Comparisons of the four Miller Range nakhlites,MIL 03346, 090030, 090032 and 090136: Textural and compositional observations of primary and secondary mineral assemblages

Abstract– Petrological and geochemical analyses of Miller Range (MIL) 03346 indicate that this meteorite originated from the same augitic cumulate layer(s) as the nakhlite Martian meteorites, but underwent rapid cooling prior to complete crystallization. As with the other nakhlites, MIL 03346 contains a secondary alteration assemblage, in this case consisting of iddingsite‐like alteration veins in olivine phenocrysts, Fe‐oxide alteration veins associated with the mesostasis, and Ca‐ and K,Fe‐sulfate veins. We compared the textural and mineralogical compositions of MIL 090030, 090032, and 090136 with MIL 03346, focusing on the composition and Raman spectra of the alteration assemblages. These observations indicate that the meteorites are paired, and that the preterrestrial olivine‐bound alteration assemblages were produced by weakly acidic brine. Although these alteration assemblages resemble similar assemblages in Nakhla, the absence of siderite and halite in the Miller Range nakhlites indicates that the parental alteration brine was comparatively HCO₃^? depleted, and less concentrated, than that which altered Nakhla. This indicates that the Miller Range nakhlite alteration brine experienced a separate evolutionary pathway to that which altered Nakhla, and therefore represents a separate branch of the Lafayette‐Nakhla evaporation sequence. Thin‐sections cut from the internal portions of these meteorites (away from any fusion crust or terrestrially exposed edge), contain little Ca‐sulfate (identified as gypsum), and no jarosite, whereas thin‐sections with terrestrially exposed edges have much higher sulfate abundances. These observations suggest that at least the majority of sulfate within the Miller Range nakhlites is terrestrially derived.     

Paired nakhlites MIL 090030, 090032, 090136, and 03346: Insights into the Miller Range parent meteorite

Abstract– Miller Range (MIL) 03346 is the most oxidized and least equilibrated nakhlite known and displays the highest amount of intercumulus phase. The discovery of three new nakhlites, MIL 090030, MIL 090032, and MIL 090136, in the Miller Range, Antarctica, geographically close to the location of MIL 03346, suggests that they may come from the same parent meteorite. In this study, we investigate the mineralogy and texture of cumulus and intercumulus phases, in situ major and trace element compositions for the cumulus phases, as well as pyroxene crystal size distribution patterns and spatial distribution patterns of MIL 090030, 090032, and 090136. Using these combined results, we conclude that the three nakhlites studied here are paired with MIL 03346. However, modal mineral abundances of MIL 090030, 090032, 090136, and 03346 exhibit variations indicating that a single sample of a Miller Range nakhlite is not modally representative of the parent meteorite and that analyses of multiple samples for a single nakhlite may be necessary to obtain representative modal data for placement in the cumulate pile. Our calculated parental melt composition based on all the paired samples confirms a previous study suggesting that the nakhlite parent melt crystallized as a closed system.     

Petrology and chemistry of MIL 03346 and its significance in understanding the petrogenesis of nakhlites on Mars

Abstract— Antarctic meteorite Miller Range (MIL) 03346 is a nakhlite composed of 79% clinopyroxene, ?1% olivine, and 20% vitrophyric intercumulus material. We have performed a petrological and geochemical study of MIL 03346, demonstrating a petrogenetic history similar to previously discovered nakhlites. Quantitative textural study of MIL 03346 indicates long (>1 × 10¹ yr) residence times for the cumulus augite, whereas the skeletal Fe‐Ti oxide, fayalite, and sulfide in the vitrophyric intercumulus matrix suggest rapid cooling, probably as a lava flow. From the relatively high forsterite contents of olivine (up to Fo₄₃) compared with other nakhlites and compositions of augite cores (Wo_38–42En_35–40Fs_22–28) and their hedenbergite rims, we suggest that MIL 03346 is part of the same or a similar Martian cumulate‐rich lava flow as other nakhlites. However, MIL 03346 has experienced less equilibration and faster cooling than other nakhlites discovered to date. Calculated trace element concentrations based upon modal abundances of MIL 03346 and its constituent minerals are identical to whole rock trace element abundances. Parental melts for augite have REE patterns that are approximately parallel with whole rock and intercumulus melt using experimentally defined partition coefficients. This parallelism reflects closed‐system crystallization for MIL 03346, where the only significant petrogenetic process between formation of augite and eruption and emplacement of the nakhlite flow has been fractional crystallization. A model for the petrogenesis of MIL 03346 and the nakhlites (Nakhla, Governador Valadares, Lafayette, Yamato‐000593, Northwest Africa (NWA) 817, NWA 998) would include: 1) partial melting and ascent of melt generated from a long‐term LREE depleted mantle source, 2) crystallization of cumulus augite (± olivine, ± magnetite) in a shallow‐level Martian magma chamber, 3) eruption of the crystal‐laden nakhlite magma onto the surface of Mars, 4) cooling, crystal settling, overgrowth, and partial equilibration to different extents within the flow, 5) secondary alteration through hydrothermal processes, possibly immediately succeeding or during emplacement of the flow. This model might apply to single—or multiple—flow models for the nakhlites. Ultimately, MIL 03346 and the other nakhlites preserve a record of magmatic processes in volcanic rocks on Mars with analogous petrogenetic histories to pyroxene‐rich terrestrial lava flows and to komatiites.     

