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Over the past three decades we have become increasingly aware of the fundamental importance of water, and aqueous alteration, on primitive solar-system bodies. Some carbonaceous and ordinary chondrites have been altered by interactions with liquid water within the first 10 million years after formation of their parent asteroids. Millimeter to centimeter-sized aggregates of purple halite containing aqueous fluid inclusions were found in the matrix of two freshly-fallen brecciated H chondrite falls, Monahans (1998, hereafter simply "Monahans") (H5) and Zag (H3-6) (Zolensky et al., 1999; Whitby et al., 2000; Bogard et al., 2001) In order to understand origin and evolution of the aqueous fluids inside these inclusions we much measure the actual fluid composition, and also learn the O and H isotopic composition of the water. It has taken a decade for laboratory analytical techniques to catch up to these particular nanomole-sized aqueous samples. We have recently been successful in (1) measuring the isotopic composition of H and O in the water in a few fluid inclusions from the Zag and Monahans halite, (2) mineralogical characterization of the solid mineral phases associated with the aqueous fluids within the halite, and (3) the first minor element analyses of the fluid itself. A Cameca ims-1270 equipped with a cryo-sample-stage of Hokkaido University was specially prepared for the O and H isotopic measurements. The cryo-sample-stage (Techno. I. S. Corp.) was cooled down to c.a. -190 C using liquid nitrogen at which the aqueous fluid in inclusions was frozen. We excavated the salt crystal surfaces to expose the frozen fluids using a 15 keV Cs+ beam and measured negative secondary ions. The secondary ions from deep craters of approximately 10 m in depth emitted stably but the intensities changed gradually during measurement cycles because of shifting states of charge compensation, resulting in rather poor reproducibility of multiple measurements of standard fluid inclusions of +/- 90 0/00(2 sigma) for delta D, and +/- 29 0/00 (2 sigma) for delta O-18. On the other hand, the reproducibility of Delta O-17 is plus or minus 8 /00 (2 sigma ) because the observed variations of isotope ratios follow a mass dependent fractionation law. Variations of delta D of the aqueous fluids range over sog,a 330(90; 2 sigma ) to +1200(90) 0/00 for Monahans and delta 300(96) 0/00 to +90(98)0/00 for Zag. Delta O-17 of aqueous fluids range over delta 16(22) 0/00 to +18(10) 0/00 for Monahans and +3(10) 0/00 to +27(11) 0/00 for Zag. These variations are larger than the reproducibility of standard analyses and suggest that isotope equilibria were under way in the fluids before trapping into halite. The mean values of delta D and Delta O-17 are +290 0/00 and +9 0/00, respectively. The mean values and the variations of these fluids are different from the representative values of ordinary chondrites, verifying our working hypothesis that the fluid inclusion-bearing halites were not indigenous to the H chondrite parent-asteroid but rather represent exogenous material delivered onto the asteroid from a separate cryovolcanically-active body. This initial isotopic work has demonstrated the feasibility of the measurements, but also revealed sample processing and analytical shortcomings that are now being addressed. Examination of solid mineral inclusions within Monahans and Zag halite grains by confocal Raman spectroscopy at the Carnegie Geophysical Laboratory has revealed them to be metal, magnetite, forsteritic olivine (Fo.98), macromolecular carbon (MMC), pyroxenes, feldspar with Raman spectral affinity to anorthoclase and, probably, fine-grained lepidocrocite (FeO(OH)). In addition, one inclusion features aliphatic material with Raman spectral features consistent with a mixture of short-chain aliphatic compounds. We have initiated analyses of the bulk composition of the fluids within the inclusions in Zag and Monahans halites at Virginia Tech by LA ICPMS using angilent 7500ce quadrupole ICPMS and a Lambda Physik GeoLas 193 nm excimer laser ablation system. Preliminary results reveal that the inclusion aqueous fluids contain highly charged cations of Ca, Mg and Fe. The minerals and compounds discovered thus far within Monahans/Zag halites are indicative of an originating body at least partly composed of unequilibrated anhydrous materials (high Fo olivine, pyroxenes, feldspars, possibly the metal) which were subjected to aqueous alteration (the halite parent brine) and containing a light organic component (the short-chain aliphatic compounds). This material was ejected from the originating body with little or no disruption, as evidenced with the presence of fluid inclusions. An actively geysering body similar to modern Enceladus (Postberg et al., 2011) may be a reasonable analogue in this respect. Also, the originating body should have been within close proximity to the H chondrite parent in order to generate the number of halite grains seen in Monahans and Zag. Other candidates for Monahans/Zag halite parent bodie(s) may include a young Ceres with its possible liquid ocean, or Main Belt comets.
