Type C Ca, Al-rich inclusions from Allende: Evidence for multistage formation

The coarse-grained, igneous, anorthite-rich (Type C) CAIs from Allende studied (100, 160, 6-1-72, 3529-40, CG5, ABC, TS26, and 93) have diverse textures and mineralogies, suggesting complex nebular and asteroidal formation histories. CAIs 100, 160, 6-1-72, and 3529-40 consist of Al,Ti-diopside (fassaite; 13-23 wt% Al₂O₃, 2-14 wt% TiO₂), Na-bearing åkermanitic melilite (0.1-0.4 wt% Na₂O; Åk_30-75), spinel, and fine-grained (∼5-10 μm) anorthite groundmass. Most of the fassaite and melilite grains have “lacy” textures characterized by the presence of abundant rounded and prismatic inclusions of anorthite ∼5-10 μm in size. Lacy melilite is pseudomorphed to varying degrees by grossular, monticellite, and pure forsterite or wollastonite. CAI 6-1-72 contains a relict Type B CAI-like portion composed of polycrystalline gehlenitic melilite (Åk_10-40), fassaite, spinel, perovskite, and platinum-group element nuggets; the Type B-like material is overgrown by lacy melilite and fassaite. Some melilite and fassaite grains in CAIs 100 and 160 are texturally similar to those in the Type B portion of 6-1-72. CAIs ABC and TS26 contain relict chondrule fragments composed of forsteritic olivine and low-Ca pyroxene; CAI 93 is overgrown by a coarse-grained igneous rim of pigeonite, augite, and anorthitic plagioclase. These three CAIs contain very sodium-rich åkermanitic melilite (0.4-0.6 wt% Na₂O; Åk_63-74) and Cr-bearing Al,Ti-diopside (up to 1.6 wt% Cr₂O₃, 1-23 wt% Al₂O, 0.5-7 wt% TiO₂). Melilite and anorthite in the Allende Type C CAI peripheries are replaced by nepheline and sodalite, which are crosscut by andradite-bearing veins; spinel is enriched in FeO. The CAI fragment CG5 is texturally and mineralogically distinct from other Allende Type Cs. It is anorthite-poor and very rich in spinel poikilitically enclosed by Na-free gehlenitic melilite (Åk_20-30), fassaite, and anorthite; neither melilite nor pyroxene have lacy textures; secondary minerals are absent. The Al-rich chondrules 3655b-2 and 3510-7 contain aluminum-rich and ferromagnesian portions. The Al-rich portions consist of anorthitic plagioclase, Al-rich low-Ca pyroxene, and Cr-bearing spinel; the ferromagnesium portions consist of fosteritic olivine, low-Ca pyroxene, and opaque nodules.We conclude that Type C CAIs 100, 160, 6-1-72, and 3529-40 formed by melting of coarse-grained Type B-like CAIs which experienced either extensive replacement of melilite and spinel mainly by anorthite and diopside (traces of secondary Na-bearing minerals, e.g., nepheline or sodalite, might have formed as well), or addition of silica and sodium during the melting event. CG5 could have formed by melting of fine-grained spinel-melilite CAI with melilite and spinel partially replaced anorthite and diopside. CAIs ABC, 93, and TS-26 experienced melting in the chondrule-forming regions with addition of chondrule-like material, such as forsteritic olivine, low-Ca pyroxene, and high-Ca pyroxene. Anorthite-rich chondrules formed by melting of the Al-rich (Type C CAI-like) precursors mixed with ferromagnesian, Type I chondrule-like precursors. The Allende Type C CAIs and Al-rich chondrules experienced fluid-assisted thermal metamorphism, which resulted in pseudomorphic replacement of melilite and anorthite by grossular, monticellite, and forsterite (100, 160, 6-1-72, 3592-40) or by grossular, monticellite, and wollastonite (ABC, 93, TS-26). The pseudomorphic replacement was followed or accompanied by iron-alkali metasomatic alteration resulting in replacement of melilite and anorthite by nepheline and sodalite, enrichment of spinel in FeO, and precipitation of salite-hedenbergite pyroxenes, wollastonite, and andradite in fractures and pores in and around CAIs.     