Petrology of the Miller Range 03346 nakhlite in comparison with the Yamato‐000593 nakhlite

Abstract— We petrologically examined the Miller Range (MIL) 03346 nakhlite. The main‐phase modal abundances are 67.7 vol% augite, 0.8 vol% olivine, and 31.5 vol% mesostasis. Among all known nakhlites, MIL 03346's modal abundance of olivine is the smallest and of mesostasis is the largest. Augite occurs as cumulus phenocrysts having a homogeneous core composition (En_36–38Fs_24–22Wo₄₀), which is identical with other nakhlites. They accompany thin ferroan rims divided into inner and outer rims with a compositional gap at the boundary between the two rims. Olivine grains have magnesian cores (Fa ≥ 55) and show normal zoning toward ferroan rims (Fa ≤ 84). Mesostasis consists mostly of glass (26.0 vol%) with minor skeletal fayalites, skeletal titanomagnetites, acicular phosphate, massive cristobalite, and sulfides. We conclude that MIL 03346 is the most rapidly cooled nakhlite among all known nakhlites based on the petrography. We obtain the intercumulus melt composition for MIL 03346 from the mass balance calculation using the modal abundances and discuss the crystallization sequence of MIL 03346 in comparison with that of Yamato (Y‐) 000593. Although magnesian olivines of Y‐000593 are phenocrystic, magnesian olivine grains of MIL 03346 seem to have texturally crystallized from the intercumulus melt. After the MIL 03346 magma intruded upward to the Martian surficial zone, the magnesian olivine crystallized, and then the ferroan inner rim formed on phenocrystic core augite. The outer rim of phenocrystic augites formed after the crystallization of skeletal fayalites and skeletal titanomagnetites, resulting in a compositional gap between the inner and outer rims. Finally, glassy mesostasis formed from the residual melt. This crystallization sequence of MIL 03346 is different from those of other nakhlites, including Y‐000593.     

Crystallization experiments of intercumulus melts for nakhlites under QFM ± 2 at 1 bar

Abstract— Crystallization of parent melts for nakhlites was experimentally studied under QFM ± 2 at one bar. Isothermal experiments suggest that melts having parent magma composition for nakhlites crystallize both augites and titanomagnetites at liquidus temperatures of 1144–1154 °C. Compositions of the augites are identical to those of phenocrystic core augites (En_36–38Fs_22–25Wo_39–40) in nakhlites. No olivines crystallize from the isothermal runs, and solidus temperature is about 1000 °C. Linear‐cooling experiments were carried out at various cooling rates (1–17 °C/h) ranging from liquidus to solidus temperatures under similar pressure conditions to the isothermal runs. Augites, titanomagnetites, and fayalites crystallized in the cooling runs, but magnesian olivines never crystallized there. Magnesian core augite in the cooling runs has the same composition as those of nakhlites. Rims of augite crystals from the cooling runs of 1–4 °C/h consist of two layers, ferroan augite inner rim and hedenbergite outer rim, which are very similar to those in the Miller Range (MIL) 03346 nakhlite. Small amounts of pyroxferroite crystallized in mesostasis and augite rims from two cooling runs. Titanomagnetites from cooling runs never accompany ilmenite lamellae as seen in nakhlites, suggesting that the subsolidus cooling rate of the cooling runs was much more rapid than those of nakhlite intercumulus melts. The cooling experiments reproduce the crystallization processes of pyroxenes and the compositional change of residual melt for a rapidly cooled magma such as MIL 03346.     

A new calibration to determine the closure temperatures of Fe‐Mg ordering in augite from nakhlites

Recently it has been shown that the relatively low closure temperature (T_c) of 500 (100)°C calculated for augite from Miller Range nakhlite (MIL 03346,13) using the available geothermometers would correspond to a slow cooling rate inconsistent with the petrologic evidence for an origin from a fast‐cooled lava flow. Moreover, previous annealing experiments combined with HR‐SC‐XRD on an augite crystal from MIL 03346 clearly showed that at 600 °C, the Fe²⁺‐Mg degree of order remained unchanged, thus suggesting that the actual T_c is close to this temperature. In order to clarify this discrepancy, we undertook an ex situ annealing experimental study at 700, 800, and 900 °C, until the equilibrium in the intracrystalline Fe²⁺‐Mg exchange is reached, using an augite crystal from Miller Range nakhlite (MIL 03346,13) with a composition of about En₃₆Fs₂₄Wo₄₀. These data allowed us to calculate the following new geothermometer calibration for Martian nakhlites: where The application of this new equation to other Martian nakhlites (NWA 988 and Nakhla) suggests that for augite with composition close to that of MIL 03346, the T_c is up to 170 °C higher with respect to the one calculated using the previous available geothermometer equation, thus suggesting a significantly faster cooling in agreement with petrologic evidence.     

