The Paris chondrite provides an excellent opportunity to study CM chondrules and refractory inclusions in a more pristine state than currently possible from other CMs, and to investigate the earliest ...stages of aqueous alteration captured within a single CM bulk composition. It was found in the effects of a former colonial mining engineer and may have been an observed fall. The texture, mineralogy, petrography, magnetic properties and chemical and isotopic compositions are consistent with classification as a CM2 chondrite. There are ∼45vol.% high-temperature components mainly Type I chondrules (with olivine mostly Fa0–2, mean Fa0.9) with granular textures because of low mesostasis abundances. Type II chondrules contain olivine Fa7 to Fa76. These are dominantly of Type IIA, but there are IIAB and IIB chondrules, II(A)B chondrules with minor highly ferroan olivine, and IIA(C) with augite as the only pyroxene. The refractory inclusions in Paris are amoeboid olivine aggregates (AOAs) and fine-grained spinel-rich Ca–Al-rich inclusions (CAIs). The CAI phases formed in the sequence hibonite, perovskite, grossite, spinel, gehlenite, anorthite, diopside/fassaite and forsterite. The most refractory phases are embedded in spinel, which also occurs as massive nodules. Refractory metal nuggets are found in many CAI and refractory platinum group element abundances (PGE) decrease following the observed condensation sequences of their host phases. Mn–Cr isotope measurements of mineral separates from Paris define a regression line with a slope of 53Mn/55Mn=(5.76±0.76)×106. If we interpret Cr isotopic systematics as dating Paris components, particularly the chondrules, the age is 4566.44±0.66Myr, which is close to the age of CAI and puts new constraints on the early evolution of the solar system. Eleven individual Paris samples define an O isotope mixing line that passes through CM2 and CO3 falls and indicates that Paris is a very fresh sample, with variation explained by local differences in the extent of alteration. The anhydrous precursor to the CM2s was CO3-like, but the two groups differed in that the CMs accreted a higherproportion of water. Paris has little matrix (∼47%, plus 8% fine grained rims) and is less altered than other CM chondrites. Chondrule silicates (except mesostasis), CAI phases, submicron forsterite and amorphous silicate in the matrix are all well preserved in the freshest domains, and there is abundant metal preserved (metal alteration stage 1 of Palmer and Lauretta (2011)). Metal and sulfide compositions and textures correspond to the least heated or equilibrated CM chondrites, Category A of Kimura et al. (2011). The composition of tochilinite–cronstedtite intergrowths gives a PCP index of ∼2.9. Cronstedtite is more abundant in the more altered zones whereas in normal highly altered CM chondrites, with petrologic subtype 2.6–2.0 based on the S/SiO2 and ∑FeO/SiO2 ratios in PCP or tochilinite–cronstedtite intergrowths (Rubin et al., 2007), cronstedtite is destroyed by alteration. The matrix in fresh zones has CI chondritic volatile element abundances, but interactions between matrix and chondrules occurred during alteration, modifying the volatile element abundances in the altered zones. Paris has higher trapped Ne contents, more primitive organic compounds, and more primitive organic material than other CMs. There are gradational contacts between domains of different degree of alteration, on the scale of ∼1cm, but also highly altered clasts, suggesting mainly a water-limited style of alteration, with no significant metamorphic reheating.
The Paris meteorite is a weakly altered CM chondrite that has been discovered recently (Hewins et al., 2014). Its matrix offers the opportunity to search for well-preserved pristine pre-accretional ...material, as well as to study the earliest stages of aqueous alteration in the CM parent body. The study of the matrix of Paris has been conducted by analytical transmission electron microscopy on focused ion beam sections extracted from matrix areas showing different degrees of aqueous alteration.
