Experimental shock decomposition of siderite and the origin of magnetite in Martian meteorite ALH 84001

Abstract Shock recovery experiments to determine whether magnetite could be produced by the decomposition of iron‐carbonate were initiated. Naturally occurring siderite was first characterized by a variety of techniques to be sure that the starting material did not contain detectable magnetite. Samples were shocked in tungsten‐alloy holders (W = 90%, Ni = 6%, Cu = 4%) to further ensure that any iron phases in the shock products were contributed by the siderite rather than the sample holder. Each sample was shocked to a specific pressure between 30 to 49 GPa. Transformation of siderite to magnetite as characterized by TEM was found in the 49 GPa shock experiment. Compositions of most magnetites are >50% Fe⁺² in the octahedral site of the inverse spinel structure. Magnetites produced in shock experiments display the same range of sizes (?50–100 nm), compositions (100% magnetite to 80% magnetite‐20% magnesioferrite), and morphologies (equant, elongated, euhedral to subhedral) as magnetites synthesized by Golden et al. (2001) and as the magnetites in Martian meteorite Allan Hills (ALH) 84001. Fritz et al. (2005) previously concluded that ALH 84001 experienced ?32 GPa pressure and a resultant thermal pulse of ?100–110°C. However, ALH 84001 contains evidence of local temperature excursions high enough to melt feldspar, pyroxene, and a silica‐rich phase. This 49 GPa experiment demonstrates that magnetite can be produced by the shock decomposition of siderite as a result of local heating to > 470°C. Therefore, magnetite in the rims of carbonates in Martian meteorite ALH 84001 could be a product of shock devolatilization of siderite as well.     

Ion microprobe U‐Th‐Pb dating of phosphates in martian meteorite ALH 84001

Abstract— Phosphates in martian meteorites are important carriers of trace elements, although, they are volumetrically minor minerals. PO₄ also has potential as a biomarker for life on Mars. Here, we report measurements of the U‐Th‐Pb systematics of phosphates in the martian meteorite ALH 84001 using the Sensitive High Resolution Ion MicroProbe (SHRIMP) installed at Hiroshima University, Japan. Eleven analyses of whitlockites and 1 analysis of apatite resulted in a total Pb/U isochron age of 4018 ± 81 Ma in the ²³⁸U/²⁰⁶Pb‐²⁰⁷Pb/²⁰⁶Pb‐²⁰⁴Pb/²⁰⁶ Pb 3‐D space, and a ²³²Th‐²⁰⁸Pb age of 3971 ± 860 Ma. These ages are consistent within a 95% confidence limit. This result is in agreement with the previously published Ar‐Ar shock age of 4.0 ± 0.1 Ga from maskelynite and other results of 3.8–4.3 Ga but are significantly different from the Sm‐Nd age of 4.50 ± 0.13 Ga based on the whole rock and pyroxene. Taking into account recent studies on textural and chemical evidence of phosphate, our result suggests that the shock metamorphic event defines the phosphate formation age of 4018 ± 81 Ma, and that since then, ALH 84001 has not experienced a long duration thermal metamorphism, which would reset the U‐Pb system in phosphates.     

Thermal history of ALH 84001 meteorite by Fe2+‐Mg ordering in orthopyroxene

Abstract— A single orthopyroxene crystal from the Martian meteorite Allan Hills (ALH) 84001 was studied by X‐ray diffraction (XRD) and electron microprobe analysis (EMPA) to retrieve information about its thermal history. Both sets of data were used to measure the Fe²⁺‐Mg order degree between the M1 and M2 sites expressed by the distribution coefficient k_D. The 529 ± 30°C closure temperature (T_c) of the Fe²⁺‐Mg ordering process of ALH 84001 orthopyroxene (Fs₂₈) was calculated using Stimpfl (2005a, 2005b) ln k_D versus 1/T equation obtained for intermediate iron sample. At this T_c, the orthopyroxene cooling rate, calculated by Ganguly's (1982) numerical method, was 0.1 °C/day. This study puts new constraints on the last high‐temperature thermal episode recorded by orthopyroxene. With reference to the geological history (Treiman 1998), we ascribe this episode to the I3 event, and we interpret the T_c of 529 °C as a lower limit for this impact heating. Our data confirm that experimentally defined physical conditions for the formation of magnetite from decomposition of carbonates took place on the Martian surface during event I3.     