The composition and structure of the Guin ungrouped iron meteorite inclusions have been investigated experimentally. The structural characteristics of polished and etched slabs of the meteorite were studied microscopically in reflected light. Modal abundances of troilite nodules and silicate inclusions were determined by weighing paper traces. The bulk composition of the silicate inclusions was calculated by combining modal phase abundances and mineral compositions. It is found that the largest silicate inclusion (2 x 4 cm) consists mostly of a shock-melted plagioclase-rich matrix surrounding large, partly melted augite grains. The oxygen isotopic composition of the inclusion is near that of LL chondrites. The inclusion is found to be similar in composition to selected melt pocket glasses in ordinary chondrites produced in situ by preferential melting of plagioclase rock due to shock compression. It is suggested that the Guin assemblage was formed by impact melting on a chondritic parent body. Silicate inclusions in IIE irons share many of the compositional and petrological characteristics of the Guin inclusions, indicating that IIE irons also formed by impact-melting of chondritic materials. Black and white photomicrographs of the silicate inclusions are provided.
Introduction: Hibonite is a primary refractory phase occurring in many CAIs, typically with spinel and perovskite. Our microstructural studies of CAIs from carbonaceous chondrites reveal a range of stacking defect densities and correlated non-stoichiometry in hibonite. We also conducted a series of annealing experiments, demonstrating that the Mg-Al substitution stabilized the formation of defect-structured hibonite. Here, we continue a detailed TEM analysis of hibonite-bearing inclusions from CM chondrites that have been well-characterized isotopically. We examine possible correlations of microstructure, morphology, mineralogy, and chemical and isotopic systematics of CM hibonites in order to better understand the formation history of hibonite in the early solar nebula. Methods: Fifteen hibonite-bearing inclusions from the Paris CM chondrite were analyzed using a JEOL 7600F SEM and a JEOL 8530F electron microprobe. In addition to three hibonite-bearing inclusions from the Murchison CM chondrite previously reported, we selected three inclusions from Paris, Pmt1-6, 1-9, and 1-10, representing a range of 26Al/27Al ratios and minor element concentrations for a detailed TEM study. We extracted TEM sections from hibonite grains using a FEI Quanta 3D field emission gun SEM/FIB. The sections were then examined using a JEOL 2500SE field-emission scanning TEM equipped with a Thermo-Noran thin window EDX spectrometer. Results and Discussion: A total of six hibonite-bearing inclusions, including two platy hibonite crystals (PLACs) and four spinel-hibonite inclusions (SHIBs), were studied. There are notable differences in chemical and isotopic compositions between the inclusions (Table 1), indicative of their different formation environment or timing. Our TEM observations show perfectly-ordered, stoichiometric hibonite crystals without stacking defects in two PLACs, 2-7-1 and 2-8-2, and in three SHIBs, Pmt1-6, 1-9, and 1-10. In contrast, SHIB 1-9-5 hibonite grains contain a low density of stacking defects linked to an increase in MgO contents, indicating complex, disordered intergrowths of stoichiometric and MgO-enriched hibonites. From the data collected to date, we find no clear correlation between the microstructures of hibonite and its morphological and mineralogical types that reflect distinct chemical and isotopic systematics [6-8,10]. Interestingly, the presence of no or few stacking defects in hibonite from the PLACs and SHIBs are in contrast to our experimental studies that produced very high densities of stacking defects in hibonite [3-5]. Unlike our experi-ments, electron microprobe data from the PLACs and SHIBs hibonite grains show a strong correlation between (Ti4++Si4+) and Mg2+ cations, suggesting that coupled substitutions of (Ti4++Mg2+) and (Si4++Mg2+) for 2Al3+ inhibit the formation of defect-structured hibonite. However, our experimental studies suggest that kinetics (e.g., cooling rate) or other thermal effects also exert a strong control on the microstructures and chemical compositions of hibonite. In Pmt1-6, elongated perovskite grains present at the hibonite grain boundaries display (121) twinning, indicative of a fast cooling (>50degC/min) after high-temperature events. Therefore, the nebular microstructural characteristics of hibonite, at least in this inclusion, would not have destroyed by subsequent high-temperature annealing. Conclusions: Our TEM observations thus far show no clear correlation in microstructures, morphological and mineralogical characteristics, and chemical and isotopic systematics of hibonites from CM chondrites. The observed variation in stacking defect densities in the hibonites may be controlled by thermal processes in the early solar nebula. A detailed TEM analysis of additional CM hibonite samples is underway to evaluate this hypothesis.