Implications of the carbonaceous chondrite Mn-Cr isochron for the formation of early refractory planetesimals and chondrules

An excellent ⁵³Mn-⁵³Cr isochron for bulk CI, CM, CO, CV, CB, and ungrouped C3 chondrites seems to suggest that each carbonaceous chondrite group acquired its Mn/Cr ratio 4568 ± 1 Myr ago. This age is indistinguishable from the age of Ca-Al-rich inclusions (CAIs), which is considered to be the start of the solar system (t₀). However, carbonaceous chondrites were not assembled until at least 1.5-5 Myr after t₀, to judge by the ²⁰⁷Pb-²⁰⁶Pb and ²⁶Al-²⁶Mg ages of the chondrules within them, and by the fact that they were not melted by heat from the decay of ²⁶Al. Presumably, therefore, these meteorites inherited their bulk Mn-Cr isochron from precursor materials which experienced Mn-Cr fractionation at t₀. As a possible physical mechanism for how the isochron was established initially, and later inherited by the carbonaceous chondrites, we propose the rapid formation at t₀ of planetesimals that were variably depleted in moderately volatile elements, and hence had variably low Mn/Cr. The planetesimals and the undepleted (high Mn/Cr) primitive dust from which they were made shared the same initial ε⁵³Cr, and therefore evolved on an isochron. We suggest that later impact-disruption of the planetesimals produced dusty debris, which became mixed, in various proportions, with unprocessed (high Mn/Cr) dust before accreting to the carbonaceous chondrite parent bodies. With mixing in a closed system, the isochron was unchanged. We infer that some debris-rich material was converted to chondrules prior to accretion. The chondrules could have been formed by flash melting of the mixed dust, or could instead have been made directly by the impact splashing of molten planetesimals, or by condensation from impact-generated vapor plumes.     

Evolution of CaAl-rich bodies in the earliest solar system: growth by incorporation

Many Type B CaAl-rich inclusions (CAI's) in the Allende carbonaceous chondrite contain two types of spinel structures, “framboids” and “palisades.” Framboids are clumps of spinel grains generally <100 μm across. Experimental studies (Wark and Lovering, 1982) show that they probably formed in situ by solid state growth processes. Palisades are texturally different and consist of ovoid shells of spinel grains that appear in thin sections as long arcs or rings with diameters ranging from ～50 μm up to 2 cm. No in situ formation process seems able to explain the variety of sizes and morphologies of palisades nor the different compositions and textures of the enclosed and enclosing materials. We therefore suggest that palisades are the spinel rims of smaller, earlier-formed Type B CAI's that were incorporated into other CAI material in various ways—by capture into liquid drops, by solid condensate overgrowths and by the partial melting or welding of agglomerates containing the bodies. As some Type B bodies have been found inside Type A host material it appears that in at least some regions, and probably generally, Type A CAI's formed after Type B. We propose that Type B CAI's are residues from the heating and incomplete evaporation of interstellar dust during the accretion of the protosolar nebula, and that Type A CAI's are later condensates from completely evaporated dust whose exotic ¹⁶O-rich component became more diluted in the gas phase.     