Motion of iron sulfide inclusions inside a shock‐melted chondrule

Abstract— We calculated the trajectories of molten spheres of iron sulfide inclusions inside a melted chondrule during the nebular shock wave heating. Our calculations included the effects of high‐velocity internal flow in the melted chondrule and apparent gravitational force caused by the drag force of nebular gas flow. The calculated results show that large iron sulfide inclusions, which have radii 0.23 times larger than those of the parent chondrules, must reach the surface of the melted chondrule within a short period of time (<<1 s). This effect will provide us with very important information about chondrule formation by nebular shock wave heating.     

Evidence for shock‐induced anhydrite recrystallization and decomposition at the UNAM‐7 drill core from the Chicxulub impact structure

Drill core UNAM‐7, obtained 126 km from the center of the Chicxulub impact structure, outside the crater rim, contains a sequence of 126.2 m suevitic, silicate melt‐rich breccia on top of a silicate melt‐poor breccia with anhydrite megablocks. Total reflection X‐ray fluorescence analysis of altered silicate melt particles of the suevitic breccia shows high concentrations of Br, Sr, Cl, and Cu, which may indicate hydrothermal reaction with sea water. Scanning electron microscopy and energy‐dispersive spectrometry reveal recrystallization of silicate components during annealing by superheated impact melt. At anhydrite clasts, recrystallization is represented by a sequence of comparatively large columnar, euhedral to subhedral anhydrite grains and smaller, polygonal to interlobate grains that progressively annealed deformation features. The presence of voids in anhydrite grains indicates SO_x gas release during anhydrite decomposition. The silicate melt‐poor breccia contains carbonate and sulfate particles cemented in a microcrystalline matrix. The matrix is dominated by anhydrite, dolomite, and calcite, with minor celestine and feldspars. Calcite‐dominated inclusions in silicate melt with flow textures between recrystallized anhydrite and silicate melt suggest a former liquid state of these components. Vesicular and spherulitic calcite particles may indicate quenching of carbonate melts in the atmosphere at high cooling rates, and partial decomposition during decompression at postshock conditions. Dolomite particles with a recrystallization sequence of interlobate, polygonal, subhedral to euhedral microstructures may have been formed at a low cooling rate. We conclude that UNAM‐7 provides evidence for solid‐state recrystallization or melting and dissociation of sulfates during the Chicxulub impact event. The lack of anhydrite in the K‐Pg ejecta deposits and rare presence of anhydrite in crater suevites may indicate that sulfates were completely dissociated at high temperature (T > 1465 °C)—whereas ejecta deposited near the outer crater rim experienced postshock conditions that were less effective at dissociation.     

Experimental generation of shock‐induced pseudotachylites along lithological interfaces

Abstract— To understand the mechanism of formation of shock‐induced pseudotachylites and particularly the role that rock heterogeneities and interfaces play in their formation, shock recovery experiments were carried out on samples consisting of two distinct lithologies (dunite and quartzite). It was possible to generate melt veins of 1–6 μm width along lithological interfaces at moderate shock pressures (6 to 34 GPa). The magnitudes of displacement along the interface, strain rate, and the kinetic heat production indicate that friction is an important heat source that largely contributes to the energy budget of the melt veins. The experimentally produced veins resemble natural S‐type pseudotachylites. The geometry of the veins depends on the orientation of the interface with respect to the shock front and includes strong variations in thickness, formation of melt pockets and injection veins, sudden changes in vein orientation, and sharp vein margins. Two types of melt were observed: vesicle‐free and vesicular melts. Dense vesicle‐free melt rock is likely to represent high‐pressure melts. Vesicular melts were also generated during shock compression, but they remained in a molten state during pressure release and continued shearing. Intermingling of comminuted olivine and melt suggests that ultracataclasis of olivine induced by a dynamic tensile failure is a precursor stage to frictional melting. Shock wave interferences at the lithological interface provide the necessary stress conditions to start dynamic failure of olivine. The composition of the frictional melts ranges from olivine‐normative to enstatite‐normative and is, thus, largely determined by olivine melting. The validity of the sequence of friction melting susceptibilities of rock‐forming minerals inferred from tectonically‐produced pseudotachylites is confirmed and can now be applied to ultra‐high strain rates during shock compression.     

