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We report a coordinated bulk Cr-Ti-H-C-N isotopic and compositional study of six carbonaceous chondrites from Antarctica that are often considered to be related and termed Yamato-like carbonaceous (CY) chondrites. These meteorites are known to have undergone extensive aqueous alteration followed by different degrees of thermal alteration, to be similar to one another in regard to mineralogy, and share affinities with both the Ivuna-like carbonaceous (CI) and Mighei-like carbonaceous (CM) chondrites. While mineralogically similar, a key difference among these samples is that chondrules have been found in some of these samples, but not in others. The aim of this study is to evaluate the relationship of these meteorites to one another, and investigate how they relate to the CI and CM chondrite groups. We find that with the addition of the isotopic compositions of these 'CY' chondrites, there is now a continuum of isotopic compositions among the carbonaceous chondrites. The CI chondrites are no longer separate in O isotopic compositions from the other carbonaceous chondrite groups in plots of Cr-O and Ti-O. We also find that the 'CY' chondrites represent two distinct populations, which correlate with their heating stage. However, the peak temperatures experienced by each population can only explain the differences in H and C isotopes and abundances and N abundances between samples, and cannot have caused the differences in N, Cr, and Ti isotopes, or all the volatile element depletions of the sample's bulk compositions. Instead, we conclude that the compositional and isotopic data of these two populations correlate with their known chondrule abundances, indicating distinct precursors for each population. We find it most likely that these samples originate from two distinct asteroids, implying that among the six samples studied here, there are not five related samples to constitute a new meteorite group. The chondrule-free heating Stage III samples are most likely heated CI chondrites, while the chondrule-bearing heating Stage IV samples could be heated CM chondrites. [ABSTRACT FROM AUTHOR]

The ungrouped dunitic achondrite Northwest Africa (NWA) 12217 contains symplectic spinel-pyroxene veins that are mineralogically identical to symplectites in other ultramafic planetary materials. The morphology and amount of chromite present in these features relative to the Cr in their olivine hosts suggest an exogenous origin. Petrological experiments show that a Cr laden sulfide liquid reacts with olivine to produce pyroxene by scavenging Mg and Fe from olivine to crystallize chromite. The liquid infiltrates cracks and grain boundaries within the olivine and produces a vein-like symplectic chromite-pyroxene mineralogy similar to that observed in NWA 12217. This process is likely responsible for forming the symplectites in the related ultramafic achondrites NWA 12319, 12562, and 13954, along with many other achondrites. The nucleosynthetic Cr isotopic composition of chromites appears to be in disequilibrium with that of silicates in NWA 12217, suggesting that the liquids responsible for the symplectite forming reaction are at least partially sourced from a different parent body and result from an impact. [ABSTRACT FROM AUTHOR]

Zn/FeT (FeT=Fe2+ + Fe3+) ratios in primitive melts have been proposed as a redox proxy to assess the redox states of the upper mantle. However, to effectively use the melt Zn/FeT ratio as a redox proxy, it is necessary to compare variations of melt Zn/FeT ratios induced by changes in oxygen fugacity (f O 2) with variations due to changes in Zn-Fe contents and mineralogy of the sources. Here we show that the melt Zn/FeT ratio variation caused by f O 2 change can be expressed as Δ(Zn m / Fe m T) = (Zn per / Fe per T)* Δ (F e m 2 + / F e m T) /(D Zn per/m / D Fe 2+ per/m). Zn/FeT ratios in most arc and MORB peridotites (Zn per / Fe per T) are 9.0 ± 1.0*10−4, and melt Fe2+/FeT ratio variation resulted from f O 2 change [ Δ (F e m 2 + / F e m T) ] can be easily obtained by the existing model. Hence, if the Zn and Fe2+ partition coefficients (D Zn per/m and D Fe 2+ per/m) between melt and peridotite are known, the melt Zn/FeT ratio variation resulting from f O 2 change can be estimated. In this study, we determined D Zn between olivine, orthopyroxene, clinopyroxene and basaltic melts at 0.75–2.5 GPa and 1250–1450 ℃. Our data show that melt composition (expressed as MgO content) dominantly controls the mineral-melt Zn partitioning under peridotite melting conditions. These data, along with published mineral-melt D Fe 2+ data, enable us to calculate appropriate D Zn per/m / D Fe 2+ per/m , which is 0.78 ± 0.02 under arc and MORB spinel peridotite melting conditions. Based on these parameters, the calculated average melt Zn/FeT ratio variation caused by per log unity f O 2 change in typical f O 2 span of arc and MORB mantles is only ∼ 0.69 ± 0.20*10−4. Alternatively, melt Zn/FeT ratio variations caused by changes in Zn-Fe contents and mineralogy of peridotites are ±1.10*10−4. These findings indicate that melt Zn/FeT ratio variation induced by one log units f O 2 change is on the same order of magnitude as those caused by changes in Zn-Fe contents and mineralogy of peridotites. Therefore, unless the precise chemical and mineralogical compositions of the mantle sources can be determined independently, the melt Zn/FeT redox proxy is unsuitable for tracing the mantle f O 2. Our study, combined with recent works on melt Cu and V/Sc redox proxies, suggests that these redox proxies, previously considered as the strongest evidence for a reduced arc mantle, might not support the idea of a reduced arc mantle. [ABSTRACT FROM AUTHOR]

Among carbonaceous chondrites, the chondrules of CB and CH stand out by being dominated by skeletal barred olivine and cryptocrystalline textures. These non-porphyritic chondrules are thought to have formed within an impact-generated plume resulting from large-scale asteroidal collisions late in disk history. Porphyritic chondrules are also present, if rare, in CB and CH chondrites and might correspond to nebular objects formed earlier in the disk. We report on the mineralogy, petrology, and oxygen isotopic compositions of porphyritic chondrules in the Isheyevo CH/CB b chondrite. These chondrules show minor element variations at both the chondrule and individual olivine grain scales, which are similar to those observed in other chondrites. In terms of oxygen isotopes, individual chondrules show contrasting behavior with either negligible, mass-dependent or mass-independent O-isotopic variations. They also display different average Δ17O, ranging from −6 ‰ to +4 ‰, anticorrelated with size, with most chondrules (8/13) showing Δ17O > 0 ‰. Our results show that porphyritic chondrules in CB (and CH) chondrites are of nebular origin and do not result from the collisional impact at the origin of other CB components. We propose that CB porphyritic chondrules originate from the chondritic impactor involved in the collision, similarly to hydrated matrix-rich clasts reported in Isheyevo. Altogether, this shows that two chondrule populations, formed by both nebular and planetary processes, co-exist in CB and CH chondrites. Isheyevo thus represents an archetypal chondrite lying at the transition between two dominant chondrule-forming regimes, nebular and impact-related. [ABSTRACT FROM AUTHOR]