富橄榄石的富Ca,Al组分集合体的矿物岩石学特征及对比研究

富Ca,Al包体、球粒和蠕虫状橄榄石集合体都是早期星云事件的产物。本文探讨了4个富橄榄石的富Ca,Al组分集合体的矿物岩石学特征,并对它们进行了对比。矿物岩石学特征表明含橄榄石边的富尖晶石—辉石型包体和富Ca,Al组分蠕虫状橄榄石集合体都属于星云直接凝聚的产物,而富钙长石—橄榄石型包体(POI)和富Ca,Al组分球粒经历过熔融结晶过程。矿物模式组成表明POI包体和富Ca,Al组分球粒可能是认识典型富Ca,Al包体与球粒之间相互关系的钥匙。蠕虫状橄榄石集合体GRV022459-2C1中尖晶石普遍具有高的FeO含量,表明其蚀变发生于高氧逸度的星云环境。球粒与粗粒富Ca,Al包体可能属于同一热事件的产物,粗粒富Ca,Al包体形成于富Ca,Al矿物富集的区域,Mg,Fe质硅酸盐球粒形成于富Ca,Al矿物缺失的区域,POI包体和富Ca,Al组分球粒可能形成于上述两个区域之间的过渡区域。     

富钙长石-橄榄石包体与其他部分典型包体W-L边的成因

球粒陨石中的富Ca、Al包体(简称CAI)形成于星云演化的最初始阶段,保存了大量星云形成和演化的各种信息。研究认为,包体的成因主要包括星云直接凝聚和熔融结晶,少部分甚至经历过高温蒸发过程。部分CAI最外层具有由一种或几种矿物组成的Warking-Lovering边(简称为W-L边),CAI和其W-L边对于认识早期星云环境和界定CAI的形成时间等均具有重要意义。目前,对于W-L边的形成过程研究并不深入,且一直存在争议。本文主要介绍了三个典型包体:C#1(富钙长石-橄榄石包体)、GRV 022459-2RI5(A型包体)和GRV 021579-3RI5(富尖晶石球粒状包体)及其W-L边的矿物岩石学和氧同位素组成特征。C#1包体明显经历过熔融结晶过程,W-L边氧同位素组成具有与包体内部矿物相似的富~(16)O同位素特征,表明W-L边的成因与包体的形成过程密切相关,形成于同一富~(16)O同位素组成区域,且W-L边属于包体熔融结晶过程后期的产物。矿物岩石学特征表明,GRV 022459-2RI5属于星云直接凝聚形成,其W-L边为包体形成过程最晚期星云凝聚产物。GRV021579-3RI5经历过熔融结晶过程,其W-L边为包体结晶最后阶段的产物。     

Formation of disk- and bowl-shaped igneous Ca,Al-rich inclusions: Constraints from their morphology,textures, mineralogy and modelling

Calcium-aluminum-rich inclusions (CAIs) are the oldest Solar System solids dated that formed by evaporation, condensation, aggregation and, sometimes, melting processes near the protoSun, and were subsequently dispersed throughout the protoplanetary disk by still poorly-understood mechanism(s). Here we report on the discovery of disk- and bowl-shaped centimeter-sized igneous CAIs in CV (Vigarano type) carbonaceous chondrites. Igneous CAIs of these shapes are not expected for crystallization of melt droplets in a low gravity field of the protoplanetary disk. We have tested several models for the formation of disk- and bowl-shaped igneous CAIs including: collision, aerodynamic deformation and shock flattening. We conclude that these CAIs resulted from aerodynamic deformation of CAI-like melt droplets and propose the following multistage formation scenario: (1) nearly complete melting and acceleration of CAIs at <30 km/s in the CAI-forming region having approximately solar dust/gas ratio; (2) aerodynamic deformation, ablation, deceleration, solidification at ∼30–40 K/min, Wark-Lovering rims formation, and deceleration of the CAIs entering a dust-rich inner disk wall; (3) radial drift of the solidified deformed CAIs towards the Sun; (4) heating and partial melting of the deformed CAIs by solar radiation that preserve their morphology; (5) cooling and crystallization of CAIs at ∼2 K/h; (5) radial transport of CAIs from their formation region to the outer disk.     