Preferred orientation distribution of shock‐induced planar microstructures in quartz and feldspar

Shocked quartz and feldspar grains commonly exhibit planar microstructures, such as planar fractures, planar deformation features, and possibly microtwins, which are considered to have formed by shock metamorphism. Their orientation and frequency are typically reported to be randomly distributed across a sample. The goal of this study is to investigate whether such microstructures are completely random within a given sample, or whether their orientation might also retain information on the direction of the local shock wave propagation. For this work, we selected samples of shatter cones, which were cut normal to the striated surface and the striation direction, from three impact structures (Keurusselkä, Finland, and Charlevoix and Manicouagan, Canada). These samples show different stages of pre‐impact tectonic deformation. Additionally, we investigated several shocked granite samples, selected at different depths along the drill core recovered during the joint IODP‐ICDP Chicxulub Expedition 364 (Mexico). In this case, thin sections were cut along two orthogonal directions, one parallel and one normal to the drill core axis. All the results refer to optical microscopy and universal‐stage analyses performed on petrographic thin sections. Our results show that such shock‐related microstructures do have a preferred orientation, but also that relating their orientation with the possible shock wave propagation is quite challenging and potentially impossible. This is largely due to the lack of dedicated experiments to provide a key to interpret the observed preferred orientation and to the lack of information on postimpact orientation modifications, especially in the case of the drill core samples.     

An abiotic origin for hydrocarbons in the Allan Hills 84001 martian meteorite through cooling of magmatic and impact‐generated gases

Abstract— Thermodynamic calculations of metastable equilibria were used to evaluate the potential for abiotic synthesis of aliphatic and polycyclic aromatic hydrocarbons (PAHs) in the martian meteorite Allan Hills (ALH) 84001. The calculations show that PAHs and normal alkanes could form metastably from CO, CO², and H² below approximately 250–300°C during rapid cooling of trapped magmatic or impact‐generated gases. Depending on temperature, bulk composition, and oxidation‐reduction conditions, PAHs and normal alkanes can form simultaneously or separately. Moreover, PAHs can form at lower H/C ratios, higher CO/CO² ratios, and higher temperatures than normal alkanes. Dry conditions with H/C ratios less than approximately 0.01–0.001 together with high CO/CO² ratios also favor the formation of unalkylated PAHs. The observed abundance of PAHs, their low alkylation, and a variable but high aromatic to aliphatic ratio in ALH 84001 all correspond to low H/C and high CO/CO² ratios in magmatic and impact gases and can be used to deduce spatial variations of these ratios. Some hydrocarbons could have been formed from trapped magmatic gases, especially if the cooling was fast enough to prevent reequilibration. We propose that subsequent impact heating(s) in ALH 84001 could have led to dissociation of ferrous carbonates to yield fine‐grain magnetite, formation of a CO‐rich local gas phase, reduction of water vapor to H², reequilibration of the trapped magmatic gases, aromatization of hydrocarbons formed previously, and overprinting of the synthesis from magmatic gases, if any. Rapid cooling and high‐temperature quenching of CO‐, H²‐rich impact gases could have led to magnetite‐catalyzed hydrocarbon synthesis     

An experimental study on kinetically‐driven precipitation of calcium‐magnesium‐iron carbonates from solution: Implications for the low‐temperature formation of carbonates in martian meteorite Allan Hills 84001

Abstract— Spherical carbonate globules of similar composition, size, and radial Ca‐, Mg‐, and Fe‐zonation to those in martian meteorite Allan Hills (ALH) 84001 were precipitated from Mg‐rich, supersaturated solutions of Ca‐Mg‐Fe‐CO₂‐H₂O at 150 °C. The supersaturated solutions (pH ? 6–7) were prepared at room temperature and contained in Teflon^TM‐lined stainless steel vessels, which were sealed and heated to 150 °C for 24 h. Experiments were also conducted at 25 °C and no globules comparable to those of ALH 84001 were precipitated. Instead, amorphous Fe‐rich carbonates were formed after 24 h and Mg‐Fe calcites formed after 96 h. These experiments suggest a possible low‐temperature inorganic origin for the carbonates in martian meteorite ALH 84001.     