The effective-medium approximation (EMA) is based on the assumption that a heterogeneous particle can have a homogeneous counterpart possessing similar scattering and absorption properties. We analyze the numerical accuracy of the EMA by comparing superposition T-matrix computations for spherical aerosol particles filled with numerous randomly distributed small inclusions and Lorenz-Mie computations based on the Maxwell-Garnett mixing rule. We verify numerically that the EMA can indeed be realized for inclusion size parameters smaller than a threshold value. The threshold size parameter depends on the refractive-index contrast between the host and inclusion materials and quite often does not exceed several tenths, especially in calculations of the scattering matrix and the absorption cross section. As the inclusion size parameter approaches the threshold value, the scattering-matrix errors of the EMA start to grow with increasing the host size parameter and or the number of inclusions. We confirm, in particular, the existence of the effective-medium regime in the important case of dust aerosols with hematite or air-bubble inclusions, but then the large refractive-index contrast necessitates inclusion size parameters of the order of a few tenths. Irrespective of the highly restricted conditions of applicability of the EMA, our results provide further evidence that the effective-medium regime must be a direct corollary of the macroscopic Maxwell equations under specific assumptions.
New techniques are presented for using a laser microprobe to determine the spallation argon systematics of calcium-aluminum inclusions. The Ar-38(s) amounts determined for melilite and anorthite in a coarse-grained inclusion from Allende are 2.9 x 10 to the -8th and 1.3 x 10 to the -8th cc/g, respectively. The ratio of the amounts is consistent with the calcium contents of these two minerals. The Ar-38(s) amount determined for a fine-grained inclusion from Allende is 1.1 x 10 to the -8th cc/g. Calcium and potassium amounts were determined from irradiated samples of the same inclusions so that production of Ar-38 from calcium during the cosmic ray exposure of Allende could be determined for these samples. The production observed was 12.4 + or - 2.1 x 10 to the -8th cc STP Ar-38/g Ca for the coarse-grained inclusion and 9.9 + or - 2.4 cc STP Ar-38/g Ca for the fine-grained inclusion. No evidence of unusual exposure was observed in the two inclusions studied.
Inclusions of glass are likely to be present in phenocrysts in volcanic rocks from Mars, because these occur in volcanic rocks from both Earth and Moon. The usefulness of the inclusions depends upon their size and composition. The compositions of tiny inclusions may be modified by diffusion during growth of the enclosing crystal, the modifications increasing with melt viscosity (silica). Slow cooling results in crystallization and possible redistribution of volatiles, the effects increasing with decreasing silica. Primary volatile concentrations are best sought in inclusions larger than about 50 micrometer diameter in olivine or chromite crystals from quickly cooled basaltic scoria. Such crystals may be present in sands, but it would be preferable to extract them from individual rocks which could be dated and compositionally characterized. This would allow eventual understanding of the role of time and place in outgassing and volcanism on Mars. Analyses of volatiles in inclusions of more siliceous glass in non-basaltic rocks will reveal whether deep outgassing occurs and whether surface volatiles are recycled. Most volcanic crystals contain inclusions, but large inclusions can be uncommon. In the case of terrestrial basalts sample masses of several hundred grams are generally sufficient.
Calcium-aluminum-rich inclusions (CAIs) are the key to understanding physical and chemical conditions in the nascent solar nebula. These inclusions have the oldest radiometric ages of solar system materials and are composed of phases that are predicted to condense early from a gas of solar composition. Thus, their chemistry and textures record conditions and processes in the earliest stages of development of the solar nebula. Type B inclusions are typically larger and more coarse grained than other types with substantial evidence that many of them were at least partially molten. Type B inclusions are further subdivided into Type B1 (possess thick melilite mantle) and Type B2 (lack melilite mantle). Despite being extensively studied, the origin of the melilite mantles of Type B1 inclusions remains uncertain. We present petrologic and chemical data for a Type B inclusion, EK-459-7-2, that bears features found in both Type B1 and B2 inclusions and likely represents an intermediate between the two types. Detailed studies of more of these intermediate objects may help to constrain models for Type B1 rim formation.