Samples collected from the surface/subsurface of C-type asteroid 162173 Ryugu by the Hayabusa2 mission were nondestructively analyzed in three dimensions (3D). Seventy-three small particles (approximately 10–180 µm in size) were observed using X-ray nanotomography, with an effective spatial resolution of approximately 200 nm. Detailed descriptions of these samples in terms of mineralogy, petrology, and variations among particles were reported. The 57 most common particles consisted of a phyllosilicate matrix containing mineral grains, mainly magnetite, pyrrhotite, dolomite and apatite. The remaining particles were mostly monomineralic particles (pyrrhotite, dolomite, breunnerite, apatite, and Mg-Na phosphate) with two unique particles (calcite in a Al 2 Si 2 O 5 (OH) 4 matrix, and CaCO 3 , phyllosilicate, and tochilinite-chronstedtite inclusions in a carbonaceous material matrix). The results confirmed that the samples correspond to Ivuna-type carbonaceous chondrites (CI chondrites) or related materials. Many small inclusions of voids and carbonaceous materials were detected in pyrrhotite, dolomite, breunnerite, and apatite. However, no fluid inclusions were observed, except for those in pyrrhotite that have already been reported. Magnetite exhibited a wide variety of morphologies, from irregular shapes (spherulites, framboids, plaquettes, and whiskers) to euhedral shapes (equants, rods, and cubes), along with transitional shapes. In contrast, the other minerals exhibit predominantly euhedral shapes (pyrrhotite: pseudo-hexagonal plates, dolomite: flattened rhombohedrons, breunnerite: largely flattened rhombohedrons, and apatite: hexagonal prisms) or aggregates of faceted crystals, except for Mg-Na phosphate. The matrices were heterogeneous with variable phyllosilicate particle sizes, Mg/Fe ratios, density (1.7 ± 0.2 g/cm3), nanoporosities (36 ± 9 %), and abundances of nanograins of Fe(-Ni) sulfides. The macroporosity of the particles was estimated as 12 ± 4 %. The observed textural relationships among the minerals suggest a precipitation sequence of: magnetite (spherulite → plaquette/framboid → rod/equant) → pyrrhotite (pentlandite → pyrrhotite) → apatite → dolomite → breunnerite → coarse phyllosilicates. Fe-bearing olivine (or low-Ca pyroxene) might have precipitated later than dolomite, indicating a high Mg activity in the aqueous solution. This precipitation sequence corresponds to a transition from irregular crystal forms (as seen in some magnetite) to regular forms of euhedral crystals (observed in some magnetite and other minerals). Based on the precipitation sequence and mineral morphologies, together with previously reported observations, a model for aqueous alteration in the Ryugu parent body was proposed as follows: CO 2 -H 2 O ice, amorphous silicates (GEMS-like material), and some minerals (mostly metal, sulfides, and anhydrous silicates) accumulated to form the parent body of Ryugu. Amorphous silicates and Fe-Ni metal quickly dissolved into the melted ice to form a highly supersaturated aqueous solution. Poorly-crystalized phyllosilicate and spherulitic magnetite precipitated first, followed by plaquette/framboidal magnetites with decreasing degree of supersaturation due to precipitation. Pseudo-hexagonal pyrrhotite plates were formed by dissolution and reprecipitation under relatively low supersaturation. Subsequently, apatite, dolomite, and breunnerite precipitated in this order in response to decreasing supersaturation. [ABSTRACT FROM AUTHOR]

Iron isotopes are a valuable tool for evaluating processes that control Fe redox cycling in modern and ancient environmental settings. However, robust evaluation of Fe isotope compositions in natural samples requires that fractionations associated with key (bio)geochemical reactions are well-defined. The reductive dissolution of Fe (oxyhydr)oxide minerals mediated by dissolved sulfide exerts a major influence on solid phase Fe mineralogy and dissolved porewater Fe profiles during early diagenesis of organic-rich sediments, but to date, no studies have investigated Fe isotope fractionations during this process. Here, we report the results of laboratory sulfidation experiments, examining apparent Fe isotope fractionations for a variety of Fe (oxyhydr)oxide minerals. The iron isotope compositions of reaction products were determined for both the reduction-dominated and dissolution-dominated steps of the reaction. The reductive step for lepidocrocite and hematite produced Fe(II) that was up to 0.25 ‰ heavier than the bulk starting mineral. By contrast, the reduction of ferrihydrite produced isotopically light Fe(II), with isotope compositions −0.1 to −0.6 ‰ lower than the initial mineral. Consistent with previous studies of the reductive dissolution of Fe (oxyhydr)oxide minerals via abiological and biological pathways, the lighter isotope was preferentially released from the mineral surface during the dissolution phase for all minerals, with dissolved Fe2+ isotope compositions up to ∼2.0 ‰ lower than the surface bound Fe(II). The magnitude of isotopic fractionation during both of these steps is directly related to rates of reaction, and is thus controlled by factors such as sulfide concentration, mineral concentration, crystal structure, surface area and pH. Our data demonstrate that dissolved Fe2+ with δ56Fe compositions approaching −1.0 ‰ is readily generated during the overall reaction, suggesting that sulfide-promoted reductive dissolution of Fe (oxyhydr)oxide minerals may contribute significantly to the generation of light Fe isotope compositions in anoxic settings. [ABSTRACT FROM AUTHOR]

The CY chondrites are a group of thermally metamorphosed carbonaceous chondrites. Although they share similarities with the CM and CI chondrites, their primary properties argue for a distinct classification. Previous studies have highlighted their isotopically heavy bulk compositions (δ17O = 10 ‰, δ18O = 21 ‰, Δ17O = 0 ‰) and exceptionally high sulphide abundances (10–30 vol%). In this work we explore their petrography and alteration history. The CYs accreted low abundances of chondrules (15–20 area%) with average apparent diameters slightly larger (∼320–340 µm) than the CM chondrites. In contrast to the CMs, the CYs record an early episode of brecciation prior to the main window of aqueous alteration. Subsequent fluid activity produced a range of alteration extents with both CY2 and CY1 chondrites documented. Phyllosilicate minerals in the CYs were a mix of serpentine and saponite (including occurrences of Na-saponite) with minor quantities of chlorite (within chondrules). An initial generation of Fe-sulphides formed by sulfidation of metal, and by precipitation from S-rich fluids. Three generations of carbonates are recognized, an early generation that infilled voids left by brecciation and co-precipitated with sulphide, a later generation that co-precipitated with magnetite and a final Fe-Mg-bearing generation which formed large (>100 µm) clasts. Only the first-generation carbonates are found in the CY2s, while the CY1s preserve all three generations. Phosphates occur as Ca-apatite or rarely as Mg-bearing apatite and have hydroxylapatite compositions, indicating low halogen activities in the alteration fluids. Refractory oxides (ilmenite and Cr-spinel) occur as precipitates adhering to the margins of phyllosilicates. They formed late in the alteration sequence and attest to oxidizing conditions. During the late-stages of aqueous alteration Fe-sulphides were replaced by magnetite. Thermal metamorphism (Stage II-IV: ∼300–750 °C) overprinted aqueous alteration leading to dehydration and recrystallization of the phyllosilicate matrix and the decomposition of some carbonate phases. Most Fe-sulphide grains survived heating without decomposition as initial partial decomposition from pyrrhotite to troilite under closed system conditions led to elevated ƒS 2 gas and resulted in a stabilizing effect. Retrograde reactions between trapped S 2 gas and metal/magnetite formed a final generation of Fe-sulphides. The survival of Fe-sulphides and their stochiometric troilite compositions are evidence for near-closed system heating. Analysis of organic matter by Raman spectroscopy supports an interpretation of short-duration heating (on the scale of minutes to days), at peak temperatures between 750 and 900 °C. Thus, an impact event was the most likely cause of metamorphic heating. [ABSTRACT FROM AUTHOR]

Gabbroic and microgabbroic shergottites are intrusive igneous rocks on Mars and exhibit a wide variety of mineralogical and geochemical properties. However, their source reservoirs, magmatic processes and the link to other shergottite subtypes are not well constrained. Northwest Africa (NWA) 13581 is a newly found permafic olivine gabbro, representing a cumulate member in the shergottite group. This sample provides new critical constraints on the characteristics of mantle sources and magmatic evolution of shergottites. The texture and mineral chemistry of NWA 13581 indicate a polybaric crystallization condition, with an increase in oxygen fugacity of approximately 1 log unit after ascent and emplacement. Geochemical studies suggest that the sample is young (150 ± 25 Ma) and may share a similar enriched mantle reservoir (initial ε176Hf i = −18.4, initial ε143Nd i = −7.1) with shergottites like Zagami (basaltic shergottite), NWA 10169 (poikilitic shergottite) and Larkman Nunatak 06319 (olivine-phyric shergottite). In addition, the presence of potassium-rich melt inclusions enclosed in early-formed minerals of NWA 13581 implies a fertile source, probably originating from a metasomatized mantle. The occurrence of similar potassium-rich components in other enriched shergottites may suggest a common process in their mantle reservoir and during crystallization. Overall, NWA 13581 resembles poikilitic shergottites closer than typical gabbroic shergottites in several aspects such as poikilitic texture, mineral chemistry, magmatic evolutionary path, and emplacement conditions. A simplified model is proposed for the formation of NWA 13581 and poikilitic shergottites in the same magma series. Magma mixing and/or assimilation are not the major mechanism that account for their slightly varied mineral modal abundances and quantitative textural characteristics. For samples derived from similar mantle sources, the textural and mineralogical diversities of shergottites are largely related to crystallization at different crustal levels. [ABSTRACT FROM AUTHOR]