Ca,Al-rich inclusions, amoeboid olivine aggregates, and Al-rich chondrules from the unique carbonaceous chondrite Acfer 094: I. mineralogy and petrology

Based on their mineralogy and petrography, ∼200 refractory inclusions studied in the unique carbonaceous chondrite, Acfer 094, can be divided into corundum-rich (0.5%), hibonite-rich (1.1%), grossite-rich (8.5%), compact and fluffy Type A (spinel-melilite-rich, 50.3%), pyroxene-anorthite-rich (7.4%), and Type C (pyroxene-anorthite-rich with igneous textures, 1.6%) Ca,Al-rich inclusions (CAIs), pyroxene-hibonite spherules (0.5%), and amoeboid olivine aggregates (AOAs, 30.2%). Melilite in some CAIs is replaced by spinel and Al-diopside and/or by anorthite, whereas spinel-pyroxene assemblages in CAIs and AOAs appear to be replaced by anorthite. Forsterite grains in several AOAs are replaced by low-Ca pyroxene. None of the CAIs or AOAs show evidence for Fe-alkali metasomatic or aqueous alteration. The mineralogy, textures, and bulk chemistry of most Acfer 094 refractory inclusions are consistent with their origin by gas-solid condensation and may reflect continuous interaction with SiO and Mg of the cooling nebula gas. It appears that only a few CAIs experienced subsequent melting. The Al-rich chondrules (ARCs; >10 wt% bulk Al₂O₃) consist of forsteritic olivine and low-Ca pyroxene phenocrysts, pigeonite, augite, anorthitic plagioclase, ± spinel, FeNi-metal, and crystalline mesostasis composed of plagioclase, augite and a silica phase. Most ARCs are spherical and mineralogically uniform, but some are irregular in shape and heterogeneous in mineralogy, with distinct ferromagnesian and aluminous domains. The ferromagnesian domains tend to form chondrule mantles, and are dominated by low-Ca pyroxene and forsteritic olivine, anorthitic mesostasis, and Fe,Ni-metal nodules. The aluminous domains are dominated by anorthite, high-Ca pyroxene and spinel, occasionally with inclusions of perovskite; have no or little FeNi-metal; and tend to form cores of the heterogeneous chondrules. The cores are enriched in bulk Ca and Al, and apparently formed from melting of CAI-like precursor material that did not mix completely with adjacent ferromagnesian melt. The inferred presence of CAI-like material among precursors for Al-rich chondrules is in apparent conflict with lack of evidence for melting of CAIs that occur outside chondrules, suggesting that these CAIs were largely absent from chondrule-forming region(s) at the time of chondrule formation. This may imply that there are several populations of CAIs in Acfer 094 and that mixing of “normal” CAIs that occur outside chondrules and chondrules that accreted into the Acfer 094 parent asteroid took place after chondrule formation. Alternatively, there may have been an overlap in the CAI- and chondrule-forming regions, where the least refractory CAIs were mixed with Fe-Mg chondrule precursors. This hypothesis is difficult to reconcile with the lack of evidence of melting of AOAs which represent aggregates of the least refractory CAIs and forsterite grains.     

The nature and origin of type B1 and B2 CaAl-rich inclusions in the Allende meteorite

The Type B CaAl-rich inclusions in the Allende carbonaceous chondrite form a continuous range from the mineralogically concentrically zoned B1 subtype to the unzoned B2 subtype. These subtypes differ in (i) structure, texture, grain size and shape, (ii) mineralogical proportions and compositions, (iii) accessory mineralogy, (iv) relative abundance of spinel framboids, (v) rim layering, (vi) major element chemistry, and (vii) degree of secondary alteration.These differences, together with observations on the crystallization of synthetic melts, suggest that the B1 inclusions crystallised relatively rapidly from molten parental material while B2 types crystallised relatively slowly close to the solidus from material that had not been completely melted.The same data are used to construct an evaporative residue model for the origin of the parental Type B materials. In the model, dust in the protosolar nebula was heated with removal of more volatile elements, leaving completely melted (Type B1) residues at the highest temperatures and incompletely melted, less highly evaporated (Type B2) residues at lower temperatures.     