Samples returned from asteroid Ryugu are chemically and mineralogically similar to CI chondrites [e.g., 1–3]. Both are predominantly composed of low-temperature aqueously formed secondary minerals, whereas high-temperature anhydrous primary minerals, such as olivine, low-Ca pyroxene, spinel, and hibonite, are rarely present. Using secondary ion mass spectrometry (SIMS; Cameca ims-1280HR at Hokkaido University), we performed O [4] and Al–Mg [5] isotope measurements of anhydrous primary minerals in samples of Ryugu and the Ivuna CI chondrite to constrain their origin.Anhydrous primary minerals in our samples of Ryugu and Ivuna occur mostly as monomineralic isolated grains embedded in hydrated matrix. Their O-isotope compositions are distributed along the slope-1 line on the O three-isotope diagram and range from Δ17O ~ –23 to 0‰. Mg-Al spinel grains are 16O-rich (Δ17O ~ –23‰). Low-Ca pyroxene grains are 16O-poor (Δ17O ~ –5‰). Olivine grains show a bimodal distribution of O-isotope composition:10 of 34 grains measured are 16O-rich (Δ17O ~ –23‰) and 24 grains are 16O-poor (Δ17O ~ –7 to 0‰). We found refractory inclusions composed of Mg-Al spinel and hibonite, one from Ryugu and one from Ivuna. Also, in Ivuna, we found an amoeboid olivine aggregate ( AOA) composed of olivine, diopside, anorthite, and Mg-Al spinel and an inclusion composed of olivine and Mg-Al spinel. The minerals in all of these inclusions are 16O-rich (Δ17O ~ –24‰).The 16O-rich grains and inclusions are mineralogically and O-isotopically similar to calcium-aluminum–rich inclusions (CAIs) and AOAs reported in other carbonaceous chondrites [6, 7]. In addition, the initial 26Al/27Al ratios of the two spinel-hibonite inclusions are inferred as ~4.4 × 10–5, also similar to most CAIs in carbonaceous chondrites [6, 8]. The range of Δ17O values for the 16O-poor olivine and low-Ca pyroxene grains is consistent withthat of these minerals in chondrules in most carbonaceous chondrites [9]. Moreover, the most frequent Δ17O value (–6‰) for Mg-rich (Mg# > 97) olivine grains is identical to those for chondrules. Although CI chondrites and Ryugu samples are devoid of chondrules, the 16O-poor grains most likely represent fragments of chondrule-like objects. The presence of both 16O-poor chondrule-like and 16O-rich refractory inclusion–like minerals in Ryugu and Ivuna suggests that some of their building blocks are similar to those of other carbonaceous chondrite groups. They both probably formed in the inner solar protoplanetary disk and were subsequently transported outward.Preliminary data for petrography of asteroid Bennu samples and chemical and isotopic compositions of theiranhydrous primary minerals will also be presented in the meeting.
Strong mixing trends on a (Th-230/Th-232) versus Th diagram show that the basalts are mixed magmas which have undergone interaction with the crust. Instantaneous Th/U ratios are less than time integrated ones but these exceed the Th/U ratios in the MORB and OIB sources. This indicates that the mantle may have undergone some metasomatic fluxing, crustal contamination of the basalts will also enhance these ratios. Early activity on the Akira plain is represented by early basalts and hawaiites. The early basalt samples are known to predate the earliest comendites. The most recent phase of activity is represented by another cinder cone 40-50 m high being feldspar and clinopyroxene phyric. Inclusions which occur in the comendites vary in size and distribution. The largest and most porphyritic are the trachytes (up to 40 cm) with alkali feldspar phases up to 6 mm and small pyroxenes in the ground mass. The second set of inclusions are smaller (up to 10 cm) and are largely aphyric. The distribution of the inclusions are not uniform, the Broad Acres (C5) lavas contain 2-5 percent. The size of the inclusions decrease from south to north, as does the abundance of the trachytic inclusions. The major element variations in the Naivasha basalts, hawaiites and magmatic inclusions are discussed.