Application of a textural geospeedometer to the late‐stage magmatic history of MIL 03346

Abstract— Dynamic crystallization experiments performed on Fe‐rich, Al‐poor basalt are employed as a textural calibration set to quantify the late‐stage igneous history of nakhlite Miller Range (MIL) 03346. The ratio of crystal‐melt surface area to volume typifying morphologically distinct populations of Ca‐pyroxene has been shown to vary as a strong function of cooling rate (Hammer 2006). Furthermore, a texture of phenocrysts surrounded by finer‐grained groundmass crystals arises by sequential nucleation events during constant‐rate cooling, but multiple populations nucleate only if the cooling rate is 72 °C h^?1. Textural analysis of meteorite MIL 03346 reveals at least two distinct populations. The Ca‐pyroxene phenocryst and microphenocryst three dimensional (3D) aspect ratios are 112 ± 8.3 and 1530 ± 160 mm^?1, respectively. By comparison with the calibration set, the range of cooling rates consistent with 3D aspect ratios of both populations in MIL 03346 is ?20 °C h^?1An additional experiment was performed approximating a conductive heat transfer profile in order to interpret and apply results of constant‐rate cooling experiments to the natural cooling of magma. Results suggest that the textures of constant‐rate experiments parallel the initial period of rapid cooling in natural magma. Initial cooling rates of ?20 °C h^?1in the lava hosting MIL 03346 occur in conductively solidifying lava at depths of?0.4 m, constraining the minimum total thickness to 0.8 m. Crystal accumulation beginning in a subsurface reservoir and continuing after lava emplacement as an inflated pahoehoe sheet satisfies all textural constraints on the late‐stage igneous history of MIL 03346.     

Expanding the application of the Eu‐oxybarometer to the lherzolitic shergottites and nakhlites: Implications for the oxidation state heterogeneity of the Martian interior

Abstract— Experimentally rehomogenized melt inclusions from the nakhlite Miller Range 03346 (MIL 03346) and the lherzolitic shergottite Allan Hills 77005 (ALH 77005) have been analyzed for their rare earth element (REE) concentrations in order to characterize the early melt compositions of these Martian meteorites and to calculate the oxygen fugacity conditions they crystallized under. D(Eu/Sm)_{pyroxene/melt} values were measured at 0.77 and 1.05 for ALH 77005 and MIL 03346, respectively. These melts and their associated whole rock compositions have similar REE patterns, suggesting that whole rock REE values are representative of those of the early melts and can be used as input into the pyroxene Eu‐oxybarometer for the nakhlites and lherzolitic shergottites. Crystallization fO₂ values of IW + 1.1 (ALH 77005) and IW + 3.2 (MIL 03346) were calculated. Whole rock data from other nakhlites and lherzolitic shergottites was input into the Eu‐oxybarometer to determine their crystallization fO₂ values. The lherzolitic shergottites and nakhlites have fO₂ values that range from IW + 0.4 to 1.6 and from IW + 1.1 to 3.2, respectively. These values are consistent with some previously determined fO₂ estimates and expand the known range of fO₂ values of the Martian interior to four orders of magnitude. The origins of this range are not well constrained. Possible mechanisms for producing this spread in fO₂ values include mineral/melt fractionation, assimilation, shock effects, and magma ocean crystallization processes. Mineral/melt partitioning can result in changes in fO₂ from the start to the finish of crystallization of 2 orders of magnitude. In addition, crystallization of a Martian magma ocean with reasonable initial water content results in oxidized, water‐rich, late‐stage cumulates. Sampling of these oxidized cumulates or interactions between reduced melts and the oxidized material can potentially account for the range of fO₂ values observed in the Martian meteorites.     

