Impact features of enstatite-rich meteorites

Enstatite-rich meteorites include EH and EL chondrites, rare ungrouped enstatite chondrites, aubrites, a few metal-rich meteorites (possibly derived from the mantle of the aubrite parent body), various impact-melt breccias and impact-melt rocks, and a few samples that may be partial-melt residues ultimately derived from enstatite chondrites. Members of these sets of rocks exhibit a wide range of impact features including mineral-lattice deformation, whole-rock brecciation, petrofabrics, opaque veins, rare high-pressure phases, silicate darkening, silicate-rich melt veins and melt pockets, shock-produced diamonds, euhedral enstatite grains, nucleation of enstatite on relict grains and chondrules, low MnO in enstatite, high Mn in troilite and oldhamite, grains of keilite, abundant silica, euhedral graphite, euhedral sinoite, F-rich amphibole and mica, and impact-melt globules and spherules. No single meteorite possesses all of these features, although many possess several. Impacts can also cause bulk REE fractionations due to melting and loss of oldhamite (CaS) – the main REE carrier in enstatite meteorites. The Shallowater aubrite can be modeled as an impact-melt rock derived from a large cratering event on a porous enstatite chondritic asteroid; it may have been shock melted at depth, slowly cooled and then excavated and quenched. Mount Egerton may share a broadly similar shock and thermal history; it could be from the same parent body as Shallowater. Many aubrites contain large pyroxene grains that exhibit weak mosaic extinction, consistent with shock-stage S4; in contrast, small olivine grains in some of these same aubrites have sharp or undulose extinction, consistent with shock stage S1 to S2. Because elemental diffusion is much faster in olivine than pyroxene, it seems likely that these aubrites experienced mild post-shock annealing, perhaps due to relatively shallow burial after an energetic impact event. There are correlations among EH and EL chondrites between petrologic type and the degree of shock, consistent with the hypothesis that collisional heating is mainly responsible for enstatite-chondrite thermal metamorphism. Nevertheless, the apparent shock stages of EL6 and EH6 chondrites tend to be lower than EL3-5 and EH3-5 chondrites, suggesting that the type-6 enstatite chondrites (many of which possess impact-produced features) were shocked and annealed. The relatively young Ar–Ar ages of enstatite chondrites record heating events that occurred long after any ²⁶Al that may have been present initially had decayed away. Impacts remain the only plausible heat source at these late dates. Some enstatite meteorites accreted to other celestial bodies: Hadley Rille (EH) was partly melted when it struck the Moon; Galim (b), also an EH chondrite, was shocked and partly oxidized when it accreted to the LL parent asteroid. EH, EL and aubrite-like clasts also occur in the polymict breccias Kaidun (a carbonaceous chondrite) and Almahata Sitta (an anomalous ureilite). The EH and EL clasts in Kaidun appear unshocked; some clasts in Almahata Sitta may have been extensively shocked on their parent bodies prior to being incorporated into the Almahata Sitta host.     

Application of iron and zinc isotopes to track the sources and mechanisms of metal loading in a mountain watershed

Here the hydrogeochemical constraints of a tracer dilution study are combined with Fe and Zn isotopic measurements to pinpoint metal loading sources and attenuation mechanisms in an alpine watershed impacted by acid mine drainage. In the tested mountain catchment, δ⁵⁶Fe and δ⁶⁶Zn isotopic signatures of filtered stream water samples varied by ∼3.5‰ and 0.4‰, respectively. The inherent differences in the aqueous geochemistry of Fe and Zn provided complimentary isotopic information. For example, variations in δ⁵⁶Fe were linked to redox and precipitation reactions occurring in the stream, while changes in δ⁶⁶Zn were indicative of conservative mixing of different Zn sources. Fen environments contributed distinctively light dissolved Fe (<−2.0‰) and isotopically heavy suspended Fe precipitates to the watershed, while Zn from the fen was isotopically heavy (>+0.4‰). Acidic drainage from mine wastes contributed heavier dissolved Fe (∼+0.5‰) and lighter Zn (∼+0.2‰) isotopes relative to the fen. Upwelling of Fe-rich groundwater near the mouth of the catchment was the major source of Fe (δ⁵⁶Fe ∼ 0‰) leaving the watershed in surface flow, while runoff from mining wastes was the major source of Zn. The results suggest that given a strong framework for interpretation, Fe and Zn isotopes are useful tools for identifying and tracking metal sources and attenuation mechanisms in mountain watersheds.     

Shock effects in “EH6” enstatite chondrites and implications for collisional heating of the EH and EL parent asteroids