The least altered matrix sample consists of amorphous silicate grains, a few hundreds of nm in size, separated from one another by an abundant porosity. The amorphous silicates enclose numerous Fe-sulfide nanograins and their average composition is close to the chondritic composition. They share many similarities with GEMS (glass with embedded metal and sulfides) grains present in chondritic-porous interplanetary dust particles and with primitive type 3.0 carbonaceous chondrites. This first discovery of GEMS-like texture in a CM chondrite suggests that GEMS grains could have been the building blocks of the CM matrices.
In more aqueously altered samples, pronounced microstructural heterogeneities were detected at the micrometer scale. The matrix consists mostly of a mixture of amorphous material and Fe-rich, spongy to fine-fibrous, poorly crystalline phyllosilicates. The porosity fraction is significantly reduced and the mixed amorphous-fibrous material frequently forms a continuous groundmass. The close association between these two material types suggests a replacement mechanism due to aqueous alteration. Chemical compositions correlate strongly with the microstructure. The amorphous material has a composition close to the chondritic value while the fine-fibrous phyllosilicate material is Fe-enriched. This Fe enrichment is found to be continuous from weakly to more heavily altered areas, in which the fibrous morphology is coarser and better crystalline. Cronstedtite with intercalated tochilinite is also found, but in pore spaces. This chemical evolution, concomitant with the maturation of the phyllosilicates, demonstrates that the early aqueous fluids that interacted with silicates in the matrix were enriched in Fe. This composition is probably the consequence of the preferential dissolution of metal and iron sulfides during the first stages of alteration. The enrichment of phyllosilicates in Mg seen in more altered CM chondrites is not observed in Paris.
We have investigated the Na distributions in Semarkona Type II chondrules by electron microprobe, analyzing olivine and melt inclusions in it, mesostasis and bulk chondrule, to see whether they ...indicate interactions with an ambient gas during chondrule formation. Sodium concentrations of bulk chondrule liquids, melt inclusions and mesostases can be explained to a first approximation by fractional crystallization of olivine
±
pyroxene. The most primitive olivine cores in each chondrule are mostly between Fa
8 and Fa
13, with 0.0022–0.0069
±
0.0013
wt.% Na
2O. Type IIA chondrule olivines have consistently higher Na contents than olivines in Type IIAB chondrules. We used the dependence of olivine–liquid Na partitioning on FeO in olivine as a measure of equilibration. Extreme olivine rim compositions are ∼Fa
35 and 0.03
wt.% Na
2O and are close to being in equilibrium with the mesostasis glass. Olivine cores compared with the bulk chondrule compositions, particularly in IIA chondrules, show very high apparent D
Na, indicating disequilibrium and suggesting that chondrule initial melts were more Na-rich than present chondrule bulk compositions. The apparent D
Na values correlate with the Na concentrations of the olivine, but not with concentrations in the bulk melt. We use equilibrium D
Na to find the Na content of the true parent liquid and estimate that Type IIA chondrules lost more than half their Na and recondensation was incomplete, whereas Type IIAB chondrules recovered most of theirs in their mesostases
.
Glass inclusions in olivine have lower Na than expected from fractionation of bulk composition liquids, and mesostases have higher Na than expected in calculated daughter liquids formed by fractional crystallization alone. These observations also require open system behavior of chondrules, specifically evaporation of Na before formation of melt inclusions followed by recondensation of Na in mesostases. Within this record of evaporation followed by recondensation, there is no indication of a stage with zero Na in the chondrules, which is predicted by models for shock wave cooling at canonical nebular pressures, suggesting high P
T.
The high Na concentrations in olivine and mesostases indicate very high P
Na while chondrules were molten. This may be explained by local, very high particle densities where Type II chondrules formed. The high P
T, P
Na and number densities of chondrules implied suggest formation in debris clouds after protoplanetary collisions as an alternative to formation after passage of shock waves through large particle-rich clumps in the disk. Encounters of partially molten chondrules should have been frequent in these dense swarms. However, in many ordinary chondrites like Semarkona, “cluster chondrites”, compound chondrules are not abundant but instead chondrules aggregated into clusters. Chondrule melting, cooling and clustering in dense swarms contributed to rapid accretion, possibly after collision, by fallback on the grandparent body and by reaccretion as a new body downrange.