Northwest Africa 5790: A previously unsampled portion of the upper part of the nakhlite pile

We present a geochemical study of recently discovered Martian meteorite Northwest Africa (NWA) 5790 and use our results to constrain its origin and relationship with the other nakhlites. This nakhlite is a clinopyroxene cumulate composed of phenocrysts of augite, olivine, and rare oxides surrounded by a mesostasis composed of vitrophyric glass, feldspars, oxides, phosphates, and fine‐grained olivines and augite. Petrography, and major and trace element compositions of the phases present are consistent with derivation of NWA 5790 from a parental magma common to all the nakhlites. Olivine cores grew from a distinct, incompatible‐element enriched magma and are surrounded by rims containing augite inclusions that grew from the nakhlite parental liquid, supporting previous arguments for xenocrystic olivine cores in nakhlites. Rare earth element microdistributions suggest derivation of NWA 5790 augites from an evolved, relatively oxidized magma, produced by augite fractionation from the common nakhlite parental liquid. Augite grain shapes and CSD patterns are consistent with rapid cooling and derivation near the top of the nakhlite cumulate pile, but patterns are distinct from other nakhlites thought to have formed near the stratigraphic top. The high mesostasis abundance (~44 vol%) indicates solidification near the top of the nakhlite pile close to locations suggested for nakhlites NWA 817 and Miller Range (MIL) 03346. However, the geochemical and petrographic characteristics of these three samples do not permit their placement in a simple stratigraphic order as would occur in a single lava flow. This lack of simple ordering suggests that the nakhlite lava flow split into multiple sections as would occur during breakouts from a single lava flow. Finally we note that NWA 5790 is unique among currently available nakhlites in having phenocryst abundances low enough to allow it to flow.     

Caleta el Cobre 022 Martian meteorite: Increasing nakhlite diversity

Caleta el Cobre (CeC) 022 is a Martian meteorite of the nakhlite group, showing an unbrecciated cumulate texture, composed mainly of clinopyroxene and olivine. Augite shows irregular core zoning, euhedral rims, and thin overgrowths enriched in Fe relative to the core. Low‐Ca pyroxene is found adjacent to olivine. Phenocrysts of Fe‐Ti oxides are titanomagnetite with exsolutions of ilmenite/ulvöspinel. Intercumulus material consists of both coarse plagioclase and fine‐grained mesostasis, comprising K‐feldspars, pyroxene, apatite, ilmenite, Fe‐Ti oxides, and silica. CeC 022 shows a high proportion of Martian aqueous alteration products (iddingsite) in olivine (45.1 vol% of olivine) and mesostasis. This meteorite is the youngest nakhlite with a distinct Sm/Nd crystallization age of 1.215 ± 0.067 Ga. Its ejection age of 11.8 ± 1.8 Ma is similar to other nakhlites. CeC 022 reveals contrasted cooling rates with similarities with faster cooled nakhlites, such as Northwest Africa (NWA) 817, NWA 5790, or Miller Range 03346 nakhlites: augite irregular cores, Fe‐rich overgrowths, fine‐grained K‐feldspars, quenched oxides, and high rare earth element content. CeC 022 also shares similarities with slower cooled nakhlites, including Nakhla and NWA 10153: pyroxene modal abundance, pyroxenes crystal size distribution, average pyroxene size, phenocryst mineral compositions, unzoned olivine, and abundant coarse plagioclase. Moreover, CeC 022 is the most magnetic nakhlite and represents an analog source lithology for the strong magnetization of the Martian crust. With its particular features, CeC 022 must originate from a previously unsampled sill or flow in the same volcanic system as the other nakhlites, increasing Martian sample diversity and our knowledge of nakhlites.     

Oxygen fugacity in the Martian mantle controlled by carbon: New constraints from the nakhlite MIL 03346

Abstract— Pyroxene structural data, along with analyses of titanomagnetite, fayalite and mesostasis of the new nakhlite Miller Range (MIL) 03346, define equilibration near 1 bar, 1100 °C, and oxygen fugacity near the FMQ buffer. There is a clear progression of oxygen fugacity (fO₂) in Martian meteorites from reduced Allan Hills (ALH) 84001 to intermediate shergottites to oxidized nakhlites. This trend can be explained by polybaric graphite‐CO‐CO₂ equilibria in the Martian mantle. Shergottites would have formed at pressures between 1.2 and 3.0 GPa, and nakhlite parent liquids formed at pressures >3.0 GPa, consistent with geochemical and petrologic data for the shergottites and nahklites. Carbon buffering in the Martian mantle could be responsible for variation in fO₂ in Martian meteorites (rather than assimilation or crustal interaction), as well as C‐H‐O fluids that could be the source of ˜30 ppb CH₄ detected by recent spacecraft missions. The conundrum of an oxidized current mantle and basalts, but reduced early mantle during core‐mantle equilibrium exists for both the Earth and Mars. A polybaric buffering role for graphite can explain this discrepancy for Mars, and thus it may not be necessary to have an oxidation mechanism like the dissociation of MgFe‐perovskite to account for the oxidized terrestrial mantle.     