Of the six chondrites that were listed as EH6 or EH6-an during the course of this study, we confirm the EH classification of Y-8404, Y-980211 and Y-980223 and the EH-an classification of Y-793225; two chondrites (A-882039 and Y-980524) are reclassified as EL (the former contains ferroan alabandite and both contain kamacite with ∼1 wt% Si). All of the meteorites contain euhedral enstatite grains surrounded by metal ± sulfide (although this texture is rare in Y-793225), consistent with enstatite crystallizing from a mixed melt. All contain enstatite with <0.04 wt% MnO; the three EH chondrites average 0.25 wt% Mn in troilite. (Literature data show that typical EH3-EH5 chondrites contain enstatite with 0.13-0.20 wt% MnO and troilite with 0.05-0.11 wt% Mn.) The three EH chondrites contain keilite [(Fe_>0.5,Mg_<0.5)S], which has been interpreted in the literature as a product of impact melting. Y-8404 and Y-980223 contain abundant silica (∼13 and ∼10 wt%, respectively), a rare phase in most enstatite chondrites. We suggest that all six meteorites have experienced impact melting; Mn was preferentially partitioned into sulfide during subsequent crystallization. The silica-rich samples may have become enriched in the aftermath of the impact by a redox reaction involving FeO and reduced Si. A-882039, Y-8404, Y-980211, Y-980223 and Y-980524 were incompletely melted; they contain rare relict chondrules and are classified as impact-melt breccias; Y-793225 is a chondrule-free impact-melt rock. If these EH and EH-an chondrites (which were previously listed as petrologic type 6) have, in fact, been impact melted, it seems plausible that collisional heating is generally responsible for EH-chondrite metamorphism. This is consistent with literature data showing that a large fraction (?0.7) of those chondrites classified EH5-7 and a significant fraction (?0.3) of those chondrites classified EH4 and EH4/5 possess textural and mineralogical properties suggestive of impact melting. In addition, ∼60% of classified EL6-7 chondrites (now including A-882039 and Y-980524) appear to have formed by impact melting. It thus seems likely that collisional heating is mainly responsible for EL- and EH-chondrite metamorphism.     

Deuterium enrichments in chondritic macromolecular material—Implications for the origin and evolution of organics, water and asteroids

Here we report the elemental and isotopic compositions of the insoluble organic material (IOM) isolated from several previously unanalyzed meteorites, as well as the reanalyses of H isotopic compositions of some previously measured samples (Alexander et al., 2007). The IOM in ordinary chondrites (OCs) has very large D enrichments that increase with increasing metamorphism and decreasing H/C, the most extreme δD value measured being almost 12,000‰. We propose that such large isotopic fractionations could be produced in the OC parent bodies through the loss of isotopically very light H₂ generated when Fe was oxidized by water at low temperatures (<200 °C). We suggest that similar isotopic fractionations were not generated in the IOM of CV and CO chondrites with similar metamorphic grades and IOM H/C ratios because proportionately less water was consumed during metamorphism, and the remaining water buffered the H isotopic composition of the IOM even a H was being lost from it.Hydrogen would also have been generated during the alteration of CI, CM and CR carbonaceous chondrites. The IOM in these meteorites exhibit a considerable range in isotopic compositions, but all are enriched in D, as well as ¹⁵N, relative to terrestrial values. We explore whether these enrichments could also have been produced by the loss of H₂, but conclude that the most isotopically anomalous IOM compositions in meteorites from these groups are probably closest to their primordial values. The less isotopically anomalous IOM has probably been modified by parent body processes. The response of IOM to these processes was complex and varied, presumably reflecting differences in conditions within and between parent bodies.The D enrichments associated with H₂ generation, along with exchange between D-rich IOM and water in the parent bodies, means that it is unlikely that any chondrites retain the primordial H isotopic composition of the water ice that they accreted. The H isotopic compositions of the most water-rich chondrites, the CMs and CIs, are probably the least modified and their compositions (δD ? −25‰) suggest that their water did not form at large radial distances from the Sun where ice is predicted to be very D-rich. Yet models to explain the O isotopic composition of inner Solar System bodies require that large amounts of ice were transported from the outer to the inner Solar System.     

Zn and Cu isotopic variations in chondrites and iron meteorites: Early solar nebula reservoirs and parent-body processes

High-precision Zn isotopic variations are reported for carbonaceous chondrites (CC), equilibrated (EOC) and unequilibrated (UOC) ordinary chondrites, iron meteorites from the IAB-IIICD (nonmagmatic) and IIIA (magmatic) groups, and metal from the Brenham pallasite. For irons, δ⁶⁵Cu values are also reported. Data have also been obtained on a coarse-grained type-B calcium-, aluminum-rich refractory inclusion (CAI) from Allende and on acid leaches of Allende (CV3), Krymka (LL3), and Charsonville (H6). Variations expressed as δ⁶⁶Zn (deviation in parts per thousand of ⁶⁶Zn/⁶⁴Zn in samples relative to a standard) spread over a range of 0.3‰ for carbonaceous chondrites, 2‰ for ordinary chondrites, and 4‰ for irons.The measured ⁶⁶Zn/⁶⁴Zn, ⁶⁷Zn/⁶⁴Zn, and ⁶⁸Zn/⁶⁴Zn ratios vary linearly with mass difference and define a common isotope fractionation line with terrestrial samples, which demonstrates that Zn was derived from an initially single homogeneous reservoir. The δ⁶⁶Zn values are correlated with meteorite compositions and slightly decrease in the order CI, CM, CV-CO, and to UOC. The isotopically light Zn of Allende CAI and the acid-resistant residues of Allende and Krymka show that the light component is associated with refractory material, presumably minerals from the spinel-group. This, together with the reverse correlation between relative abundances of light Zn isotopes and volatile element abundances, suggests that Zn depletion in planetary bodies with respect to CI cannot be ascribed to devolatilization of CI-like material. These observations rather suggest that refractory material reacted with a gas phase enriched in the lighter Zn isotopes. Alternatively, chondrules with their associated rims should carry a light Zn isotopic signature. The δ⁶⁶Zn values of unequilibrated chondrites are rather uniform, whereas equilibrated chondrites show distinctly more isotopic variability.The values of δ⁶⁵Cu-δ⁶⁶Zn in irons define two trends. The moderate and positively correlated Cu and Zn isotope variations in IIIA and pallasite samples probably reflect crystallization of silicate, sulfide, and solid metal from the liquid metal. The range of δ⁶⁶Zn values of the IAB-IIICD group is large (>3‰) and contrasts with the moderate fractionation of Cu isotopes. We interpret this feature and the negative δ⁶⁶Zn-δ⁶⁵Cu correlation as reflecting mixing, possibly achieved by percolation, between metals from a regolith devolatilized at low temperature (enriched in heavy zinc) and metallic liquids formed within the parent body.     