Understanding the genetic relationship between different chondritic components will help to decipher their origin and dynamical evolution within the protoplanetary disk. Here, we obtain insight into these processes by acquiring O-isotope data from 17 Al-rich chondrules from unequilibrated ordinary chondrites (OCs, petrologic type ≤ 3.2) and four Al-rich chondrules from the CO3.1 carbonaceous chondrite Dar al Gani (DaG) 083. These particular kinds of chondrules are of special interest, as it is suggested that their precursors may have contained refractory material related to Ca,Al-rich inclusions (CAIs) and amoeboid olivine aggregates (AOAs). The four investigated Al-rich chondrules from the CO3.1 chondrite Dar al Gani 083 consist of olivine, low-Ca pyroxene, Ca pyroxene, and spinel phenocrysts embedded in mostly Na-rich glassy mesostasis. Two chondrules have a homogeneous O-isotopic composition and two are heterogeneous in their O-isotopic composition. One chondrule contains relict spinel grains with a Δ17O value of −24.3 ± 1.3‰, indicative of 16O-rich precursor refractory material, similar to constituents of CAIs and AOAs. The presence of CAI-like precursors for the Al-rich chondrules from CO chondrites is consistent with their previously reported presence of 50Ti excesses (Ebert et al., 2018). The Al-rich chondrules in the ordinary chondrites studied consist of olivine, low-Ca pyroxene, Ca pyroxene, and, occasionally, spinel phenocrysts embedded in mostly Na-rich glassy mesostasis. Hibonite is present in one Al-rich chondrule. The vast majority of these chondrules have heterogeneous O-isotopic compositions: Chondrule glasses are 16O-depleted compared to chondrule phenocrysts; the Δ17O values of the former approach those of aqueously formed fayalite and magnetite grains in type 3 OCs, ∼ +5‰. We infer that the chondrule glasses experienced O-isotope exchange with an aqueous fluid on the OC parent asteroids. Chondrule phenocrysts, like spinel, olivine, low-Ca pyroxene, and Ca pyroxene, were not affected by this isotope exchange and preserved their initial O-isotope compositions. The phenocrysts within individual chondrules have similar Δ17O, whereas the inter-chondrule Δ17O values range from −4.5 to +1.4‰, i.e., they are in general 16O enriched relative to the majority of ferromagnesian type I and type II porphyritic chondrules in OCs having Δ17O of ∼ +1‰. Because no relict grains were identified in the Al-rich chondrules from ordinary chondrites, the original O-isotopic composition of the refractory precursor material remains unknown. Additional detailed Na measurements within olivine grains show no major changes in the Na content of the chondrule melt during their crystallization. This implies either that the Na was part of the precursor material or that the Na was enriched in the chondrule melt/glass after crystallization of the olivines. [ABSTRACT FROM AUTHOR]

Cosmic symplectites (COSes), consisting mainly of nanoscaled symplectic intergrowths of magnetite and Fe-Ni sulfides, have extremely heavy oxygen isotopic compositions and are considered tracers of 16O-poor primordial ice in the early solar system. We examined the three-dimensional microstructure and mineralogy of one COS particle, COS#1, in the Acfer 094 carbonaceous chondrite and investigated its origin. Synchrotron-radiation based X-ray computed nanotomography revealed a presence of micro-inclusions inside COS#1. The largest inclusion consists mainly of high-temperature phases of anhydrous sodium sulfate (Na 2 SO 4) and elemental sulfur, which seem to have been formed from a Na 2 SO 4 -S eutectic melt. COS#1 showed a trilayered structure surrounding the large inclusion: the innermost coarse-grained layer consisting mainly of 100–200 nm-sized magnetite and Fe-sulfide, the symplectite layer consisting mainly of nanoscaled symplectic intergrowths of magnetite and Fe-Ni sulfides, and the outermost Fe-oxide layer. The symplectite layer comprises the major volume of COS#1 and shows the pseudomorphic structure of precursor Fe-Ni metal grains. The coarse-grained layer seems to have been formed via metal–salt interaction (hot corrosion) at high temperatures, where the precursor Fe-Ni metals contacted with the Na 2 SO 4 -S melt. The symplectite formed simultaneously with the coarse-grained layer due to high-speed diffusion of sulfur and oxygen inside the metal grains. The high-temperature metal–salt interactions should have occurred before the incorporation of COS#1 into the meteorite parent body. The precursor of COS#1 should have consisted of Fe-Ni metals and O-Na-S-rich material. The two reductive and oxidative components seem to have formed separately and got together by some mechanical mixing processes in nebula. The COS#1 precursor was heated in a short period and the O-Na-S-rich material melted. The melt induced the hot corrosion of the Fe-Ni metals and was subsequently cooled and solidified. Subsequently, it was incorporated into the meteorite parent body as COS#1. In the parent body, aqueous alteration occurred and formed the outermost Fe-oxide layer on the COS#1 surface. [ABSTRACT FROM AUTHOR]

The upper continental crust is formed from chemically diverse granitic plutons. Active debate surrounds the range of physical conditions (P-T-X- f O 2) and differentiation processes which occur in mush bodies that solidify to form plutons. Transition metal stable isotopes are increasingly employed to trace magmatic processes in both extrusive lavas and intrusive plutonic suites, with a focus on analysis of whole rock powders. However, studies of plutonic suites often overlook the complex textures represented within coarse grained samples, and how these will influence whole rock isotopic compositions. Here we examine the calc-alkaline Boggy Plain Zoned Pluton, SE Australia, which closely approximates closed system behaviour during magmatic differentiation. We combine petrological examination with Fe and Zn isotopic analysis of biotite, hornblende and magnetite mineral separates and whole rock powders. Whole rock Fe isotopic composition (as δ56Fe) increases from 0.038‰ to 0.171‰ with decreasing MgO content, while mineral separates display heavy Fe isotope enrichment in the order magnetite > biotite = hornblende > pyroxene. A lack of correlation between whole rock Fe and Zn isotopic compositions suggests that the Fe isotopic variation is predominantly driven by closed system fractional crystallisation: specifically by the balance between crystallisation of isotopically heavy magnetite, and isotopically light silicates. To demonstrate this quantitatively, temperature dependent mineral-melt fractionation factors were derived from the mineral separate data (Δ56Fe mag-melt = 0.17 × 106/T2 and Δ56Fe bt/hbd-melt = −0.12 × 106/T2) and used to construct models that successfully reproduce the observed Fe isotopic variation during fractional crystallisation. These fractionation factors are compared to theoretical and empirical estimates from previous studies. We highlight that accurate determinations of temperature and modal mineralogy are critical when modelling Fe isotopic variations in plutonic suites. Successful interpretation of equilibrium Fe isotopic fractionation in a relatively simple calc-alkaline suite like the Boggy Plain Zoned Pluton paves the way for Fe isotopes to be used to investigate more complex mush bodies. [ABSTRACT FROM AUTHOR]