Estimating shock pressures based on high‐pressure minerals in shock‐induced melt veins of L chondrites

Abstract— Here we report the transmission electron microscopy (TEM) observations of the mineral assemblages and textures in shock‐induced melt veins from seven L chondrites of shock stages ranging from S3 to S6. The mineral assemblages combined with phase equilibrium data are used to constrain the crystallization pressures, which can be used to constrain shock pressure in some cases. Thick melt veins in the Tenham L6 chondrite contain majorite and magnesiowüstite in the center, and ringwoodite, akimotoite, vitrified silicate‐perovskite, and majorite in the edge of the vein, indicating crystallization pressure of ?25 GPa. However, very thin melt veins (5–30 μm wide) in Tenham contain glass, olivine, clinopyroxene, and ringwoodite, suggesting crystallization during transient low‐pressure excursions as the shock pressure equilibrated to a continuum level. Melt veins of Umbarger include ringwoodite, akimotoite, and clinopyroxene in the vein matrix, and Fe₂SiO₄‐spinel and stishovite in SiO₂‐FeO‐rich melt, indicating a crystallization pressure of ?18 GPa. The silicate melt veins in Roy contain majorite plus ringwoodite, indicating pressure of ?20 GPa. Melt veins of Ramsdorf and Nakhon Pathon contain olivine and clinoenstatite, indicating pressure of less than 15 GPa. Melt veins of Kunashak and La Lande include albite and olivine, indicating crystallization at less than 2.5 GPa. Based upon the assemblages observed, crystallization of shock veins can occur before, during, or after pressure release. When the assemblage consists of high‐pressure minerals and that assemblage is constant across a larger melt vein or pocket, the crystallization pressure represents the equilibrium shock pressure.     

High‐pressure phases in shock‐induced melt veins of the Umbarger L6 chondrite: Constraints of shock pressure

Abstract— We report a previously undocumented set of high‐pressure minerals in shock‐induced melt veins of the Umbarger L6 chondrite. High‐pressure minerals were identified with transmission electron microscopy (TEM) using selected area electron diffraction and energy‐dispersive X‐ray spectroscopy. Ringwoodite (Fa₃₀), akimotoite (En₁₁Fs₈₉), and augite (En₄₂Wo₃₃Fs₂₅) were found in the silicate matrix of the melt vein, representing the crystallization from a silicate melt during the shock pulse. Ringwoodite (Fa₂₇) and hollandite‐structured plagioclase were also found as polycrystalline aggregates in the melt vein, representing solid state transformation or melting with subsequent crystallization of entrained host rock fragments in the vein. In addition, Fe₂SiO₄‐spinel (Fa₆₆‐Fa₉₉) and stishovite crystallized from a FeO‐SiO₂‐rich zone in the melt vein, which formed by shock melting of FeO‐SiO₂‐rich material that had been altered and metasomatized before shock. Based on the pressure stabilities of the high‐pressure minerals, ringwoodite, akimotoite, and Ca‐clinopyroxene, the melt vein crystallized at approximately 18 GPa. The Fe₂SiO₄‐spinel + stishovite assemblage in the FeO‐SiO₂‐rich melts is consistent with crystallization of the melt vein matrix at the pressure up to 18 GPa. The crystallization pressure of ?18 GPa is much lower than the 45–90 GPa pressure one would conclude from the S6 shock effects in melt veins (Stöffler et al. 1991) and somewhat less than the 25–30 GPa inferred from S5 shock effects (Schmitt 2000) found in the bulk rock.     