The formation and alteration of the Renazzo-like carbonaceous chondrites I: Implications of bulk-oxygen isotopic composition

To better understand the role of aqueous alteration on the CR chondrite parent asteroid, a whole-rock oxygen isotopic study of 20 meteorites classified as Renazzo-like carbonaceous chondrites (CR) was conducted. The CR chondrites analyzed for their oxygen isotopes were Dhofar 1432, Elephant Moraine (EET) 87770, EET 92042, EET 96259, Gao-Guenie (b), Graves Nunataks (GRA) 95229, GRA 06100, Grosvenor Mountains (GRO) 95577, GRO 03116, LaPaz Ice Field (LAP) 02342, LAP 04720, Meteorite Hills (MET) 00426, North West Africa (NWA) 801, Pecora Escarpment (PCA) 91082, Queen Alexandra Range (QUE) 94603, QUE 99177, and Yamato-793495 (Y-793495). Three of the meteorites, Asuka-881595 (A-881595), GRA 98025, and MET 01017, were found not to be CR chondrites. The remaining samples concur petrographically and with the well-established oxygen-isotope mixing line for the CR chondrites. Their position along this mixing line is controlled both by the primary oxygen-isotopic composition of their individual components and their relative degree of aqueous alteration. Combined with literature data and that of this study, we recommend the slope for the CR-mixing line to be 0.70 ± 0.04 (2σ), with a δ¹⁷O-intercept of −2.23 ± 0.14 (2σ).Thin sections of Al Rais, Shi?r 033, Renazzo, and all but 3 samples analyzed for oxygen isotopes were studied petrographically. The abundance of individual components is heterogeneous among the CR chondrites, but FeO-poor chondrules and matrix are the most abundant constituents and therefore, dominate the whole-rock isotopic composition. The potential accreted ice abundance, physico-chemical conditions of aqueous alteration (e.g. temperature and composition of the fluid) and its duration control the degree of alteration of individual CR chondrites. Combined with literature data, we suggest that LAP 02342 was exposed to lower temperature fluid during alteration than GRA 95229. With only two falls, terrestrial alteration of the CR chondrites complicates the interpretation of their whole rock isotopic composition, particularly in the most aqueously altered samples, and those with relatively higher matrix abundances. We report that QUE 99177 is the isotopically lightest whole rock CR chondrite known (δ¹⁸O = −2.29‰, δ¹⁷O = −4.08‰), possibly due to isotopically light unaltered matrix; which shows that the anhydrous component of the CR chondrites is isotopically lighter than previously thought. Although it experienced aqueous alteration, QUE 99177 provides the best approximation of the pristine CR-chondrite parent body’s oxygen-isotopic composition, before aqueous alteration took place. Using this value as a new upper limit on the anhydrous component of the CR chondrites, water/rock ratios were recalculated and found to be higher than previously thought; ratios now range from 0.281 to 1.157. We also find that, according to their oxygen isotopes, a large number of CR chondrites appear to be minimally aqueously altered; although sample heterogeneity complicates this interpretation.     

Variations of Li and Mg isotope ratios in bulk chondrites and mantle xenoliths

We present whole rock Li and Mg isotope analyses of 33 ultramafic xenoliths from the terrestrial mantle, which we compare with analyses of 30 (mostly chondritic) meteorites. The accuracy of our new Mg isotope ratio measurement protocol is substantiated by a combination of standard addition experiments, the absence of mass independent effects in terrestrial samples and our obtaining identical values for rock standards using two different separation chemistries and three different mass-spectrometric introduction systems. Carbonaceous, ordinary and enstatite chondrites have irresolvable mean stable Mg isotopic compositions (δ²⁵Mg = −0.14 ± 0.06; δ²⁶Mg = −0.27 ± 0.12‰, 2SD), but our enstatite chondrite samples have lighter δ⁷Li (by up to ∼3‰) than our mean carbonaceous and ordinary chondrites (3.0 ± 1.5‰, 2SD), possibly as a result of spallation in the early solar system. Measurements of equilibrated, fertile peridotites give mean values of δ⁷Li = 3.5 ± 0.5‰, δ²⁵Mg = −0.10 ± 0.03‰ and δ²⁶Mg = −0.21 ± 0.07‰. We believe these values provide a useful estimate of the primitive mantle and they are within error of our average of bulk carbonaceous and ordinary chondrites. A fuller range of fresh, terrestrial, ultramafic samples, covering a variety of geological histories, show a broad positive correlation between bulk δ⁷Li and δ²⁶Mg, which vary from −3.7‰ to +14.5‰, and −0.36‰ to + 0.06‰, respectively. Values of δ⁷Li and δ²⁶Mg lower than our estimate of primitive mantle are strongly linked to kinetic isotope fractionation, occurring during transport of the mantle xenoliths. We suggest Mg and Li diffusion into the xenoliths is coupled to H loss from nominally anhydrous minerals following degassing. Diffusion models suggest that the co-variation of Mg and Li isotopes requires comparable diffusivities of Li and Mg in olivine. The isotopically lightest samples require ∼5-10 years of diffusive ingress, which we interpret as a time since volatile loss in the host magma. Xenoliths erupted in pyroclastic flows appear to have retained their mantle isotope ratios, likely as a result of little prior degassing in these explosive events. High δ⁷Li, coupled with high [Li], in rapidly cooled arc peridotites may indicate that these samples represent fragments of mantle wedge that has been metasomatised by heavy, slab-derived fluids. If such material is typically stirred back into the convecting mantle, it may account for the heavy δ⁷Li seen in some oceanic basalts.     