Northwest Africa 7533, a polymict Martian breccia, consists of fine‐grained clast‐laden melt particles and microcrystalline matrix. While both melt and matrix contain medium‐grained ...noritic‐monzonitic material and crystal clasts, the matrix also contains lithic clasts with zoned pigeonite and augite plus two feldspars, microbasaltic clasts, vitrophyric and microcrystalline spherules, and shards. The clast‐laden melt rocks contain clump‐like aggregates of orthopyroxene surrounded by aureoles of plagioclase. Some shards of vesicular melt rocks resemble the pyroxene‐plagioclase clump‐aureole structures. Submicron size matrix grains show some triple junctions, but most are irregular with high intergranular porosity. The noritic‐monzonitic rocks contain exsolved pyroxenes and perthitic intergrowths, and cooled more slowly than rocks with zoned‐pyroxene or fine grain size. Noritic material contains orthopyroxene or inverted pigeonite, augite, calcic to intermediate plagioclase, and chromite to Cr‐bearing magnetite; monzonitic clasts contain augite, sodic plagioclase, K feldspar, Ti‐bearing magnetite, ilmenite, chlorapatite, and zircon. These feldspathic rocks show similarities to some rocks at Gale Crater like Black Trout, Mara, and Jake M. The most magnesian orthopyroxene clasts are close to ALH 84001 orthopyroxene in composition. All these materials are enriched in siderophile elements, indicating impact melting and incorporation of a projectile component, except for Ni‐poor pyroxene clasts which are from pristine rocks. Clast‐laden melt rocks, spherules, shards, and siderophile element contents indicate formation of NWA 7533 as a regolith breccia. The zircons, mainly derived from monzonitic (melt) rocks, crystallized at 4.43 ± 0.03 Ga (Humayun et al. ) and a 147Sm‐143Nd isochron for NWA 7034 yielding 4.42 ± 0.07 Ga (Nyquist et al. ) defines the crystallization age of all its igneous portions. The zircon from the monzonitic rocks has a higher Δ17O than other Martian meteorites explained in part by assimilation of regolith materials enriched during surface alteration (Nemchin et al. ). This record of protolith interaction with atmosphere‐hydrosphere during regolith formation before melting demonstrates a thin atmosphere, a wet early surface environment on Mars, and an evolved crust likely to have contaminated younger extrusive rocks. The latest events recorded when the breccia was on Mars are resetting of apatite, much feldspar and some zircons at 1.35–1.4 Ga (Bellucci et al. ), and formation of Ni‐bearing pyrite veins during or shortly after this disturbance (Lorand et al. ).
The large number of pallasite parent bodies suggests that their formation was a common event in asteroid evolution. New microprobe data has been generated for pallasite olivines and chromites that ...indicate subsolidus redox processes, while literature data has been collated and correlated to form new results and interpretations. The new data include information on metal compositions; the metal cooling rates; the formation of round and fragmental olivine; the close-packing of olivine; the crystallization of the phosphates, phosphoran olivine and orthopyroxene; and the bulk pallasite P and S contents. A model for Main Group pallasites has been developed using fractional melting of a chondritic precursor to make a multi-layered parent body. One portion of this contains a gradational metal–olivine (pallasite) texture. Concentric downward crystallization of the molten metal is indicated, based on cooling rates and metal compositions. Fractional crystallization of the residual silicate and metallic melts produces the minor phases on cooling. Comparisons to and a brief review of past models, particularly those utilizing mixing, have been made.