40Ar‐39Ar age determinations of lunar basalt meteorites Asuka 881757, Yamato 793169, Miller Range 05035, La Paz Icefield 02205, Northwest Africa 479, and basaltic breccia Elephant Moraine 96008

Abstract— ⁴⁰Ar‐³⁹Ar data are presented for the unbrecciated lunar basaltic meteorites Asuka (A‐) 881757, Yamato (Y‐) 793169, Miller Range (MIL) 05035, LaPaz Icefield (LAP) 02205, Northwest Africa (NWA) 479 (paired with NWA 032), and basaltic fragmental breccia Elephant Moraine (EET) 96008. Stepped heating ⁴⁰Ar‐³⁹Ar analyses of several bulk fragments of related meteorites A‐881757, Y‐793169 and MIL 05035 give crystallization ages of 3.763 ± 0.046 Ga, 3.811 ± 0.098 Ga and 3.845 ± 0.014 Ga, which are comparable with previous age determinations by Sm‐Nd, U‐Pb Th‐Pb, Pb‐Pb, and Rb‐Sr methods. These three meteorites differ in the degree of secondary ⁴⁰Ar loss with Y‐793169 showing relatively high Ar loss probably during an impact event ?200 Ma ago, lower Ar loss in MIL 05035 and no loss in A‐881757. Bulk and impact melt glass‐bearing samples of LAP 02205 gave similar ages (2.985 ± 0.016 Ga and 2.874 ± 0.056 Ga) and are consistent with ages previously determined using other isotope pairs. The basaltic portion of EET 96008 gives an age of 2.650 ± 0.086 Ga which is considered to be the crystallization age of the basalt in this meteorite. The Ar release for fragmental basaltic breccia EET 96008 shows evidence of an impact event at 631 ± 20 Ma. The crystallization age of 2.721 ± 0.040 Ga determined for NWA 479 is indistinguishable from the weighted mean age obtained from three samples of NWA 032 supporting the proposal that these meteorites are paired. The similarity of ⁴⁰Ar‐³⁹Ar ages with ages determined by other isotopic systems for multiple meteorites suggests that the K‐Ar isotopic system is robust for meteorites that have experienced a significant shock event and not a prolonged heating regime.     

The formation environment of potassic‐chloro‐hastingsite in the nakhlites MIL 03346 and pairs and NWA 5790: Insights from terrestrial chloro‐amphibole

Potassic‐chloro‐hastingsite has been found in melt inclusions in MIL 03346, its paired stones, and NWA 5790. It is some of the most chlorine‐rich amphibole ever analyzed. In this article, we evaluate what crystal chemistry, terrestrial analogs, and experiments have shown about how chlorine‐dominant amphibole (chloro‐amphibole) forms and apply these insights to the nakhlites. Chloro‐amphibole is rare, with about a dozen identified localities on Earth. It is always rich in potassium and iron and poor in titanium. In terrestrial settings, its presence has been interpreted to result from medium to high‐grade alteration (>400 °C) of a protolith by an alkali and/or iron chloride‐rich aqueous fluid. Ferrous chloride fluids exsolved from mafic magmas can cause such alteration, as can crustal fluids that have reacted with rock and lost H₂O in preference to chloride, resulting in concentrated alkali chloride fluids. In the case of the nakhlites, an aqueous alkali‐ferrous chloride fluid was exsolved from the parental melt as it crystallized. This aqueous chloride fluid itself likely unmixed into chloride‐dominant and water‐dominant fluids. Chloride‐dominant fluid was trapped in some melt inclusions and reacted with the silicate contents of the inclusion to form potassic‐chloro‐hastingsite.     

The Miller Range 090340 and 090206 meteorites: Identification of new brachinite‐like achondrites with implications for the diversity and petrogenesis of the brachinite clan