Oxygen isotopic compositions of chondrules from the metal-rich chondrites Isheyevo (CH/CBb), MAC 02675 (CBb) and QUE 94627 (CBb)

It has been recently suggested that (1) CH chondrites and the CB_b/CH-like chondrite Isheyevo contain two populations of chondrules formed by different processes: (i) magnesian non-porphyritic (cryptocrystalline and barred) chondrules, which are similar to those in the CB chondrites and formed in an impact-generated plume of melt and gas resulted from large-scale asteroidal collision, and (ii) porphyritic chondrules formed by melting of solid precursors in the solar nebula. (2) Porphyritic chondrules in Isheyevo and CH chondrites are different from porphyritic chondrules in other carbonaceous chondrites ( [Krot et al., 2005], [Krot et al., 2008a] and [Krot et al., 2008b]). In order to test these hypotheses, we measured in situ oxygen isotopic compositions of porphyritic (magnesian, Type I and ferroan, Type II) and non-porphyritic (magnesian and ferroan cryptocrystalline) chondrules from Isheyevo and CB_b chondrites MAC 02675 and QUE 94627, paired with QUE 94611, using a Cameca ims-1280 ion microprobe.On a three-isotope oxygen diagram (δ¹⁷O vs. δ¹⁸O), compositions of chondrules measured follow approximately slope-1 line. Data for 19 magnesian cryptocrystalline chondrules from Isheyevo, 24 magnesian cryptocrystalline chondrules and 6 magnesian cryptocrystalline silicate inclusions inside chemically-zoned Fe,Ni-metal condensates from CB_b chondrites have nearly identical compositions: Δ¹⁷O = −2.2 ± 0.9‰, −2.3 ± 0.6‰ and −2.2 ± 1.0‰ (2σ), respectively. These observations and isotopically light magnesium compositions of cryptocrystalline magnesian chondrules in CB_b chondrites (Gounelle et al., 2007) are consistent with their single-stage origin, possibly as gas-melt condensates in an impact-generated plume. In contrast, Δ¹⁷O values for 11 Type I and 9 Type II chondrules from Isheyevo range from −5‰ to +4‰ and from −17‰ to +3‰, respectively. In contrast to typical chondrules from carbonaceous chondrites, seven out of 11 Type I chondrules from Isheyevo plot above the terrestrial fractionation line. We conclude that (i) porphyritic chondrules in Isheyevo belong to a unique population of objects, suggesting formation either in a different nebular region or at a different time than chondrules from other carbonaceous chondrites; (ii) Isheyevo, CB and CH chondrites are genetically related meteorites: they contain non-porphyritic chondrules produced during the same highly-energetic event, probably large-scale asteroidal collision; (iii) the differences in mineralogy, petrography, chemical and whole-rock oxygen isotopic compositions between CH and CB chondrites are due to various proportions of the nebular and the impact-produced materials.     

Manganese-chromium isotope systematics of enstatite meteorites

We present results of a study of the ⁵³Mn-⁵³Cr isotope systematics in the enstatite chondrites and achondrites (aubrites). The goal of this study was to explore the capabilities of this isotope system to obtain chronological information on these important classes of meteorites and to investigate the original distribution in the inner solar system of the short-lived radionuclide ⁵³Mn. Our earlier work (Lugmair and Shukolyukov, 1998; Shukolyukov and Lugmair, 2000a) has shown that the asteroid belt bodies are characterized by essentially the same initial ⁵³Mn abundance. However, we have found the presence of a gradient in the abundance of the radiogenic ⁵³Cr between the earth-moon system, Mars, and the asteroid Vesta. If this gradient is considered as a function of the heliocentric distance a linear radial dependence is indicated. This can be explained either by an early, volatility controlled Mn/Cr fractionation in the nebula or by an original radially heterogeneous distribution of ⁵³Mn. The enstatite chondrites are suggested to form in the inner zones of the solar nebula, much closer to the Sun than the ordinary chondrites. Therefore, their investigation may be an important test on the hypothesis on a radial heterogeneity in the initial ⁵³Mn.We have studied the bulk samples of the EH4-chondrites Indarch and Abee and the EL6-chondrite Khairpur. Although these meteorites have essentially the same Mn/Cr ratio as the ordinary chondrites, the relative abundance of the radiogenic ⁵³Cr is three times smaller than in the ordinary chondrites. Because these meteorites are primitive (undifferentiated) and no Mn/Cr fractionation had occurred within their parent bodies, this difference is a strong argument in favor of an initially heterogeneous distribution of ⁵³Mn in the early inner solar system. This finding is also consistent with formation of the enstatite chondrites in the inner zones of the solar nebula. Using the characteristic ⁵³Cr excess of the enstatite chondrites and the observed gradient, their place of origin falls at about 1.4 AU or somewhat closer to the Sun (i.e. >1.0-1.4 AU).We also present chronological results for the enstatite chondrites and achondrites. The ‘absolute’ ⁵³Mn-⁵³Cr ages of the EH4-chondrites are old: ∼4565 Ma. The EL6-chondrite Khairpur is ∼4.5 Ma younger, which is in good agreement with the ¹²⁹I-¹²⁹Xe data from the literature. The age of the aubrite Peña Blanca Spring appears to be similar to those of the enstatite chondrites while that of the aubrite Bishopville is at least ∼10 Ma younger, which is also in agreement with the ¹²⁹I-¹²⁹Xe data. The results from bulk samples of aubrites indicate that the last Mn/Cr fractionation in their parent body occurred ∼ 4563 Ma ago and imply an evolution of the Mn-Cr isotope system in an environment with an higher than chondritic Mn/Cr ratio for several millions of years.     