Fine-grained, spinel-rich inclusions (FGIs) are abundant in CV3 chondrites and exhibit textures and compositions that are consistent with a condensation origin. We have conducted a systematic investigation of FGIs from two reduced CV3 chondrites, Leoville and Efremovka, which has revealed a number of microscale variations in the primary mineralogies and textures of nodules, and provided further insights into the origins of FGIs. Nodules in individual FGIs vary in size and exhibit variations in their mineralogical zonation, resulting in significant heterogeneity within each FGI. In individual FGIs, nodules with a small size (typically < 10 μm) commonly form clusters, whereas larger nodules (often > 20 μm) are either embedded in the mass of small nodules or occur as shells surrounding clusters of small nodules. The size difference is associated with a difference in mineralogy: small nodules typically contain single or a few spinel/melilite grains as cores, while the spinel/melilite cores of large nodules are polycrystalline and more compact. Transmission Electron Microscope observations show that the nodules have complex microstructures, including the presence of fine-grained spinel, the close association of fine-grained Al-Ti-diopside with spinel, and a crystallographic orientation relationship between adjacent clinoenstatite and diopside grains. Our microstructural observations indicate that disequilibrium condensation played an important role in the formation of FGIs, consistent with some previous studies. Specifically, the presence of spinel-cored and melilite-dominant nodules, as well as the different occurrences of spinel (in the cores and on the periphery), suggest that formation of these nodules occurred under disequilibrium conditions, which may be caused by physical isolation of condensates. Nodules in FGIs show textural and compositional similarities with other types of non-igneous CAIs: hibonite-spinel inclusions and fluffy Type A CAIs. We suggest that mineralogically-distinct nodules are micrometer-sized counterparts of different types of non-igneous CAIs and record an evolutionary condensation sequence in the solar nebula. It is likely that different nodules in individual FGIs formed in the same gaseous reservoir, but at different times. The mechanism of physical isolation of condensates probably controlled the accretion behavior of nodules with different mineralogies and sizes, resulting in the observed distribution patterns of nodules. On the other hand, some mineralogically-zoned FGIs, with a Mg-rich core and a Ca-rich mantle, can be better explained by condensation, followed by transport of the inclusions to a different region of the protoplanetary disk. [ABSTRACT FROM AUTHOR]

In order to understand the mechanism of vanadium (V) isotope fractionation during magmatic differentiation, we analyzed the V isotopic compositions of eruptive pumices, olivine-phyric basalts, and differentiated segregation veins from the Kilauea Iki lava lake, Hawaii. Most olivine-phyric samples contain whole rock δ51V ranging from −0.95‰ to −0.80‰ similar to the average value of the bulk silicate Earth (BSE; −0.91‰ ± 0.09‰), reflecting the composition of melt coexisting with olivine. One eruptive pumice is similar to most of the olivine-phyric samples with a δ51V value of −0.89‰, while the other eruptive pumice and the two highest-MgO olivine-phyric samples have δ51V shifting to slightly higher values of −0.81‰ to −0.63‰. For the segregation veins, the whole rock δ51V values vary from −0.81‰ to −0.53‰, suggesting an average mineral-melt fractionation factor (Δ51V mineral-melt) of about −0.15‰ during fractional crystallization. The late differentiated veins exhibit the highest δ51V, δ56Fe, and δ49Ti values, showing isotope fractionation driven by the crystallization of Fe–Ti oxides. The estimated Δ51V mineral-melt value for Kilauea Iki samples is much smaller than that reported for Hekla basalts from Iceland and Anatahan lavas from Mariana (−0.5‰ to −0.4‰; Prytulak et al., 2017), which may reflect differences in magma differentiation in terms of the timing of Fe–Ti oxide saturation, and the amount and mineralogy of the Fe–Ti oxides. [ABSTRACT FROM AUTHOR]

A ∼175 µm refractory inclusion, A-COR-01 from one of the least altered carbonaceous chondrites, ALHA 77307 (CO3.0), has been found to bear unique characteristics that indicate that it is one of the first solids to have formed at the very birth of the solar system while isotopic reservoirs were still evolving rapidly. Its core is composed mainly of hibonite and corundum, the two phases predicted to condense first from a gas of solar composition, and like many common types of Calcium-, Aluminium-rich Inclusions (CAIs) is surrounded by a rim of diopside. Core minerals in A-COR-01 are very 16O-rich (Δ17O Core = −32.5 ± 3.3 (2SD) ‰) while those in the rim display an O isotopic composition (Δ17O Rim = −24.8 ± 0.5 (2SD) ‰) indistinguishable from that found in the vast majority of the least altered CAIs. These observations indicate that this CAI formed in a very 16O-rich reservoir and either recorded the subsequent evolution of this reservoir or the transit to another reservoir. The origin of A-COR-01in a primitive reservoir is consistent with the very low content of excess of radiogenic 26Mg in its core minerals corresponding to the inferred initial 26Al/27Al ratio ((26Al/27Al) 0 = (1.67 ± 0.31) × 10−7), supporting a very early formation before injection and/or homogenisation of 26Al in the protoplanetary disk. Possible reservoir evolution and short-lived radionuclide (SLRs) injection scenarios are discussed and it is suggested that the observed isotope composition resulted from mixing of a previously un-observed early reservoir with the rest of the disk. [ABSTRACT FROM AUTHOR]

• The terrestrial mantle is heterogeneous in δ60/58Ni. • Fertile mantle pyroxenites range to very light δ60/58Ni. • Iron-rich lithologies & samples with less radiogenic 143Nd/144Nd have lighter δ60/58Ni. • Ultramafic xenoliths show systematic but limited inter-mineral δ60/58Ni fractionation. • Light δ60/58Ni in the mantle may fingerprint subducted components. High precision nickel stable isotopic compositions (δ60/58Ni) are reported for 22 peridotite xenoliths from the USA (Kilbourne Hole, New Mexico), Tanzania, and Cameroon. For a subset of these, δ60/58Ni is also reported for their constituent mineral separates (olivine, orthopyroxene, clinopyroxene, and spinel). Bulk peridotites show significant heterogeneity in Ni isotopic composition, ranging from +0.02‰ to +0.26‰. Unmetasomatised fertile peridotites from three localities, define an average δ60/58Ni of +0.19±0.09‰ (n = 18). This value is comparable to previous estimates for the δ60/58Ni of the bulk silicate earth (BSE), but is unlikely to be representative, given observed heterogeneity, presented here and elsewhere. Samples with reaction rims and interstitial glass (interpreted as petrographic indications of minor metasomatism) were excluded from this average; their Ni isotopic compositions extend to lighter values, spanning nearly the entire range observed in peridotite worldwide. Dunites (n = 2) are lighter in δ60/58Ni than lherzolites and harzburgites from the same location, and pyroxenites (n = 5) range from +0.16‰ to as light as −0.38‰. The δ60/58Ni in the Kilbourne Hole xenoliths correlate negatively with bulk-rock Fe concentration and positively with 143Nd/144Nd, providing evidence that light δ60/58Ni is associated with mantle fertility and enrichment. The trend between δ60/58Ni and Fe concentration in bulk rocks appears to be global, replicated across the peridotites in this work from other localities, and in literature data. The inter-mineral fractionations are small; the maximum difference between heaviest and lightest phase is 0.12‰. This provides evidence that bulk rock δ60/58Ni variation does not result from differences in modal mineralogy, fractional crystallization or degrees of partial melting. The δ60/58Ni fractionation appears to be an equilibrium effect and usually is in the decreasing order spinel > olivine = orthopyroxene > clinopyroxene. However, the fractionation between clinopyroxene and orthopyroxene varies in magnitude and sign, and is correlated with pyroxene Si/Fe positively, and Fe/Mg negatively. The magnitude of inter-pyroxene fractionation also correlates with other pyroxene compositional ratios (e.g. La/Sm clinopyroxene); as well as bulk rock δ60/58Ni, and [U]. These data provide evidence that Ni isotopes fractionate at the bulk rock and mineral scale in response to mantle enrichment processes, possibly related to recycling of isotopically light subducted components. [ABSTRACT FROM AUTHOR]

