorphic envelope. This interpretation is compatible with the K-Rb relationships of these rocks and with the O and Sr isotopic geochemistry.The proportion of contaminating lead in the charnockitic dykes can be estimated at 55 ± 15% considering the border facies jotunite as the uncontaminated parental magma and the least radiogenic gneiss of the metamorphic envelope as the contaminant.     

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.     

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

Isotopic concentrations of the noble gases have been measured in several different phases of Elephant Moraine A79001 and in whole rock samples of Zagami and Allan Hills A77005, three meteorites which belong to the rare group of SNC achondrites that may have originated from the planet Mars. Shocked phases of EETA79001 contain a trapped Ar, Kr, and Xe component characterized by ${}^{84}\text{Kr}{}^{132}\text{Xe}$ ～15, ${}^{40}\text{Ar}{}^{36}\text{Ar}\text{> 2000}$, ${}^{129}\text{Xe}{}^{132}\text{Xe ≥ 2}$, and ${}^4\text{He}{}^{40}\text{Ar}\text{≤ 0.1}$. These elemental and isotopic ratios are unlike those for any other noble gas component except analyses of the Martian atmosphere made by Viking spacecraft. The isotopic composition of the trapped Kr shows an approximate 1% per mass unit enrichment of lighter isotopes compared to terrestrial Kr, and the traped Xe may show either a fission component or a fractionated enrichment of heavier isotopes compared to terrestrial Xe. It is hypothesized that these gases represent a portion of the Martian atmosphere which was shock-implanted into EETA79001, and that they constitute direct evidence of a Martian origin for the shergottite meteorites. Cosmic ray-produced gases in the eight known SNC meteorites form three distinct groups with exposure ages of ～11 MY (Chassigny and the nakhlites), ～2.6 MY (Shergotty, Zagami, and ALHA77005), and ～0.5 MY (EETA79001). These ages suggest three distinct events and cannot have been produced by irradiation for a common time under greatly different shielding. Comparison of cosmogenic ${}^3\text{He}{}^{21}\text{Ne}$ measured in EETA79001 with two independent models for the production of this ratio as a function of shielding indicates that this meteorite was irradiated in space as a relatively small object. If the SNC meteorites were ejected from Mars ～ 180 My ago, the shock age of the shergottites, they must have been relatively large objects (>6 meters diameter) which experienced at least three space collisions to initiate cosmic ray exposure. Ejection from Mars by three events at the times of initiation of cosmic ray exposure would permit the ejected objects to have been much smaller (<1 meter diameter), but would require three such events on 1.3 Gy Martian terraine in the past ～10 MY and would not explain the common 180 MY shock age seen in all four shergottites.