The stable carbon isotopes in enstatite chondrites and Cumberland Falls

The carbon isotopic composition of the total carbon in the enstatite chondrites Indarch, Abee, St. Marks, Pillistfer, Hvittis and Daniel's Kuil and the enstatite achondrite Cumberland Falls has been measured. The empirical relationhip between carbon isotopic composition and total carbon content is distinct from that of carbonaceous and ordinary chondrites. Within the enstatite chondrite group the average ¹³C content increases with petrographic type: E4 < E5 < E6. Daniel's Kuil shows the largest ¹³C enrichment in the bulk carbon of any meteorite. The carbon isotopic composition is most clearly correlated with the abundance of the elements Zn, Cd and In. Insofar as these elements may hold the key to the understanding of enstatite chondrites, more detailed combined carbon isotope and trace element studies of these meteorites will play an important role in the deciphering of their history.     

Noble gas and oxygen isotope studies of aubrites: A clue to origin and histories

Noble gas measurements were performed for nine aubrites: Bishopville, Cumberland Falls, Mayo Belwa, Mount Egerton, Norton County, Peña Blanca Spring, Shallowater, ALHA 78113 and LAP 02233. These data clarify the origins and histories, particularly cosmic-ray exposure and regolith histories, of the aubrites and their parent body(ies). Accurate cosmic-ray exposure ages were obtained using the ⁸¹Kr-Kr method for three meteorites: 52 ± 3, 49 ± 10 and 117 ± 14 Ma for Bishopville, Cumberland Falls and Mayo Belwa, respectively. Mayo Belwa shows the longest cosmic-ray exposure age determined by the ⁸¹Kr-Kr method so far, close to the age of 121 Ma for Norton County. These are the longest ages among stony meteorites. Distribution of cosmic-ray exposure ages of aubrites implies 4-9 break-up events (except anomalous aubrites) on the parent body. Six aubrites show “exposure at the surface” on their parent body(ies): (i) neutron capture ³⁶Ar, ⁸⁰Kr, ⁸²Kr and/or ¹²⁸Xe probably produced on the respective parent body (Bishopville, Cumberland Falls, Mayo Belwa, Peña Blanca Spring, Shallowater and ALHA 78113); and/or (ii) chondritic trapped noble gases, which were likely released from chondritic inclusions preserved in the aubrite hosts (Cumberland Falls, Peña Blanca Spring and ALHA 78113). The concentrations of ¹²⁸Xe from neutron capture on ¹²⁷I vary among four measured specimens of Cumberland Falls (0.5-76 × 10⁻¹⁴ cm³STP/g), but are correlated with those of radiogenic ¹²⁹Xe, implying that the concentrations of (¹²⁸Xe)_n and (¹²⁹Xe)_rad reflect variable abundances of iodine among specimens. The ratios of (¹²⁸Xe)_n/(¹²⁹Xe)_rad obtained in this work are different for Mayo Belwa (0.045), Cumberland Falls (0.015) and Shallowater (0.001), meaning that neutron fluences, radiogenic ¹²⁹Xe retention ages, or both, are different among these aubrites. Shallowater contains abundant trapped Ar, Kr and Xe (2.2 × 10⁻⁷, 9.4 × 10⁻¹⁰ and 2.8 × 10⁻¹⁰ cm³STP/g, respectively) as reported previously (Busemann and Eugster, 2002). Isotopic compositions of Kr and Xe in Shallowater are consistent with those of Q (a primordial noble gas component trapped in chondrites). The Ar/Kr/Xe compositions are somewhat fractionated from Q, favoring lighter elements. Because of the unbrecciated nature of Shallowater, Q-like noble gases are considered to be primordial in origin. Fission Xe is found in Cumberland Falls, Mayo Belwa, Peña Blanca Spring, ALHA 78113 and LAP 02233. The majority of fission Xe is most likely ²⁴⁴Pu-derived, and about 10-20% seems to be ²³⁸U-derived at ¹³⁶Xe. The observed (¹³⁶Xe)_Pu corresponds to 0.019-0.16 ppb of ²⁴⁴Pu, from which the ²⁴⁴Pu/U ratios are calculated as 0.002-0.009. These ratios resemble those of chondrites and other achondrites like eucrites, suggesting that no thermal resetting of the Pu-Xe system occurred after ∼4.5 Ga ago. We also determined oxygen isotopic compositions for four aubrites with chondritic noble gases and a new aubrite LAP 02233. In spite of their chondritic noble gas signatures, oxygen with chondritic isotopic compositions was found only in a specimen of Cumberland Falls (Δ¹⁷O of ∼0.3‰). The other four aubrites and the other two measured specimens of Cumberland Falls are concurrent with the typical range for aubrites.     