Miller Range (MIL) 090340 and MIL 090206 are olivine‐rich achondrites originally classified as ureilites. We investigate their petrography, mineral compositions, olivine Cr valences, equilibration temperatures, and (for MIL 090340) oxygen isotope compositions, and compare them with ureilites and other olivine‐rich achondrites. We conclude that they are brachinite‐like achondrites that provide new insights into the petrogenesis of brachinite clan meteorites. MIL 090340,6 has a granoblastic texture and consists of ~97 modal % by area olivine (Fo = molar Mg/[Mg+Fe] = 71.3 ± 0.6). It also contains minor to trace augite, chromite, chlorapatite, orthopyroxene, metal, troilite, and terrestrial Fe‐oxides. Approximately 80% by area of MIL 090206,5 has a granoblastic texture of olivine (Fo 72.3 ± 0.1) plus minor augite and chromite, similar to MIL 090340 but also containing minor plagioclase. The rest of the section consists of a single crystal of orthopyroxene (~11 × 3 mm), poikilitically enclosing rounded grains of olivine (Fo = 76.1 ± 0.6), augite, chromite, metal, and sulfide. Equilibration temperatures for MIL 090340 and MIL 090206, calculated from olivine‐spinel, olivine‐augite, and two‐pyroxene thermometry range from ~800 to 930 °C. In both samples, symplectic intergrowths of Ca‐poor orthopyroxene + opaque phases (Fe‐oxides, sulfide, metal) occur as rims on and veins/patches within olivine. Before terrestrial weathering, the opaques were probably mostly sulfide, with minor metal. All petrologic properties of MIL 090340 and MIL 090206 are consistent with those of brachinite clan meteorites, and largely distinct from those of ureilites. Oxygen isotope compositions of olivine in MIL 090340 (δ¹⁸O = 5.08 ± 0.30‰, δ¹⁷O = 2.44 ± 0.21‰, and Δ¹⁷O = ?0.20 ± 0.12‰) are also within the range of brachinite clan meteorites, and well distinguished from ureilites. Olivine Cr valences in MIL 090340 and the granoblastic area of MIL 090206 are 2.57 ± 0.06 and 2.59 ± 0.07, respectively, similar to those of three brachinites also analyzed here (Brachina, Hughes 026, Nova 003). They are higher than those of olivine in ureilites, even those containing chromite. The valence systematics of MIL 090340, MIL 090206, and the three analyzed brachinites (lower Fo = more oxidized Cr) are consistent with previous evidence that brachinite‐like parent bodies were inherently more oxidized than the ureilite parent body. The symplectic orthopyroxene + sulfide/metal assemblages in MIL 090340, MIL 090206, and many brachinite clan meteorites have superficial similarities to characteristic “reduction rims” in ureilites. However, they differ significantly in detail. They likely formed by reaction of olivine with S‐rich fluids, with only minor reduction. MIL 090340 and the granoblastic area of MIL 090206 are similar in modal mineralogy and texture to most brachinites, but have higher Fo values typical of brachinite‐like achondrites. The poikilitic pyroxene area of MIL 090206 is more typical of brachinite‐like achondrites. The majority of their properties suggest that MIL 090340 and MIL 090206 are residues of low‐degree partial melting. The poikilitic area of MIL 090206 could be a result of limited melt migration, with trapping and recrystallization of a small volume of melt in the residual matrix. These two samples are so similar in mineral compositions, Cr valence, and cosmic ray exposure ages that they could be derived from the same lithologic unit on a common parent body.     

Chemical compositions and classifica tion of five thermally altered carbonaceous chondrites

To establish the chemical group provenance of the five thermally altered carbonaceous chondrites Asuka (A‐) 881551, Asuka‐882113, Elephant Moraine (EET) 96026, Mulga (west), and Northwest Africa (NWA) 3133, we quantified 44 trace elements in each of them. We also analyzed Larkman Nunatak (LAR) 04318 (CK4), Miller Range (MIL) 090001 (CR2), Roberts Massif (RBT) 03522 (CK5) as reference samples as their chemical group affinity is already recognized. We conclude that Asuka‐881551, Asuka‐882113, and Mulga (west) are thermally metamorphosed CK chondrites. Compositionally, Elephant Moraine 96026 most resembles the CV chondrites. NWA 3133 is the most significantly thermally altered carbonaceous chondrite in our suite of samples. It is completely recrystallized (no chondrules or matrix remain), but its bulk composition is consistent with a CV–CK clan provenance. The thermally labile element (e.g., Se, Te, Zn, and Bi) depletion in NWA 3133 indicates a chemically open system during the heating episode. It remains unclear if the heat necessary for its thermal alteration of NWA 3133 was due to the decay of ²⁶Al or was impact related. Finally, we infer that MIL 090001, Mulga (west), and NWA 3133 show occasional compositional signatures indicative of terrestrial alteration. The alteration is especially evident within the elements Sr, Ba, La, Ce, Th, U, and possibly Sb. Despite the alteration, we can still confidently place each of the altered chondrites within an established chemical group or clan.     

Extraterrestrial amino acids identified in metal‐rich CH and CB carbonaceous chondrites from Antarctica

Carbonaceous chondrites contain numerous indigenous organic compounds and could have been an important source of prebiotic compounds required for the origin of life on Earth or elsewhere. Extraterrestrial amino acids have been reported in five of the eight groups of carbonaceous chondrites and are most abundant in CI, CM, and CR chondrites but are also present in the more thermally altered CV and CO chondrites. We report the abundance, distribution, and enantiomeric and isotopic compositions of simple primary amino acids in six metal‐rich CH and CB carbonaceous chondrites that have not previously been investigated for amino acids: Allan Hills (ALH) 85085 (CH3), Pecora Escarpment (PCA) 91467 (CH3), Patuxent Range (PAT) 91546 (CH3), MacAlpine Hills (MAC) 02675 (CBb), Miller Range (MIL) 05082 (CB), and Miller Range (MIL) 07411 (CB). Amino acid abundances and carbon isotopic values were obtained by using both liquid chromatography time‐of‐flight mass spectrometry and fluorescence, and gas chromatography isotope ratio mass spectrometry. The δ¹³C/¹²C ratios of multiple amino acids fall outside of the terrestrial range and support their extraterrestrial origin. Extracts of CH chondrites were found to be particularly rich in amino acids (13–16 parts per million, ppm) while CB chondrite extracts had much lower abundances (0.2–2 ppm). The amino acid distributions of the CH and CB chondrites were distinct from the distributions observed in type 2 and 3 CM and CR chondrites and contained elevated levels of β‐, γ‐, and δ‐amino acids compared to the corresponding α‐amino acids, providing evidence that multiple amino acid formation mechanisms were important in CH and CB chondrites.     