Jarosite is a common mineral in acidic, sulfate-rich environments where it is critical in regulating the acidity of aquatic systems and the mobility of trace elements and potential contaminants. This research aims to understand jarosite formation and recrystallization in these environments by examining the stable iron isotope geochemistry of jarosite at two coastal sites in Victoria, Australia: Fossil Beach and Southside Beach. Jarosite occurs at high abundance as beds, veins, surface coatings and nodules within oxidized zones of sulfidic sediment outcrops and as pebbles, cobbles, and boulders at the base of the outcrops within the intertidal zone, making these two beaches ideal natural laboratories. Synchrotron powder X-ray diffraction (XRD) and ICP-MS results indicate that samples are comprised predominantly of natrojarosite, often with substantial K substitution. Rietveld refinement of XRD patterns shows that most jarosite samples are a solid-solution of Na-K jarosite, differing from previous observations that (near-)end-member mixing predominantly occurs in nature. The iron isotope composition of the jarosite samples have δ56Fe values between −1.91 and +1.24‰ (relative to IRMM-014), an exceptionally large range that partially overlaps with the δ56Fe values of the sulfidic sediment precursor (−0.54 to +1.30‰). There is a negative relationship between the alkali ratio [Na/(Na + K)] and iron isotope composition, with the heavier iron isotopes preferentially partitioned into K-rich jarosite. The large range in δ56Fe values of jarosite likely results from a combination of the variable δ56Fe values of the precursor sulfides, thermodynamic differences between Na- versus K-bearing jarosite, and an open-system Rayleigh distillation during jarosite formation. [ABSTRACT FROM AUTHOR]

We used X-Ray Diffraction (XRD) and Rietveld refinement to determine the modal mineralogy of 118 lunar regolith samples (<150 µm size fraction) from all landed Apollo missions. Data were calibrated with mineral mixtures and compared to results based on an X-ray digital imaging procedure for six soils obtained by the Lunar Soil Characterization Consortium. Agreement between XRD and digital imaging for all minerals detectable in the six soils is excellent (R2 = 0.953). XRD-based ternary plots (plagioclase-total pyroxene-olivine) vary from plagioclase-dominated (highlands as represented by Apollo 16 samples) to substantial mafic abundances at the mare sites. Olivine varies in relative abundance, with the Apollo 17 mare sites having the largest abundances. Olivine reaches 20 wt% at Apollo 17, but is a minor component at Apollo 14. The results agree with trends in mineral abundances obtained from reflectance spectroscopy for the Apollo sites. In a global context, however, the spectral data display a trend of increasing olivine at roughly constant pyroxene/plagioclase, reaching values of 40% olivine in the plagioclase-pyroxene-olivine ternary plot (e.g., Eratosthenian flows in Procellarum), indicating the presence of significant volumes of olivine-rich rock types on unsampled regions of the lunar surface. [ABSTRACT FROM AUTHOR]

Here we report the relative degrees of thermal metamorphism for five Antarctic Ornans-like carbonaceous (CO) chondrites, including Dominion Range (DOM) 08006, as determined from the Cr-content of their FeO-rich (ferroan) olivine. These five CO3 chondrites complete the previously poorly-defined CO3.00 to 3.2 chondrite metamorphic trend. DOM 08006 appears to be a highly primitive CO chondrite of petrologic type 3.00. We report the detailed mineralogy and petrography of DOM 08006 using a coordinated, multi-technique approach. The interchondrule matrix in DOM 08006 consists of unequilibrated mixtures of silicate, metal, and sulfide minerals and lacks Fe-rich rims on silicates indicating that DOM 08006 has only experienced minimal, if any, thermal metamorphism. This is also reflected by the Co/Ni ratios of Ni-rich and Ni-poor metal, a sensitive indicator of thermal metamorphism, and the presence of euhedral chrome-spinel grains, which typically become subhedral to anhedral during progressive metamorphism. DOM 08006 matrix shows minor evidence for aqueous alteration and while the presence of magnetite surrounding metal in chondrules indicates that there has been some interaction with fluid, much metal remains and none of the sulfides analyzed show evidence of being formed by aqueous alteration. Furthermore, the plagioclase of ∼50% of chondrules analyzed show resolvable excess silica indicating that these chondrules have experienced minimal, if any, reprocessing in the CO parent body. Noble gas data for DOM 08006 show that it contains the highest concentrations of trapped 36Ar and 132Xe of all CO chondrites analyzed to date, further indicating that DOM 08006 is the most primitive CO chondrite known. The cosmic ray exposure age of DOM 08006 is estimated to be ∼19 Ma. The minimally altered nature of DOM 08006 demonstrates that it is an extremely important sample for providing valuable insight into early Solar System conditions. At a total weight of 667 g, a significant amount of material is available for a wide array of future studies. [ABSTRACT FROM AUTHOR]

The weathering of basalt has implications for the global carbon cycle on Earth as well as for understanding sedimentary processes on other terrestrial bodies dominated by a basaltic crust (e.g., Mars), but yet studies in mafic terrains are limited in comparison to their felsic counterpart. Our work details the compositional transformations resulting from the sedimentation process of first-cycle sediments generated in a basalt dominated watershed of southwest Iceland. By sampling multiple sites along the Hvítá S river transport pathway and analyzing the sedimentology, geochemistry, and mineralogy, this work provides a geologically integrated approach to understanding a fluvial source-to-sink system in mafic terrains. Environmental conditions such as climate, hydrology, and transport distance all influence the overall sediment composition, and in response, chemical weathering, physical abrasion, sorting, transport, and mixing are all sedimentary processes unraveled in the geochemical and mineralogical relationships of individual grain size bins. Chemical weathering initiates in the upper reaches of the watershed with the alteration of primary mafic phases to form secondary weathering products. As sediment continues to move downstream, the entire sediment suite becomes more altered, and the extent of chemical weathering is intensified, as evidenced by a higher abundance of clay minerals and glassy material. Fluvial sorting separates detritus by particle size and differentiates them by compositional gradients in geochemistry and mineralogy. As grain size decreases, mafic minerals become less abundant and the finer grain sizes are preferentially enriched in immature weathering minerals and mineraloids (e.g., smectite clays and X-ray amorphous phases). This grain size trend is also correlated with elemental fractionation, illustrated most notably by the clay size fraction (<2 μm) hosting the most altered material in river sediments. However, we note that the environmental conditions of Iceland (e.g., a cold climate and glacial reworking) result in limited element mobility when compared to more temperate climates around the world. Therefore, we suggest that the clay size fraction of river sediments provide a valuable target for understanding the intensity of weathering in these systems, particularly in a colder climate where mineralogical transformations are not always accompanied by a high degree of elemental loss. In addition to weathering and sorting, trace element abundances suggest the mixing of sediments from varying provenances. While the Hvítá S watershed is dominated by basalt, even minor amounts of evolved volcanics (e.g., andesites) contribute to the overall sediment composition. Overall, this work fills a knowledge gap in sedimentation processes in basaltic terrains on Earth, while additionally providing a valuable terrestrial analog for ancient fluvial-deltaic environments preserved in the sedimentary rock record of Mars (e.g., Gale Crater and Jezero Crater). [ABSTRACT FROM AUTHOR]