Alteration minerals,fluids, and gases on early Mars: Predictions from 1‐D flow geochemical modeling of mineral assemblages in meteorite ALH 84001

Clay minerals, although ubiquitous on the ancient terrains of Mars, have not been observed in Martian meteorite Allan Hills (ALH) 84001, which is an orthopyroxenite sample of the early Martian crust with a secondary carbonate assemblage. We used a low‐temperature (20 °C) one‐dimensional (1‐D) transport thermochemical model to investigate the possible aqueous alteration processes that produced the carbonate assemblage of ALH 84001 while avoiding the coprecipitation of clay minerals. We found that the carbonate in ALH 84001 could have been produced in a process, whereby a low‐temperature (~20 °C) fluid, initially equilibrated with the early Martian atmosphere, moved through surficial clay mineral and silica‐rich layers, percolated through the parent rock of the meteorite, and precipitated carbonates (thereby decreasing the partial pressure of CO₂) as it evaporated. This finding requires that before encountering the unweathered orthopyroxenite host of ALH 84001, the fluid permeated rock that became weathered during the process. We were able to predict the composition of the clay minerals formed during weathering, which included the dioctahedral smectite nontronite, kaolinite, and chlorite, all of which have been previously detected on Mars. We also calculated host rock replacement in local equilibrium conditions by the hydrated silicate talc, which is typically considered to be a higher temperature hydrothermal phase on Earth, but may have been a common constituent in the formation of Martian soils through pervasive aqueous alteration. Finally, goethite and magnetite were also found to precipitate in the secondary alteration assemblage, the latter associated with the generation of H₂. Apparently, despite the limited water–rock interaction that must have led to the formation of the carbonates ~ 3.9 Ga ago, in the vicinity of the ALH 84001 source rocks, clay formation would have been widespread.     

Multi‐generational carbonate assemblages in martian meteorite Allan Hills 84001: Implications for nucleation,growth, and alteration

Abstract— The carbonate mineralogy of several complex carbonate‐rich regions in Allan Hills (ALH) 84001 has been examined. These regions contain familiar forms of carbonate, as well as textural forms previously unreported including carbonate rosettes, planiform “slab” carbonates, distinct “post‐slab” magnesites, and carbonates interstitial to feldspathic glass and orthopyroxene. Slab carbonates reveal portions of the carbonate growth sequence not seen in the rosettes and suggest that initial nucleating compositions were calcite‐rich. The kinetically controlled growth of rosettes and slab carbonates was followed by an alteration event that formed the magnesite‐siderite layers on the exterior surfaces of the carbonate. Post‐slab magnesite, intimately associated with silica glass, is compositionally similar to the magnesite in these exterior layers but represents a later generation of carbonate growth. Feldspathic glasses had little or no thermal effect on carbonates, as indicated by the lack of thermal decomposition or any compositional changes associated with glass/carbonate contacts.     

Unconfined shock experiments: A pilot study into the shock‐induced melting and devolatilization of calcite

We shocked calcite in an unconfined environment by launching small marble cylinders at 0.8–5.5 km s^?1 into aluminum or copper plates, producing shock stresses between 5 and 79 GPa. The resulting 5–20 mm craters contained intimately mixed clastic and molten projectile residues over the entire pressure range, with melting commencing already at 5 GPa. Stoichiometrically pure calcite melts were not observed as all melts contained target metal. Some of these residues were distinctly depleted in CO₂ and some contained even tiny CaO crystals, thus illustrating partial to complete loss of CO₂. We interpret a thin seam of finely crystalline calcite to be the product of back reactions between CaO and CO₂. The amount of carbonate residue in these craters, especially those at low velocities (<2 km s^?1), is dramatically less than that of silicate impactors in similar cratering experiments, and we suggest that this is due to substantial outgassing of CO₂. Similarly, the volume of carbonate melts relative to the volume of limestone or dolomite in many terrestrial crater structures seems insignificant as well, as is the volume of carbonate melt compared to the volume of impact melts derived from silicates. These volume considerations suggest that volatilization of CO₂ is the dominant process in carbonate‐containing targets. Because we have difficulties in explaining naturally occurring calcite melts by shock processes in dolomite‐dominated targets, we speculate—essentially via process of elimination—that such carbonate melt blebs might be condensation products from an impact‐produced vapor cloud.     