Distribution of aliphatic amines in CO,CV, and CK carbonaceous chondrites and relation to mineralogy and processing history

The analysis of water‐soluble organic compounds in meteorites provides valuable insights into the prebiotic synthesis of organic matter and the processes that occurred during the formation of the solar system. We investigated the concentration of aliphatic monoamines present in hot acid water extracts of the unaltered Antarctic carbonaceous chondrites, Dominion Range (DOM) 08006 (CO3) and Miller Range (MIL) 05013 (CO3), and the thermally altered meteorites, Allende (CV3), LAP 02206 (CV3), GRA 06101 (CV3), Allan Hills (ALH) 85002 (CK4), and EET 92002 (CK5). We have also reviewed and assessed the petrologic characteristics of the meteorites studied here to evaluate the effects of asteroidal processing on the abundance and molecular distributions of monoamines. The CO3, CV3, CK4, and CK5 meteorites studied here contain total concentrations of amines ranging from 1.2 to 4.0 nmol g^?1 of meteorite; these amounts are 1–3 orders of magnitude below those observed in carbonaceous chondrites from the CI, CM, and CR groups. The low‐amine abundances for CV and CK chondrites may be related to their extensive degree of thermal metamorphism and/or to their low original amine content. Although the CO3 meteorites, DOM 08006 and MIL 05013, do not show signs of thermal and aqueous alteration, their monoamine contents are comparable to those observed in moderately/extensively thermally altered CV3, CK4, and CK5 carbonaceous chondrites. The low content of monoamines in pristine CO carbonaceous chondrites suggests that the initial amounts, and not asteroidal processes, play a dominant role in the content of monoamines in carbonaceous chondrites. The primary monoamines, methylamine, ethylamine, and n‐propylamine constitute the most abundant amines in the CO3, CV3, CK4, and CK5 meteorites studied here. Contrary to the predominance of n‐ω‐amino acid isomers in CO3 and thermally altered meteorites, there appears to be no preference for the larger n‐amines.     

Petrology and oxygen isotopic compositions of calcium‐aluminum‐rich inclusions in primitive CO3.0‐3.1 chondrites

The petrologic and oxygen isotopic characteristics of calcium‐aluminum‐rich inclusions (CAIs) in CO chondrites were further constrained by studying CAIs from six primitive CO3.0‐3.1 chondrites, including two Antarctic meteorites (DOM 08006 and MIL 090010), three hot desert meteorites (NWA 10493, NWA 10498, and NWA 7892), and the Colony meteorite. The CAIs can be divided into hibonite‐bearing inclusions (spinel‐hibonite spherules, monomineralic grains, hibonite‐pyroxene microspherules, and irregular/nodular objects), grossite‐bearing inclusions (monomineralic grains, grossite‐melilite microspherules, and irregular/nodular objects), melilite‐rich inclusions (fluffy Type A, compact type A, monomineralic grains, and igneous fragments), spinel‐pyroxene inclusions (fluffy objects resembling fine‐grained spinel‐rich inclusions in CV chondrites and nodular/banded objects resembling those in CM chondrites), and pyroxene‐anorthite inclusions. They are typically small (98.4 ± 54.4 µm, 1SD) and comprise 1.54 ± 0.43 (1SD) area% of the host chondrites. Melilite in the hot desert and Colony meteorites was extensively replaced by a hydrated Ca‐Al‐silicate during terrestrial weathering and converted melilite‐rich inclusions into spinel‐pyroxene inclusions. The CAI populations of the weathered COs are very similar to those in CM chondrites, suggesting that complete replacement of melilite by terrestrial weathering, and possibly parent body aqueous alteration, would make the CO CAIs CM‐like, supporting the hypothesis that CO and CM chondrites derive from similar nebular materials. Within the CO3.0‐3.1 chondrites, asteroidal alteration significantly resets oxygen isotopic compositions of CAIs in CO3.1 chondrites (?¹⁷O: ?25 to ?2‰) but left those in CO3.0‐3.05 chondrites mostly unchanged (?¹⁷O: ?25 to ?20‰), further supporting the model whereby thermal metamorphism became evident in CO chondrites of petrologic type ≥3.1. The resistance of CAI minerals to oxygen isotope exchange during thermal metamorphism follows in the order: melilite + grossite < hibonite + anorthite < spinel + diopside + forsterite. Meanwhile, terrestrial weathering destroys melilite without changing the chemical and isotopic compositions of melilite and other CAI minerals.     