Silicon isotopes in meteorites and planetary core formation

The silicon (Si) isotope compositions of 42 meteorite and terrestrial samples have been determined using MC-ICPMS with the aim of resolving the current debate over their compositions and the implications for core formation. No systematic δ³⁰Si differences are resolved between chondrites (δ³⁰Si = −0.49 ± 0.15‰, 2σ_SD) and achondrites (δ³⁰Si = −0.47 ± 0.11‰, 2σ_SD), although enstatite chondrites are consistently lighter (δ³⁰Si = −0.63 ± 0.07‰, 2σ_SD) in comparison to other meteorite groups. The data reported here for meteorites and terrestrial samples display an average difference Δ³⁰Si_{BSE−meteorite∗} = 0.15 ± 0.10‰, which is consistent within uncertainty with previous studies. No effect from sample heterogeneity, preparation, chemistry or mass spectrometry can be identified as responsible for the reported differences between current datasets. The heavier composition of the bulk silicate Earth is consistent with previous conclusions that Si partitioned into the metal phase during metal-silicate equilibration at the time of core formation. Fixing the temperature of core formation to the peridotite liquidus and using an appropriate metal silicate fractionation factor (ε ∼0.89), the Δ³⁰Si_{BSE−meteorite∗} value from this study indicates that the Earth core contains at least 2.5 and possibly up to 16.8 wt% Si.     

The origin and history of ordinary chondrites: A study by iron isotope measurements of metal grains from ordinary chondrites

Chondrules and chondrites provide unique insights into early solar system origin and history, and iron plays a critical role in defining the properties of these objects. In order to understand the processes that formed chondrules and chondrites, and introduced isotopic fractionation of iron isotopes, we measured stable iron isotope ratios ⁵⁶Fe/⁵⁴Fe and ⁵⁷Fe/⁵⁴Fe in metal grains separated from 18 ordinary chondrites, of classes H, L and LL, ranging from petrographic types 3-6 using multi-collector inductively coupled plasma mass spectrometry. The δ⁵⁶Fe values range from −0.06 ± 0.01 to +0.30 ± 0.04‰ and δ⁵⁷Fe values are −0.09 ± 0.02 to +0.55 ± 0.05‰ (relative to IRMM-014 iron isotope standard). Where comparisons are possible, these data are in good agreement with published data. We found no systematic difference between falls and finds, suggesting that terrestrial weathering effects are not important in controlling the isotopic fractionations in our samples. We did find a trend in the ⁵⁶Fe/⁵⁴Fe and ⁵⁷Fe/⁵⁴Fe isotopic ratios along the series H, L and LL, with LL being isotopically heavier than H chondrites by ∼0.3‰ suggesting that redox processes are fractionating the isotopes. The ⁵⁶Fe/⁵⁴Fe and ⁵⁷Fe/⁵⁴Fe ratios also increase with increasing petrologic type, which again could reflect redox changes during metamorphism and also a temperature dependant fractionation as meteorites cooled. Metal separated from chondrites is isotopically heavier by ∼0.31‰ in δ⁵⁶Fe than chondrules from the same class, while bulk and matrix samples plot between chondrules and metal. Thus, as with so many chondrite properties, the bulk values appear to reflect the proportion of chondrules (more precisely the proportion of certain types of chondrule) to metal, whereas chondrule properties are largely determined by the redox conditions during chondrule formation. The chondrite assemblages we now observe were, therefore, formed as a closed system.     

Isotopic fractionation of Cu in tektites

Tektites are terrestrial natural glasses of up to a few centimeters in size that were produced during hypervelocity impacts on the Earth’s surface. It is well established that the chemical and isotopic composition of tektites is generally identical to that of the upper terrestrial continental crust. Tektites typically have very low water content, which has generally been explained by volatilization at high temperature; however, the exact mechanism is still debated. Because volatilization can fractionate isotopes, comparing the isotopic composition of volatile elements in tektites with those of their source rocks may help to understand the physical conditions during tektite formation.Interestingly, volatile chalcophile elements (e.g., Cd and Zn) seem to be the only elements for which isotopic fractionation is known so far in tektites. Here, we extend this study to Cu, another volatile chalcophile element. We have measured the Cu isotopic composition for 20 tektite samples from the four known different strewn fields. All of the tektites (except the Muong Nong-types) are enriched in the heavy isotopes of Cu (1.98 < δ⁶⁵Cu < 6.99) in comparison to the terrestrial crust (δ⁶⁵Cu ≈ 0) with no clear distinction between the different groups. The Muong Nong-type tektites and a Libyan Desert Glass sample are not fractionated (δ⁶⁵Cu ≈ 0) in comparison to the terrestrial crust. To refine the Cu isotopic composition of the terrestrial crust, we also present data for three geological reference materials (δ⁶⁵Cu ≈ 0).An increase of δ⁶⁵Cu with decreasing Cu abundance probably reflects that the isotopic fractionation occurred by evaporation during heating. A simple Rayleigh distillation cannot explain the Cu isotopic data and we suggest that the isotopic fractionation is governed by a diffusion-limited regime. Copper is isotopically more fractionated than the more volatile element Zn (δ^66/64Zn up to 2.49‰). This difference of behavior between Cu and Zn is predicted in a diffusion-limited regime, where the magnitude of the isotopic fractionation is regulated by the competition between the evaporative flux and the diffusive flux at the diffusion boundary layer. Due to the difference of ionic charge in silicates (Zn²⁺ vs. Cu⁺), Cu has a diffusion coefficient that is larger than that of Zn by at least two orders of magnitude. Therefore, the larger isotopic fractionation in Cu than in Zn in tektites is due to the significant difference in their respective chemical diffusivity.     