Shock‐induced changes in density and porosity in shock‐metamorphosed crystalline rocks,Haughton impact structure,Canada

Abstract– Shock metamorphism can occur at transient pressures that reach tens of GPa and well over 1000 °C, altering the target material on both megascopic and microscopic scales. This study explores the effects of shock metamorphism on crystalline, quartzofeldspathic basement material from the Haughton impact structure on Devon Island, Arctic Canada. Shock levels were assigned to samples based on petrographic examination of main mineral phases. Conventional shock classification schemes proved to incompletely describe the Haughton samples so a modified shock classification system is presented. Fifty‐two crystalline bedrock samples from the clast‐rich impact melt rocks in the crater, and one reference site outside of the crater, were classified using this system. The shock levels range from 0 to 7 (according to the new shock stage classification proposed here, i.e., stages 0–IV after the Stöffler classification), indicating shock pressures ranging from 0 to approximately 80 GPa. The second aspect of this study involved measuring bulk physical characteristics of the shocked samples. The bulk density, grain density, and porosity were determined using a water displacement method, a bead displacement method, and a Hepycnometer. Results suggest a nonlinear, negative correlation between density and shock level such that densities of crystalline rocks with original densities of approximately 3 g cm^?3 are reduced to <1.0 g cm^?3 at high shock levels. The results also show a positive nonlinear correlation between porosity and shock level. These data illustrate the effect of shock on the bulk physical characteristics of crystalline rocks, and has implications for assessing the habitability of shocked rocks.     

High‐pressure phases in shock‐induced melt of the unique highly shocked LL6 chondrite Northwest Africa 757

Northwest Africa 757 is unique in the LL chondrite group because of its abundant shock‐induced melt and high‐pressure minerals. Olivine fragments entrained in the melt transform partially and completely into ringwoodite. Plagioclase and Ca‐phosphate transform to maskelynite, lingunite, and tuite. Two distinct shock‐melt crystallization assemblages were studied by FIB‐TEM analysis. The first melt assemblage, which includes majoritic garnet, ringwoodite plus magnetite‐magnesiowüstite, crystallized at pressures of 20–25 GPa. The other melt assemblage, which consists of clinopyroxene and wadsleyite, solidified at ~15 GPa, suggesting a second veining event under lower pressure conditions. These shock features are similar to those in S6 L chondrites and indicate that NWA 757 experienced an intense impact event, comparable to the impact event that disrupted the L chondrite parent body at 470 Ma.     

Resolution of impact‐related microstructures in lunar zircon: A shock‐deformation mechanism map

Abstract– The microstructures of lunar zircon grains from breccia samples 72215, 73215, 73235, and 76295 collected during the Apollo 17 mission have been characterized via optical microscopy, cathodoluminescence imaging, and electron backscatter diffraction mapping. These zircon grains preserve deformation microstructures that show a wide range in style and complexity. Planar deformation features (PDFs) are documented in lunar zircon for the first time, and occur along {001}, {110}, and {112}, typically with 0.1–25 μm spacing. The widest PDFs associated with {112} contain microtwin lamellae with 65°/<110> misorientation relationships. Deformation bands parallel to {100} planes and irregular low‐angle (<10°) boundaries most commonly have <001> misorientation axes. This geometry is consistent with a dislocation glide system with <100>{010} during dislocation creep. Nonplanar fractures, recrystallized domains with sharp, irregular interfaces, and localized annealing textures along fractures are also observed. No occurrences of reidite were detected. Shock‐deformation microstructures in zircon are explained in terms of elastic anisotropy of zircon. PDFs form along a limited number of specific {hkl} planes that are perpendicular to directions of high Young’s modulus, suggesting that PDFs are likely to be planes of longitudinal lattice damage. Twinned {112} PDFs also contain directions of high shear modulus. A conceptual model is proposed for the development of different deformation microstructures during an impact event. This “shock‐deformation mechanism map” is used to explain the relative timing, conditions, and complexity relationships between impact‐related deformation microstructures in zircon.     