Rhyolite-hosted hydrothermal systems in the continental crust contain valuable energy and mineral resources that make them of special interest across several scientific disciplines. Despite extensive research on these systems, the temperature-dependence of chemical reactions between host rocks and aqueous-rich fluids and the mineralogical transformations resulting from these reactions are not well quantified. To expand our understanding of the controlling processes operating in these systems, we carried out seven laboratory experiments in which rhyolite was reacted with deionized water at 150 °C to 350 °C and 25 MPa. An additional experiment at 200 °C was carried out to examine the effect of dissolved CO 2 on the reactions. The overarching goal of this experimental study was to provide new insights on the temperature-dependence of water-rock interaction in continental hydrothermal systems. We applied a wide range of chemical, isotopic and mineralogical methods to analyze the reacted rhyolite and waters, and the major observations are: (1) the rhyolite progressively hydrates with increasing temperature between 150 °C to a maximum of 8.2 wt% H 2 O at 275 °C; hydration then decreases until 350 °C in conjunction with the destruction of the rhyolite glass and crystallization of secondary mineral phases; (2) the ratio of molecular water (H 2 O m) to hydroxyl (OH−) of the water that is dissolved in the reacted rhyolite decreases from ∼7 at 150 °C to ∼4 at 250 °C; (3) the main secondary minerals formed are the zeolite ferrierite (T ≥ 275 °C); biotite, albite and cristobalite mainly form at higher experimental temperatures (T ≥ 300 °C); (4) the reacted waters are nearly saturated with respect to amorphous silica; (5) at temperatures ≥ 275 °C nearly all the chlorine is leached into solution; (6) fluorine leaching from the rhyolite gradually increases between 150 °C and 250 °C, but then gradually decreases at higher temperatures and is incorporated into a secondary mineral phase; (7) dissolved CO 2 in the water enhances alkali metal cation leaching from the rhyolite; and (8) calculated Na-K and silica geothermometer temperatures differ from the experimental temperatures by varying amounts. In addition, apart from some small lithium isotope fractionation at temperatures ≤ 250 °C, the stable isotopes of boron, lithium and chlorine do not fractionate during rhyolite-water reactions, and the stable isotope compositions of these species in the reacted water are similar to those in the reactant rhyolite. These results provide new insights for a broad range of applications, including quantifying processes involving rhyolite glass hydration (obsidian hydration dating, perlite formation and discriminating secondary from magmatic water in rhyolitic matrix-glass of volcanic pyroclasts), for geothermal energy and mineral deposit exploration and for monitoring volcanoes. [ABSTRACT FROM AUTHOR]

Soil organic matter (SOM) improves soil fertility and mitigates disturbance related to climate and land use change. Microbial necromass (the accumulated cellular residues of microorganisms) comprises the majority of soil C, yet the formation and persistence of necromass in relation to mineralogy is poorly understood. We tested whether soil minerals had different microbial necromass association mechanisms. Specifically, we tested whether microbial necromass directly sorbed to mineral surfaces or was consumed by live microorganisms prior to mineral association. Applying Raman microspectroscopy with 13C enriched microbial necromass to quantify microbe-mineral interactions, we show that mineralogy alters the initial mechanism of microbial necromass association. In the presence of K-feldspar (lower abiotic C preservation potential), microbial necromass required assimilation by live microorganisms for mineral retention. In contrast, with amorphous aluminum hydroxide (higher abiotic C preservation potential) microbial necromass was retained predominately through abiotic sorption, and was subsequently protected from microbial decomposition. Despite different mechanisms, both minerals retained similar quantities of microbial necromass under biotic conditions. Mineralogy determined not only the quantity of mineral-associated C, but the distinct pathway of microbial necromass association. These findings show the utility of Raman microspectroscopy as a technique to study microbe-mineral interactions, and imply that heterogeneity in mineral-organic interactions could result in gradients of organic matter stability. [ABSTRACT FROM AUTHOR]

A trace element study of Mg-rich cryptocrystalline (CC) and ferrous radiating pyroxene (RP) chondrules, covering from the ultra-refractory Zr to the volatile K, was performed to better understand the processes involved in chondrule formation and their subsequent evolution. The shape, textures and bulk chemical compositions (CC and RP) of the studied chondrules indicate that they once must have been hypersthene-olivine normative liquids that were quenched. Their chondritic Ca/Al ratio and the positive Yb vs. La correlation around primordial values point to a cosmochemical process as responsible of chondrules formation. Based on their REE patterns, and regardless of their mineralogy, chondrules are divided in two populations: Fractioned-REE (F-REE) and Unfractionated-REE (U-REE). Both populations show different evolution paths, while cooling of the nebula gas and give new hints about chondrule-forming reservoirs. [ABSTRACT FROM AUTHOR]

Abstract Ultrarefractory (UR) phases in calcium-aluminum-rich inclusions (CAIs) could have formed at higher temperature compared to common CAI minerals and thus they potentially provide constraints on very high temperature processes in the solar nebula. We report a detailed characterization of the mineralogy, petrology and oxygen isotopic composition of an UR phase davisite (CaScAlSiO 6) bearing CAI from a reduced type CV chondrite. The CAI is an irregular-shaped, compound inclusion that consists of five units that are composed of melilite + spinel + Al,Ti-rich pyroxene ± perovskite with various modal abundances of minerals and lithologies, and surrounded by the Wark-Lovering (WL) rim. Davisite occurs only in one lithological unit that consists of three chemically and isotopically distinct parts: (i) 16 O-poor (- 20 ‰ ⩽ δ 18 O ⩽ 0 ‰) regions with reversely-zoned melilite and davisite; (ii) 16 O-rich (- 50 ‰ ⩽ δ 18 O ⩽ - 40 ‰) regions consisting of unzoned, gehlenitic melilite, Al,Ti-rich diopside and spinel; and (iii) spinel framboids composed of 16 O-rich spinel and 16 O-poor melilite. Absence of secondary iron- and/or alkali-rich phases, occurrence of low-iron, manganese-enriched (LIME) olivine, and random distribution of the oxygen isotopic heterogeneity indicate that primitive chemical and isotopic compositions are preserved in the inclusion. The occurrence of chemical and isotopic heterogeneities with sharp boundaries in the CAI indicates formation of the inclusion by an aggregation of mineral assemblages formed and processed separately at different time and/or space in the solar nebula. Although isotope exchange between 16 O-rich solids and 16 O-poor gases prior to the final agglomeration of the CAI cannot be ruled out, we suggest that modification of chemical and isotopic composition of porous CAI precursors or aggregation of isotopically distinct mineral assemblages are alternative scenarios for the origin of oxygen isotopic heterogeneity in CAIs. In either case, coexistence of spatially and/or temporally distinct 16 O-rich and 16 O-poor gaseous reservoirs at the earliest stage of the solar system formation is required. The grain-scale oxygen isotopic disequilibrium in the CAI indicate that post-formation heating of the inclusion (i.e., the WL rim formation event) was short (e.g., ≲ 10 3 h at 1400 K; ≲ 10 5 h at 1100 K), which can be achieved by rapid outward transport of the CAI. High Ti3+/Titot ratios of pyroxene from CAI interior and the rim and LIME composition of the olivine rim document that the entire CAI formation process took place under highly reducing conditions. [ABSTRACT FROM AUTHOR]

Abstract Chondrules are a major component of chondritic meteorites. Understanding their formation conditions provides fundamental insights about how the early solar system formed and evolved. We studied the textures of ∼650 chondrules from all three groups (H, L, LL) of ordinary chondrites, in 2-dimensional (2D) sections through the meteorites. About 40% of the chondrules are mineralogically zoned. They consist of an olivine-rich core, which is surrounded by a low-Ca pyroxene-rich rim. Chondrules sectioned through their low-Ca pyroxene rim do not appear as zoned chondrules, hence, considering such sectioning effects, their true fraction might be as high as ∼50%. Mineralogical zonation is, therefore, a typical chondrule texture in basically all ordinary chondrites, and records a fundamental process during chondrule formation. Chondrules were open systems, and initially olivine-rich chondrules reacted with their surrounding gas to form low-Ca pyroxene rims. Zoned and unzoned chondrules have the same range of bulk compositions, thus ordinary chondrite chondrules were likely affected by two sequential episodes: in the first episode, gaseous SiO was added to all chondrules, thereby forming low-Ca pyroxene rims around all chondrules. In the second episode, only a portion of the chondrules were reheated, thereby remelting and homogenizing their initial pyroxene rims, but retaining their bulk compositions. It is therefore likely that all chondrules in ordinary chondrites were affected by gas-melt interactions during their formation. Open system exchange is consistent with previous studies of chondrule formation and can explain many chondrule textures and bulk chondrule compositional variations in single meteorites. Hence, the open system behaviour recorded in zoned chondrules provides a pivotal constraint on chondrule formation conditions. [ABSTRACT FROM AUTHOR]