Our understanding of early solar system fluids took a dramatic turn a decade ago with the discovery of fluid inclusion-bearing halite (NaCl) crystals in the matrix of two freshly fallen brecciated H chondrite falls, Monahans and Zag. Both meteorites are regolith breccias, and contain xenolithic halite (and minor admixed sylvite -- KCl, crystals in their regolith lithologies. The halites are purple to dark blue, due to the presence of color centers (electrons in anion vacancies) which slowly accumulated as 40K (in sylvite) decayed over billions of years. The halites were dated by K-Ar, Rb-Sr and I-Xe systematics to be 4.5 billion years old. The "blue" halites were a fantastic discovery for the following reasons: (1) Halite+sylvite can be dated (K is in sylvite and will substitute for Na in halite, Rb substitutes in halite for Na, and I substitutes for Cl). (2) The blue color is lost if the halite dissolves on Earth and reprecipitates (because the newly-formed halite has no color centers), so the color serves as a "freshness" or pristinity indicator. (3) Halite frequently contains aqueous fluid inclusions. (4) Halite contains no structural oxygen, carbon or hydrogen, making them ideal materials to measure these isotopic systems in any fluid inclusions. (5) It is possible to directly measure fluid inclusion formation temperatures, and thus directly measure the temperature of the mineralizing aqueous fluid. In addition to these two ordinary chondrites halite grains have been reliably reported in several ureilites, an additional ordinary chondrite (Jilin), and in the carbonaceous chondrite (Murchison), although these reports were unfortunately not taken seriously. We have lately found additional fluid inclusions in carbonates in several additional carbonaceous chondrites. Meteoritic aqueous fluid inclusions are apparently relatively widespread in meteorites, though very small and thus difficult to analyze.
Here we focus on spinel-cored spherule calcium-aluminum rich inclusions (CAI), dominantly ~75-80 microns in diameter in the CO3.1 chondrite Miller Range 90019, which make up ~ 12 % of the fine-grained CAIs in one thin section. Their mineralogical content ranges from rare grossite- and hibonite-bearing varieties, through perovskite-melilitebearing, to fassaite-bearing and finally anorthitebearing. Non-spherical CAIs have been divided into 4 other groups, defined based on mineralogical abundances. We also characterized a group of AOAs from this sample. No glass has been recognized in any inclusions. Some relatively evolved members (anorthite-, spinel- + fassaite-bearing) among the spherules are found engulfed in AOAs. We characterized the bulk compositions of ~145 CAIs and AOAs in this meteorite, derived from EDS-x-ray mapping of the inclusions. We determined bulk compositions both with and without Wark-Lovering rims (when present), which are largely composed of diopside forsterite. The balance of the inclusions appear to have not been melted or partially melted, but rather they have textures that indicate they are condensates, often modified by extensive reaction with nebular gases. This presents the opportunity to examine effects on the bulk compositions of spherules resulting potentially from melting plus evaporation. Other aspects of this suite of refractory inclusions have been discussed in these abstracts. Oxygen isotope variations in one spherule were presented in [4]. The latter study showed a complex history of reaction with nebular gases possessing a variety of Oisotope compositions. Additional O isotopic studies of inclusions in this work are included in Mane et al.
Fluid inclusions are naturally occurring mineral features that preserve trapped fluid phases inside a solid phase. These cavities exist as a closed system, recording the environmental conditions present during entrapment – both physical and chemical. As a result, fluid inclusions are great candidates for directly studying past fluid activity on extraterrestrial bodies within the Solar System. On Earth, fluid inclusions are abundant as they occur within numerous host minerals. They are a powerful tool for accurately and directly understanding the driving processes in various geological environments. In contrast, extraterrestrial fluid inclusions have only been positively identified on three separate occasions within host materials ranging from ordinary chondrites to C/B-type asteroid mission return samples. The possibility of directly studying the fluids involved in aqueous alteration and accurately constraining their heliocentric distances drives the hunt for these elusive capsules. Our goals are to locate new fluid inclusion candidates (hereon referred to as candidates) and assess whether fluid inclusions are a common feature within meteoritic carbonates and why they may have eluded detection for so long. We also aim to characterize the host grain’s mineralogical properties and assess the potentially preferential conditions for fluid entrapment on the asteroid parent body.
The coarse-grained, Ca-rich inclusions in the Allende meteorite are the highest-temperature condensates from the cooling solar nebula and, as such, the oldest solid objects in the solar system. All refractory elements with condensation points above the accretion temperature of the inclusions whose concentrations in them have been measured are seen to be present in the inclusions in unfractionated proportion to one another relative to Cl chondrites when data are averaged for a large number of inclusions. Observational data for U and theoretical data for both U and Pu suggest that these elements exhibited refractory behavior in the solar nebula. An experiment is proposed in which fissiogenic Xe and U contents are measured in a suite of these inclusions to obtain the Pu-244/U-238 ratio of the solar system at the time of initial condensation with an uncertainty of plus or minus 15%.