Cooling rates are one of the few fundamental constraints on models of chondrule formation. In this study, we used Cu and Ga diffusion profiles in metal grains to determine the cooling rates of type I ...chondrules in the Renazzo CR2 chondrite. To improve previous estimations of cooling rates obtained using this method, we used CT scanning and serial polishing of our sections to analyze equatorial sections of large metal grains. Through the cores of these metal grains situated at the surface of chondrules, the cooling rates calculated range from 21 to 86 K h−1 for a peak temperature Tp ~ 1623–1673 K. A metal grain embedded in the core of a chondrule exhibits a cooling rate of 1.2 K h−1 at a Tp ~ 1573 K. We also measured Cu‐Ga diffusion profiles from nonequatorial sections of metal grains and calculated a lower range of cooling rates of 15–69 K h−1 for Tp ~ 1473–1603 K compared to our results from equatorial sections. The high cooling rates inferred from the lightning model (several thousand K h−1) are clearly at odds with the values obtained in this work. The X‐wind model predicts cooling rates (~6–10 K h−1) lower than most of our results. The cooling rates calculated here are in close agreement with those inferred from shock wave models, in particular for temperatures at which olivine crystallizes (from ~10 to several hundreds K h−1 between 1900 and 1500 K). However, the chemical compositions of metal grains in Renazzo are consistent with the splashing model, in which a spray of metal droplets originated from a partially molten planetesimal. Volatile siderophile element depletion is explained by evaporation before metal was engulfed within silicate droplets. Liquid metal isolated from the liquid silicate crystallized during cooling, reacted with the ambient gas, and then re‐accreted within partially molten chondrules.
– Chondrule compositions suggest either ferroan precursors and evaporation, or magnesian precursors and condensation. Type I chondrule precursors include granoblastic olivine aggregates (planetary or ...nebular) and fine‐grained (dustball) precursors. In carbonaceous chondrites, type I chondrule precursors were S‐free, while type II chondrules have higher Fe/Mn than in ordinary chondrites. Many type II chondrules contain diverse forsteritic relicts, consistent with polymict dustball precursors. The relationship between finer and coarser grained type I chondrules in ordinary chondrites suggests more evaporation from more highly melted chondrules. Fe metal in type I, and Na and S in type II chondrules indicate high partial pressures in ambient gas, as they are rapidly evaporated at canonical conditions. The occurrence of metal, sulfide, or low‐Ca pyroxene on chondrule rims suggests (re)condensation. In Semarkona type II chondrules, Na‐rich olivine cores, Na‐poor melt inclusions, and Na‐rich mesostases suggest evaporation followed by recondensation. Type II chondrules have correlated FeO and MnO, consistent with condensation onto forsteritic precursors, but with different ratios in carbonaceous chondrites and ordinary chondrites, indicating different redox history. The high partial pressures of lithophile elements require large dense clouds, either clumps in the protoplanetary disk, impact plumes, or bow shocks around protoplanets. In ordinary chondrites, clusters of type I and type II chondrules indicate high number densities and their similar oxygen isotopic compositions suggest recycling together. In carbonaceous chondrites, the much less abundant type II chondrules were probably added late to batches of type I chondrules from different O isotopic reservoirs.
The sulfur isotope budget of Martian regolith breccia (NWA 7533) has been addressed from conventional fluorination bulk rock analyses and ion microprobe in situ analyses. The bulk rock analyses yield ...865 ± 50 ppm S in agreement with LA‐ICP‐MS analyses. These new data support previous estimates of 80% S loss resulting from terrestrial weathering of NWA 7533 pyrite. Pyrite is by far the major S host. Apatite and Fe oxyhydroxides are negligible S carriers, as are the few tiny igneous pyrrhotite–pentlandite sulfide grains included in lithic clasts so far identified. A small nonzero Δ33S (−0.029 ± 0.010‰) signal is clearly resolved at the 2σ level in the bulk rock analyses, coupled with negative CDT‐normalized δ34S (−2.54 ± 0.10‰), and near‐zero Δ36S (0.002 ± 0.09‰). In situ analyses also yield negative Δ33S values (−0.05 to −0.30‰) with only a few positive Δ33S up to +0.38‰. The slight discrepancy compared to the bulk rock results is attributed to a possible sampling bias. The occurrence of mass‐independent fractionation (MIF) supports a model of NWA 7533 pyrite formation from surface sulfur that experienced photochemical reaction(s). The driving force that recycled crustal S in NWA 7533 lithologies—magmatic intrusions or impact‐induced heat—is presently unclear. However, in situ analyses also gave negative δ34S values (+1 to −5.8‰). Such negative values in the hydrothermal setting of NWA 7533 are reflective of hydrothermal sulfides precipitated from H2S/HS‐ aqueous fluid produced via open‐system thermochemical reduction of sulfates at high temperatures (>300 °C).