Thermal metamorphism of primitive meteorites—XL The enstatite meteorites: origin and evolution of a parent body

We report neutron activation data for Ag, As, Bi, Cd, Co, Cs, Cu, Ga, In, Rb, Se, Te, Tl and Zn in samples of Abee heated at temperatures of 1000–1400°C in a low-pressure environment (initially ~ 10^?5 atm H₂) and in 9 enstatite achondrites (aubrites) and the silicate portion of the unique stony-iron, Mt Egerton. Trace element losses in heated Abee progress with temperature, the lowest retention being 2.4 × 10^?6 of initial contents. These data indicate trace element loss above 1000°C via diffusion-controlled processes having apparent activation energies of 8–55 kcal/mol ; only Co exhibits a significantly higher energy. These trace element data and those for aubrites, Mt Egerton and E4–6 chondrites, and mineralogic and isotopic evidence link all enstatite meteorites to a common parent body. Volatile, mobile elements vary inversely with cobalt content in aubrites and Mt Egerton but directly in E4–6 chondrites; this is inconsistent with all genetic models positing fractionation of such elements during nebular condensation and accretion. However, the data are consistent with the idea that aubrites and Mt. Egerton reflect fractional crystallization of a magma produced from enstatite chondrite-like parent material (probably E6) and late introduction of chalcophiles and mobile elements transported by FeS-Fe eutectic from an E4–6 region experiencing open-system metamorphism. As suggested earlier, the only primary process that affected enstatite meteorites involved fractionation of non-volatile lithophiles from sulfides and metal during condensation and accretion of chondritic parent material from the nebula. If, as seems likely, volatile/mobile elements reflect secondary processes, they can only be used to establish alteration conditions within the enstatite parent body and not to estimate temperatures during primary nebular condensation and accretion.     

Compositional differences in enstatite chondrites based on carbon and nitrogen stable isotope measurements

Carbon and nitrogen abundance and isotopic compositions, from four EH4, one EH5, five EL6 chondrites and one aubrite, were determined by using stepped pyrolysis (N only) and combustion (N and C) extractions in attempts to distinguish the components present. Carbon contents range from 0.15 to 0.70 wt%, with no systematic relationship between carbon content and meteorite group or petrologic type. Whole-rock δ¹³C values range from −28.5 to −4.1 %., Most C occurs as graphite and when temperature steps above 700°C are considered, there is a difference between EH4,5 (δ¹³C = −9.1 to -5.8%.) and EL6 chondrites (δ¹³C = −6.7 to +4.2%.). Carbon in Bustee aubrite is isotopically lighter (δ¹³C = −24%.) than in any enstatite chondrite.

Nitrogen occurs as osbornite, sinoite and in isostructural substitution for oxygen in silicate lattice sites. Nitrogen abundances and isotopic compositions are more variable than C, due to the heterogenous distribution of N-bearing minerals. Three EL6's containing osbornite have higher N concentrations than other type 6 enstatite chondrites. Sinoite, where present, is depleted in ¹⁵N relative to osbornite. Nitrogen in the Bustee aubrite has a similar abundance and δ¹⁵N value to those of EL6's, again dominated by the presence of osbornite.

In addition to the refractory C-and N-bearing minerals there is also organic material (largely terrestrial contamination) and evidence for at least two “exotic” components. The first is a host for Xe (HL) and is characterized by δ¹³C <-−47%. and δ¹⁵N ≤−73%., whereas the second is less well-defined, but is marked by δ¹⁵N = +269%.     

Stable Cu and Zn isotope ratios as tracers of sources and transport of Cu and Zn in contaminated soil

Copper and Zn metals are produced in large quantities for different applications. During Cu production, large amounts of Cu and Zn can be released to the environment. Therefore, the surroundings of Cu smelters are frequently metal-polluted. We determined Cu and Zn concentrations and Cu and Zn stable isotope ratios (δ⁶⁵Cu, δ⁶⁶Zn) in three soils at distances of 1.1, 3.8, and 5.3 km from a Slovak Cu smelter and in smelter wastes (slag, sludge, ash) to trace sources and transport of Cu and Zn in soils. Stable isotope ratios were measured by multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) in total digests. Soils were heavily contaminated with concentrations up to 8087 μg g⁻¹ Cu and 2084 μg g⁻¹ Zn in the organic horizons. The δ⁶⁵Cu values varied little (−0.12‰ to 0.36‰) in soils and most wastes and therefore no source identification was possible. In soils, Cu became isotopically lighter with increasing depth down to 0.4 m, likely because of equilibrium reactions between dissolved and adsorbed Cu species during transport of smelter-derived Cu through the soil. The δ⁶⁶Zn_IRMM values were isotopically lighter in ash (−0.41‰) and organic horizons (−0.85‰ to −0.47‰) than in bedrock (−0.28‰) and slag (0.18‰) likely mainly because of kinetic fractionation during evaporation and thus allowed for separation of smelter-Zn from native Zn in soil. In particular in the organic horizons large variations in δ⁶⁶Zn values occur, probably caused by biogeochemical fractionation in the soil-plant system. In the mineral horizons, Zn isotopes showed only minor shifts to heavier δ⁶⁶Zn values with depth mainly because of the mixing of smelter-derived Zn and native Zn in the soils. In contrast to Cu, Zn isotope fractionation between dissolved and adsorbed species was probably only a minor driver in producing the observed variations in δ⁶⁶Zn values. Our results demonstrate that metal stable isotope ratios may serve as tracer of sources, vertical dislocation, and biogeochemical behavior in contaminated soil.     