Microdistributions and petrogenetic implications of rare earth elements in polymict ureilites

Abstract— Polymict ureilites contain various mineral and lithic clasts not observed in monomict ureilites, including plagioclase, enstatite, feldspathic melt clasts and dark inclusions. This paper investigates the microdistributions and petrogenetic implications of rare earth elements (REEs) in three polymict ureilites (Elephant Moraine (EET) 83309, EET 87720 and North Haig), focusing particularly on the mineral and lithic clasts not found in monomict ureilites. As in monomict ureilites, olivine and pyroxene are the major heavy (H)REE carriers in polymict ureilites. They have light (L)REE‐depleted patterns with little variation in REE abundances, despite large differences in major element compositions. The textural and REE characteristics of feldspathic melt clasts in the three polymict ureilites indicate that they are most likely shocked melt that sampled the basaltic components associated with ureilites on their parent body. Simple REE modeling shows that the most common melt clasts in polymict ureilites can be produced by 20–30% partial melting of chondritic material, leaving behind a ureilitic residue. The plagioclase clasts, as well as some of the high‐Ca pyroxene grains, probably represent plagioclase‐pyroxene rock types on the ureilite parent body. However, the variety of REE patterns in both plagioclase and melt clasts cannot be the result of a single igneous differentiation event. Multiple processes, probably including shock melting and different sources, are required to account for all the REE characteristics observed in lithic and mineral clasts. The C‐rich matrix in polymict ureilites is LREE‐enriched, like that in monomict ureilites. The occurrence of Ce anomalies in C‐rich matrix, dark inclusions and the presence of the hydration product, iddingsite, imply significant terrestrial weathering. A search for ²⁶Mg excesses, from the radioactive decay of ²⁶Al, in the polymict ureilite EET 83309 was negative.     

Noble gases in iddingsite from the Lafayette meteorite: Evidence for liquid water on Mars in the last few hundred million years

Abstract— We analyzed noble gases from 18 samples of weathering products (“iddingsite”) from the Lafayette meteorite. Potassium‐argon ages of 12 samples range from near zero to 670 ± 91 Ma. These ages confirm the martian origin of the iddingsite, but it is not clear whether any or all of the ages represent iddingsite formation as opposed to later alteration or incorporation of martian atmospheric ⁴⁰Ar. In any case, because iddingsite formation requires liquid water, this data requires the presence of liquid water near the surface of Mars at least as recently as 1300 Ma ago, and probably as recently as 650 Ma ago. Krypton and Xe analysis of a single 34 μg sample indicates the presence of fractionated martian atmosphere within the iddingsite. This also confirms the martian origin of the iddingsite. The mechanism of incorporation could either be through interaction with liquid water during iddingsite formation or a result of shock implantation of adsorbed atmospheric gas. Our strongest conclusion is that the iddingsite in Lafayette formed on Mars, in agreement with the microstratigraphic arguments of Gooding et al. (1991) and Treiman et al. (1993). A preterrestrial origin of the iddingsite is required both by the many non‐zero K‐Ar ages and by the presence of Xe that is isotopically distinct from any terrestrial Xe. The Xe is accompanied by Kr, but the Kr and Xe have been fractionated if they are derived from the present martian atmosphere. This is presumably the result of either incorporation via interaction with liquid water (Drake et al., 1994; Bogard and Garrison, 1998) or by adsorption from the martian atmosphere, perhaps accompanied by shock (see also Gilmour et al., 1998, 1999). Although the iddingsite is enriched in Kr and Xe compared to whole‐rock analyses, it is not clear whether iddingsite is the dominant carrier of the atmospheric‐derived gas (Drake et al., 1994) or merely a minor carrier (Gilmour et al., 1999). Our ⁴⁰Ar‐³⁹Ar experiment was disappointing, in that it mostly served to confirm that the iddingsite, which contains fine‐grained clays, is susceptible to recoil loss of ³⁹Ar during irradiation. Only one sample of five gave a clear signal of radiogenic or extraterrestrial ⁴⁰Ar, and that was only by 3°. Potassium‐argon ages of the second set of samples were more successful, ranging from near 0 to 670 ± 91 Ma. It is not clear whether any or all of the ages represent iddingsite formation, as opposed to later alteration. The fact that a Rb‐Sr experiment (Shih et al., 1998) gave an apparent age for iddingsite of 679 ± 66 Ma (2a) suggests that perhaps formation of iddingsite occurred (or began) ～650 Ma ago and that some samples either formed, or were thermally altered, later. The ages could be even younger than 650 Ma, if the samples have incorporated martian atmospheric ⁴⁰Ar. This means that liquid water was certainly present on Mars in the last 1300 Ma (the formation age of Lafayette), and probably within the last 650 Ma.