The formation of phosphoran olivine by crystallization from a melt was investigated experimentally using a one atmosphere furnace, using San Carlos olivine (Mg,Fe)
2SiO
4 mixed with either iron ...phosphide (FeP) or magnesium pyrophosphate (Mg
2P
2O
7). Both dynamic crystallization and isothermal experiments produced phosphoran olivine as zoned single crystals and as overgrowths surrounding normal, phosphorus-free olivine grains. The crystallization pathways that form phosphoran olivine were traced and confirm that it is a metastable phase that can crystallize from a phosphorus-rich melt over timescales of hours to days. Removal of the P and equilibration of the olivine however requires weeks to months in the presence of silicate melt. Phosphoran olivine with up to 27 wt% P
2O
5 was generated and up to 69% of the Si tetrahedral sites were replaced by P. The substitution of Si by P into olivine was confirmed as 4
VIM
+2 + 2
IVSi
+4
↔
3
VIM
+2 + 2
IVP
+5 +
VI. Phosphoran olivine compositions that vary from (Mg,Fe)
2SiO
4 to (Mg,Fe)
1.65
0.35Si
0.3P
0.7O
4 have been produced in these experiments.
Phosphoran pyroxene was also generated in a few experiments and forms when phosphoran olivine reacts with either tridymite or melt. It has compositions compatible with protopyroxene, orthopyroxene, pigeonite and sub-calcic augite, and can contain up to 31.5 wt% P
2O
5. Like phosphoran olivine, it is also a metastable phase. Phosphorus replaces Si in pyroxene by the following substitution methods: 8
IVSi
+4
↔
3
IVSi
+4 + 4
IVP
+5 +
IV with Al entering the structure by the exchange 2
IVSi
+4
↔
IVAl
+3 +
IVP
+5. Phosphoran pyroxene compositions vary from (Mg,Fe)
8Si
8O
24 to (Mg,Fe)
8Si
3P
4O
24.
Martian regolith breccia NWA 7533 (and the seven paired samples) is unique among Martian meteorites in showing accessory pyrite (up to 1% by weight). Pyrite is a late mineral, crystallized after the ...final assembly of the breccia. It is present in all of the lithologies, i.e., the fine‐grained matrix (ICM), clast‐laden impact melt rocks (CLIMR), melt spherules, microbasalts, lithic clasts, and mineral clasts, all lacking magmatic sulfides due to degassing. Pyrite crystals show combinations of cubes, truncated cubes, and octahedra. Polycrystalline clusters can reach 200 μm in maximum dimensions. Regardless of their shape, pyrite crystals display evidence of very weak shock metamorphism such as planar features, fracture networks, and disruption into subgrains. The late fracture systems acted as preferential pathways for partial replacement of pyrite by iron oxyhydroxides interpreted as resulting from hot desert terrestrial alteration. The distribution and shape of pyrite crystals argue for growth at moderate to low growth rate from just‐saturated near neutral (6 < pH<10), H2S‐HS‐rich fluids at minimum log fO2 of >FMQ + 2 log units. It is inferred from the maximum Ni contents (4.5 wt%) that pyrite started crystallizing at 400–500 °C, during or shortly after a short‐duration, relatively low temperature, thermal event that lithified and sintered the regolith breccias, 1.4 Ga ago as deduced from disturbance in several isotope systematics.
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