The compositional classification of chondrites: II The enstatite chondrite groups

We present new data from a neutron activation analysis of four enstatite chondrites including the taxonomically important St. Sauveur, and discuss the classification of enstatite chondrites. The enstatite chondrites can be divided into two compositionally distinct sets; in one set abundances of nonrefractory siderophiles and moderately volatile chalcophiles and alkalis are 1.5–2.0× higher than in the other. A well-resolved compositional hiatus separates these two sets. The differences in composition are as great as those between the groups of ordinary chondrites, and therefore it appears best to treat these sets as separate groups. By analogy with the symbols used for ordinary chondrites we propose to designate the high-Fe, high siderophile group EH and the low-Fe, low-siderophile group EL. Known members of the EH group belong to petrologic types 4 and 5, whereas all EL members are petrologic type 6. Within the EH group no correlation is observed between petrologic type and abundance of nonrefractory siderophiles or moderately volatiles or alkalis.Two physical properties show only modest overlap between the EH and EL groups. Cosmic-ray ages for EH chondrites are 0.5–7 Ma, while those for EL chondrites are 4–18 Ma. Relative to Bjurböle, I-Xe formation intervals are $\text{?1.3 ± 0.6}$ Ma for EH chondrites and $\text{2.9 ± 0.5}$ Ma for EL chondrites. The weight of the chemical and physical evidence indicates that the EH and EL groups formed separate bodies at similar distances from the Sun.The available evidence for Shallowater and Happy Canyon, two strongly recrystallized silicate-rich meteorites containing > 40 mg/g Fe-Ni, indicates that the former is an enstatite-clan chondrite altered by loss of sulfide- and plagioclase-rich melts, whereas the latter is intermediate in composition between EL chondrites and the chondritic silicates in the Pine River IAB-anomalous meteorite.     

Iodine-Xenon dating of chondrules from the Qingzhen and Kota Kota enstatite chondrites

Initial ¹²⁹I/¹²⁷I values (I-Xe ages) have been obtained for individual mineralogically characterized chondrules and interchondrule matrix from the enstatite chondrites Qingzhen (EH3) and Kota Kota (EH3). In view of the absence of aqueous alteration and the low-peak metamorphic temperatures experienced by these meteorites, we suggest that the I-Xe ages for the chondrules record the event in which they were formed. These ages are within the range recorded for chondrules from ordinary chondrites, demonstrating that chondrules formed during the same time interval in the source regions of both ordinary chondrites and enstatite chondrites. The timing of this chondrule-forming episode or episodes brackets the I-Xe closure age of planetesimal bodies such as the Shallowater aubrite parent body. Although chondrule formation need not have occurred close to planetesimals, the existence of planetesimals at the same time as chondrule formation provides constraints on models of this process. Whichever mechanisms are proposed to form and transport chondrules, they must be compatible with models of the protosolar nebula which predict the formation of differentiated bodies on the same timescale at the same heliocentric distance.     

Oxygen isotope measurements of individual unmelted Antarctic micrometeorites

We present oxygen isotope measurements of 28 unmelted Antarctic micrometeorites measuring 150-250 μm (long axis) collected in the South Pole water well. The micrometeorites were all unmelted and classified as either fine-grained, scoriaceous, coarse-grained or composite (a mix of two other classes). Spot analyses were made of each micrometeorite type using an ion microprobe. The oxygen isotope values were measured relative to standard mean ocean water (SMOW) and range from δ¹⁸O = 3‰ to 60‰ and δ¹⁷O = −1‰ to 32‰, falling along the terrestrial fractionation line (TFL) within 2σ errors. Several analytical spots (comprising multiple phases) were made on each particle. Variability in the oxygen isotope ratios was observed among micrometeorite types, between micrometeorites of the same type and between analytical spots on a single micrometeorite indicating that micrometeorites are isotopically heterogeneous. In general, the lowest isotope values are associated with the coarse-grained micrometeorites whereas most of the fine-grained and scoriaceous micrometeorites have an average δ¹⁸O ? 22‰, suggesting that the matrix in micrometeorites is isotopically heavier than the anhydrous silicate phases. The oxygen isotope values for the coarse-grained micrometeorites, composed mainly of anhydrous phases, do not lie along the carbonaceous chondrite anhydrous mineral (CCAM) line, as observed for olivines, pyroxenes and some kinds of chondrules in carbonaceous chondrites, suggesting that coarse-grained MMs are not related to chondrules, as previously thought. Our measurements span the same range as values found for melted micrometeorites in other studies. Although four of the micrometeorites have oxygen isotope values lying along the TFL, close to the region where the bulk CI carbonaceous chondrites are found, 21 particles have very enriched ¹⁷O and ¹⁸O values that have not been reported in previous analyses of chondrite matrix material, suggesting that they could be a new type of Solar System object. The parent bodies of the micrometeorites with higher ¹⁸O values may be thermal metamorphosed carbonaceous asteroids that have not been found as meteorites either because they are friable asteroids that produce small particles rather than rocks upon collision with other bodies, or because the rocks they produce are too friable to survive atmospheric entry.