Abstract An important question regarding the formation of the solar system is how planetary bodies developed from dust and ice into the planets and planetary bodies. A particularly interesting topic is the thermal evolution of carbonaceous chondrites and volatile-rich clasts that could have originated from CM- and CI-like parent bodies. Two types of these volatile-rich clasts, which are a particular type of dark clasts, can be found. These clasts are mineralogically very similar to CM and CI chondrites and can occasionally be found in achondritic meteorites. Mineral assemblages suggest that both CM and CI chondrites as well as volatile-rich clasts experienced low peak temperatures. However, these mineral assemblages only offer large estimated temperature ranges to describe the thermal history of CM and CI chondrites, and the thermal history of volatile-rich clasts has not been previously described. In this study, to gain a better understanding of the thermal history of both CM and CI chondrites and volatile-rich clasts, we estimated peak temperatures of 30 volatile-rich clasts (16 CI-, and 14 CM-like) in 10 different host meteorites (4 polymict ureilites, 5 polymict eucrites and 1 howardite) by Raman carbon thermometry. An automated method was developed in order to describe over 4000 collected Raman spectra using four pseudovoigt functions. The full width half maximum (FWHM) of the D1-band was then used to calculate peak temperatures. Results were then compared to Raman data of 8 different well-studied carbonaceous chondrites (including CI and CM chondrites) to evaluate the suggestion that volatile-rich clasts are composed of similar material to the equivalent CI and CM chondrites. Our results show that the peak temperatures experienced by CI-like clasts range between 30–110 °C with an average of about 65 ± 25 °C; the peak temperatures experienced by CM-like clasts range from 50 to 110 °C with an average of about 70 ± 25 °C. Six of the 8 studied carbonaceous chondrites (CM, CI, CR or C2 ungr) also plot in the same low-temperature range between 50 °C and 75 °C and can thus be considered to have formed under similar temperature conditions as the volatile-rich clasts. This is in agreement with previous suggestions, based on their mineral compositions that volatile-rich clasts and CI and CM carbonaceous chondrites are composed of similar materials. The peak temperatures for carbonaceous chondrites determined in this study considerably reduce the range of temperature estimates proposed previously for these chondrites by different methods. By highlighting the ability of our methodology to evaluate data in an automated way, this study shows that Raman carbon thermometry is a good analytical technique for obtaining information about peak temperatures in small and delicate samples. [ABSTRACT FROM AUTHOR]

Abstract Growth pathways of calcium (Ca) phosphate minerals are still under debate, but non-classical growth pathways, which encompass any mode of growth involving attachment of primary particles instead of monomer ions, are currently thought to dominate over classical mechanisms under a wide range of growth conditions. Cation desolvation during ion-by-ion growth is associated with the preferential uptake of isotopically light Ca in Ca-bearing phases, so the Ca isotope composition of Ca-bearing minerals can help to elucidate the dominant growth mechanism. Here, we combine stable Ca isotope analysis with mineralogical characterization and nanoscale imaging of growth features to determine for the first time the rate-dependent Ca isotope fractionation during seeded growth of hydroxyapatite (HAP) involving an octacalcium phosphate (OCP) precursor. Our data reveal that growth rates are strongly attenuated by pH, and that Ca isotope fractionation between the solid and growth solution is independent of growth rate between 1.9 × 10−9 and 2.8 × 10−8 mol Ca m−2 s−1. Moreover, nanoscale images of surface topography reveal direct deposition of primary particles on the HAP seed surface following sustained growth, providing visual evidence of a non-classical growth pathway. Together, these findings support the hypothesis that hydroxyapatite growth is dominantly non-classical. The process of cluster nucleation from the bulk solution and attachment of these clusters to the seeded HAP apparently does not involve a significant kinetic isotope effect, which implies that abiogenically formed Ca-phosphates likely preserve the Ca isotope composition of the fluid from which the crystals originated. [ABSTRACT FROM AUTHOR]

The use of molybdenum as a quantitative paleo-atmosphere redox sensor is predicated on the assumption that Mo is hosted in sulfides in the upper continental crust (UCC). This assumption is tested here by determining the mineralogical hosts of Mo in typical Archean, Proterozoic, and Phanerozoic upper crustal igneous rocks, spanning a compositional range from basalt to granite. Common igneous sulfides such as pyrite and chalcopyrite contain very little Mo (commonly below detection limits of around 10 ng/g) and are not a significant crustal Mo host. By contrast, volcanic glass and Ti-bearing phases such as titanite, ilmenite, magnetite, and rutile contain significantly higher Mo concentrations (e.g., up to 40 µg/g in titanite), and can account for the whole-rock Mo budget in most rocks. However, mass balance between whole-rock and mineral data is not achieved in 4 out of 10 granites analyzed with in-situ methods, where Mo may be hosted in undetected trace molybdenite. Significant Mo depletion ( i.e. , UCC-normalized Mo/Ce < 1) occurs in nearly every granitic rock analyzed here, but not in oceanic basalts or their differentiates (Greaney et al., 2017; Jenner and O’Neill, 2012). On average, granites are missing ∼60% of their expected Mo contents. There are two possible reasons for this: (1) Mo partitions into an aqueous magmatic vapor/fluid phase that is expelled from cooling plutons, and/or (2) Mo is partitioned into titaniferous phases during partial melting and fractional crystallization of an evolving magma. The first scenario is likely given the high solubility of oxidized Mo. However, correlations between Mo/Ce and Nb/La in several plutonic suites suggest fractionating phases such as rutile or Fe-Ti oxides may sequester Mo in lower crustal rocks or in subducting slabs in arc settings. [ABSTRACT FROM AUTHOR]

It is generally agreed that the CM chondrites are remarkably compositionally uniform. To date, this observation has largely been based on major and selected trace element bulk elemental abundances. Here, we examine the trace element compositional uniformity of the CM chondrites in detail. We quantified the abundances of 43 trace elements in 21 CM chondrites displaying variable degrees of petrographically identified aqueous alteration. With these data, we used graphic and standard statistical methods for examining evidence for compositional differences with respect to degree of aqueous alteration. The results show that suites of variably aqueously altered CM chondrites have readily apparent and statistically significant trace element compositional differences. Higher degrees of aqueous alteration are associated with depleted bulk trace elemental abundances; however, when the variable mineralogy and hydration (H 2 O or OH) are taken into account, the compositional differences between variably aqueously altered suites of CM chondrites largely disappear. Nevertheless, some trace elements still show statistically significant differences between suites of CM chondrites that experienced extensive and milder degrees of aqueous alteration. These elements are observed to be redox sensitive species (e.g. Mn, Zn, Mo, Re, U), whose mobilities between aqueous solutions and solids are mediated by complex ions whose solubilities are sensitive to a complicated combination of either the presence of Mn or Fe (oxy)hydroxide surfaces, specific redox environments, solution pH, presence of organic matter, and phyllosilicate surface binding. The studies suggest that the apparent compositional differences of these elements reflect an evolving redox environment during the history of the CM chondrites. It is unclear if the compositional differences between variably aqueously altered CM chondrites are the result of anisochemical (open system) aqueous alteration for some redox condition sensitive trace elements on the CM parent body or bodies or if the differences are the result of the meteorites’ terrestrial residence. [ABSTRACT FROM AUTHOR]