Experimental reproduction of tectonic deformation lamellae in quartz and comparison to shock‐induced planar deformation features

Abstract— Planar features can develop in quartz during comparatively slow tectonic deformation and during very fast dynamic shock metamorphism. Despite their very different structural nature, tectonically induced deformation lamellae have sometimes been mistaken as shock‐induced planar deformation features (PDFs). To understand the formation of deformation lamellae and to address the substantial differences between them and PDFs, we have conducted deformation experiments on single crystals of quartz in a Griggs‐type apparatus, at a temperature of 800 °C, a confining pressure of 12 kbar, and a strain rate of 0.7–1.1 · 10^?6. The deformed samples were analyzed with transmission electron microscopy (TEM) and compared to natural PDFs from the Ries Crater, Germany. TEM revealed that tectonic deformation lamellae are associated with numerous sub‐parallel curved subgrain walls, across which the orientation of the crystal changes slightly. The formation of deformation lamellae is due to glide‐ and climb‐controlled deformation in the exponential creep regime. In contrast, the PDFs in shocked quartz from the Ries are perfectly planar, crystallographically controlled features that originally represented amorphous lamellae. Due to post‐shock annealing and hydrothermal activity they are recrystallized and decorated with fluid inclusions.     

Secondary‐volatiles linked metallic iron in eucrites: The dual‐origin metals of Camel Donga

The unique occurrence of abundant (~1 vol%) near‐pure‐Fe metal in the Camel Donga eucrite is more complicated than previously believed. In addition to that component of groundmass metal, scattered within the meteorite are discrete nodules of much higher kamacite abundance. We have studied the petrology and composition of two of these nodules in the form of samples we call CD2 and CD3. The nodules are ovoids 11 (CD2) to 15 (CD3) mm across, with metal, or inferred preweathering metal, abundances of 12–17 vol% (CD2 is unfortunately quite weathered). The CD3 nodule also includes at its center a 5 mm ovoid clumping (6 vol%) of F‐apatite. Both nodules are fine‐grained, so the high Fe metal and apatite contents are clearly not flukes of inadequate sampling. The metals within the nodules are distinctly Ni‐rich (0.3–0.6 wt%) compared to the pure‐Fe (Ni generally 0.01 wt%) groundmass metals. Bulk analyses of three pieces of the CD2 nodule show that trace siderophile elements Ir, Os, and Co are commensurately enriched; Au is enriched to a lesser degree. The siderophile evidence shows the nodules did not form by in situ reduction of pyroxene FeO. Moreover, the nodules do not show features such as silica‐phase enrichment or pyroxene with reduced FeO (as constrained by FeO/MgO and especially FeO/MnO) predicted by the in situ reduction model. The oxide minerals, even in groundmass samples well away from the nodules, also show little evidence of reduction. Although the nodule boundaries are generally sharp, groundmass‐metal Ni content is anti‐correlated with distance from the CD3 nodule. We infer that the nodules represent materials that originated within impactors into the Camel Donga portion of the eucrite crust, but probably were profoundly altered during later metamorphism/metasomatism. Origin of the pure‐Fe groundmass metal remains enigmatic. In situ reduction probably played an important role, and association in the same meteorite of the Fe‐nodules is probably significant. But the fluid during alteration was probably not (as previously modeled) purely S and O, of simple heat‐driven internal derivation. We conjecture a two‐stage metasomatism, as fluids passed through Camel Donga after impact heating of volatile‐rich chondritic masses (survivors of gentle accretionary impacts) within the nearby crust. First, reduction to form troilite may have been triggered by fluids rich in S₂ and CO (derived from the protonodules?), and then in a distinct later stage, fluids were (comparatively) H₂O‐rich, and thus reacted with troilite to form pure‐Fe metal along with H₂S and SO₂. The early eucrite crust was in places a dynamic fluid‐bearing environment that hosted complex chemical processes, including some that engendered significant diversity among metal+sulfide alterations.