The recent fall of the relatively unaltered CM chondrite Maribo provides a unique opportunity to study the early stages of aqueous alteration on the CM chondrite parent body. We show using transmission electron microscopy of a matrix FIB-section from Maribo that this meteorite mainly appears to consist of tochilinite-cronstedtite intergrowths (TCIs), but also contains regions of amorphous or nanocrystalline silicates, anhydrous silicates and FeNi metal aggregates with thin iron oxide rims, suggesting that it experienced aqueous alteration to a relatively small degree. A comparison of Maribo with increasingly altered CM chondrites such as Jbilet Winselwan and Bells shows that during progressive aqueous alteration (1) the TCIs are replaced by coarser sulfides and increasingly Mg-rich serpentine, and (2) the abundance of 15 N -rich hotspots increases, whereas the magnitude of their 15 N enrichment decreases. We observe that the overall N isotope variability related to aqueous alteration is an order of magnitude lower than the variability observed between different chondrite groups. We suggest these high order differences are the result of heterogeneous accretion of insoluble or soluble organic carriers of 15 N to the different chondrite parent bodies. D/H ratios of matrices from Maribo, Jbilet Winselwan and Bells increase with progressive aqueous alteration, a trend that is opposite to expectations of mixing between D-poor water and D-rich organic matter. We argue that this behaviour cannot be related to Fe oxidation or serpentinization reactions and subsequent loss of D-poor H 2 gas. We offer an alternative hypothesis and suggest that CM chondrites experienced two-stage aqueous alteration. During the first stage occurring at relatively low temperature, mixing of increasing amounts of D-poor water with D-rich organic matter results in a decrease of D/H ratio with increasing degree of alteration. During the second stage of alteration occurring at relatively high temperature (T < 300 °C), decomposition of TCIs in CMs of petrologic type <2.7 releases gaseous D-poor water that results in increase of the D/H ratio of the CM matrices. Finally, we report on changes in the organic structure of Maribo, Jbilet Winselwan and Bells using Carbon-K and Nitrogen-K edge electron energy loss spectroscopy. The organic matter initially has higher aromatic/aliphatic ratios (e.g., Maribo) and lower abundances of ketone and carboxyl functional groups, which we suggest are the result of chemical degradation of double bonded carbon from oxidation during hydrothermal alteration. Consequently, we propose that the organic matter of the CM chondrite Paris, for which lower aromatic/aliphatic ratios have been observed, may have been different from Maribo, perhaps reflecting the early accretion of Paris relative to Maribo. [ABSTRACT FROM AUTHOR]

Shallow-water carbonate sediments constitute one of the most abundant and widely used archives of Earth’s surface evolution. One of the main limitations of this archive is the susceptibility of the chemistry of carbonate sediments to post-depositional diagenesis. Here, we develop a numerical model of marine carbonate diagenesis that tracks the elemental and isotopic composition of calcium, magnesium, carbon, oxygen, and strontium, during dissolution of primary carbonates and re-precipitation of secondary carbonate minerals. The model is ground-truthed using measurements of geochemical proxies from sites on and adjacent to the Bahamas platform (Higgins et al., 2018) and authigenic carbonates in the organic-rich deep marine Monterey Formation (Blättler et al., 2015). Observations from these disparate sedimentological and diagenetic settings show broad covariation between bulk sediment calcium and magnesium isotopes that can be explained by varying the extent to which sediments undergo diagenesis in seawater-buffered or sediment-buffered conditions. Model results indicate that the covariation between calcium and magnesium isotopes can provide a semi-quantitative estimate of the extent and style (fluid-buffered vs. sediment-buffered) of early marine diagenesis. When applied to geochemical signatures in ancient carbonate rocks, the model can be used to quantify the impact of early marine diagenesis on other geochemical proxies of interest (e.g. carbon and oxygen isotopes). The increasing recognition of early marine diagenesis as an important phenomenon in shallow-water carbonate sediments makes this approach essential for developing accurate records of the chemical and climatic history of Earth from the chemical and isotopic composition of carbonate sediments. [ABSTRACT FROM AUTHOR]

It has long since been noted that minor element (Me) partitioning into biogenic carbonates is sometimes different from Me partitioning into inorganically precipitated carbonates. The prime example is the partitioning coefficient, which might be lower or even higher than the one of inorganically precipitated carbonate. Such a difference is usually termed “vital effect” and is seen as indicative of a biologically modified minor element partitioning. Over the last three decades interest in conceptual biomineralization models compatible with minor element and isotope fractionation has been steadily increasing. However, inferring features of a biomineralization mechanism from Me partitioning is complicated, because not all partitioning coefficients show vital effects in every calcium carbonate producing organism. Moreover, the partitioning coefficient is not the only aspect of Me partitioning. Other aspects include polymorph specificity and rate dependence. Patellogastropod limpets are ideally suited for analysing Me partitioning in terms of biomineralization models, because they feature both aragonitic and calcitic shell parts, so that polymorph specificity can be tested. In this study, polymorph-specific partitioning of the minor elements Mg, Li, B, Sr, and U into shells of the patellogastropod limpet Patella caerulea from within and outside a CO 2 vent site at Ischia (Italy) was investigated by means of LA-ICP-MS. The partitioning coefficients of U, B, Mg, and Sr (in aragonite) differed from the respective inorganic ones, while the partitioning coefficients of Li and Sr (in calcite) fell within the range of published values for inorganically precipitated carbonates. Polymorph specificity of Me partitioning was explicable in terms of inorganic precipitation in the case of Sr and Mg, but not Li and B. Seawater carbon chemistry did not have the effect on B partitioning that was expected on the basis of data on inorganic precipitates and foraminifera. Carbon chemistry did affect Mg (in aragonite) and Li, but only the effect on Mg was explicable in terms of calcification rate. On the one hand, these results show that Me partitioning in P. caerulea is incompatible with a direct precipitation of shell calcium carbonate from the extrapallial fluid. On the other hand, our results are compatible with precipitation from a microenvironment formed by the mantle. Such a microenvironment was proposed based on data other than Me partitioning. This is the first study which systematically employs a multi-element, multi-aspect approach to test the compatibility of Me partitioning with different conceptual biomineralization models. [ABSTRACT FROM AUTHOR]

This paper investigates the mineralogy and noble gas composition of a unique micrometeorite from the Transantarctic Mountains, #45c.29. The magnetite rim and the particle interior with olivine, pyroxene and magnetite relict grains (30–250 µm in size) set in a vesicular mesostasis are typical features of coarse-grained, partially melted micrometeorites. Particle #45c.29 stands out from other micrometeorites of this type by the texture of the mesostasis made of abundant plagioclase and augite laths, the remarkably high Ni contents in magnetite and olivine relict grains, and by the similarly high abundance of cosmogenic noble gases ( 21 Ne cos up to 1.62 × 10 −7 cm 3 STP/g and 38 Ar up to 7.2 × 10 −8 cm 3 STP/g). The high Ni content of Fa 26 olivine relict grains (NiO ∼ 0.65 wt%), the high Ni (NiO ∼ 0.8 wt%) and Ti (TiO 2 ∼ 0.3 wt%) contents of magnetite relicts, and the oxygen isotope composition of a sample of the particle (δ 18 O ∼ 2.3‰, δ 17 O ∼ −1.5‰), suggest a parentage with rare equilibrated CK chondrites. Pyroxene and plagioclase are not expected to crystallize during atmospheric entry of micrometeoroids. Their occurrence in #45c.29 may be explained by the Ca-, Al- and Na- rich composition of its precursor – in agreement with the high abundance of plagioclase reported in the matrix of CK chondrites – if combined with a relatively low cooling rate and, therefore, unusual atmospheric entry parameters (velocity/angle) of the micrometeoroid. Given these specific entry parameters, the particle has recorded unique information on mineralogical and textural transformations of micrometeoroids during atmospheric entry, with solid-state oxidation of the olivine relict grains in the igneous rim, and partial melting of relict mineral phases and relict/melt reactions in the particle interior. The cosmogenic 21 Ne/ 22 Ne ratio of 0.94 ± 0.02 is incompatible with major production by cosmogenic ray irradiation of a small particle in space. We propose that micrometeorite #45c.29 mostly records an earlier irradiation stage, in a meteoroid or more likely near the surface (<20 cm in depth) of an asteroid. In contrast, most of the other unmelted and scoriaceous micrometeorites analyzed for noble gases – if coming from asteroidal sources of the Main Belt – seem to have sampled deeper parts of their parent body, where they were shielded from cosmic rays and from where they were excavated during high-energy disruptive processes. [ABSTRACT FROM AUTHOR]