Early core formation in asteroids and late accretion of chondrite parent bodies: Evidence from Hf-W in CAIs, metal-rich chondrites, and iron meteorites

The ¹⁸²Hf-¹⁸²W isotopic systematics of Ca-Al-rich inclusions (CAIs), metal-rich chondrites, and iron meteorites were investigated to constrain the relative timing of accretion of their parent asteroids. A regression of the Hf-W data for two bulk CAIs, various fragments of a single CAI, and carbonaceous chondrites constrains the ¹⁸²Hf/¹⁸⁰Hf and ε_W at the time of CAI formation to (1.07 ± 0.10) × 10⁻⁴ and −3.47 ± 0.20, respectively. All magmatic iron meteorites examined here have initial ε_W values that are similar to or slightly lower than the initial value of CAIs. These low ε_W values may in part reflect ¹⁸²W-burnout caused by the prolonged cosmic ray exposure of iron meteorites, but this effect is estimated to be less than ∼0.3 ε units for an exposure age of 600 Ma. The W isotope data, after correction for cosmic ray induced effects, indicate that core formation in the parent asteroids of the magmatic iron meteorites occurred less than ∼1.5 Myr after formation of CAIs. The nonmagmatic IAB-IIICD irons and the metal-rich CB chondrites have more radiogenic W isotope compositions, indicating formation several Myr after the oldest metal cores had segregated in some asteroids.Chondrule formation ∼2-5 Myr after CAIs, as constrained by published Pb-Pb and Al-Mg ages, postdates core formation in planetesimals, and indicates that chondrites do not represent the precursor material from which asteroids accreted and then differentiated. Chondrites instead derive from asteroids that accreted late, either farther from the Sun than the parent bodies of magmatic iron meteorites or by reaccretion of debris produced during collisional disruption of older asteroids. Alternatively, chondrites may represent material from the outermost layers of differentiated asteroids. The early thermal and chemical evolution of asteroids appears to be controlled by the decay of ²⁶Al, which was sufficiently abundant (initial ²⁶Al/²⁷Al >1.4 × 10⁻⁵) to rapidly melt early-formed planetesimals but could not raise the temperatures in the late-formed chondrite parent asteroids high enough to cause differentiation. The preservation of the primitive appearance of chondrites thus at least partially reflects their late formation rather than their early and primitive origin.     

Silicon isotopes in the inner Solar System: Implications for core formation, solar nebular processes and partial melting

We report Si isotopic data on a suite of terrestrial mantle-derived samples, meteorites and a lunar sample. Our data on co-existing mantle minerals, peridotites and basalts demonstrate lack of any resolvable high temperature fractionation during igneous processes. We show that the δ³⁰Si of the bulk silicate Earth (BSE) is identical, within analytical uncertainties, to carbonaceous and ordinary chondrites (CHUR). Based on our data the difference between δ³⁰Si_BSE and δ³⁰Si_CHUR is 0.035 ± 0.035. Whole-rock differentiated meteorites from different parent bodies (Mars, Vesta) and a lunar breccia sample also show similar δ³⁰Si suggesting broad-scale Si isotope homogeneity in the inner Solar System with an average δ²⁹Si = −0.20 ± 0.01 and δ³⁰Si = −0.39 ± 0.02 relative to the NBS28 Si isotope standard.A difference between δ³⁰Si_BSE and δ³⁰Si_CHUR of 0.035, as observed in our study, translates to less than 1.67 wt.% Si in the core considering a continuous accretion model whereas estimates using a batch model are even lower. Within uncertainties (±0.035‰) in the δ³⁰Si difference between the BSE and CHUR, a maximum of 3.84 wt.% Si could be present in the Earth’s core whereas at δ³⁰Si_BSE-δ³⁰Si_CHUR = 0, there is no requirement of Si in the Earth’s core. Such low Si in the core necessitates the presence of other light elements in the core to explain its density deficit. Our data also places constraints on the oxidation state of the Earth’s mantle during core segregation. The uncertainties in estimating the concentration of oxidized Fe in the mantle during the first 90% of accretion arise from uncertainties in the estimates of the equilibrium partition coefficient of silicon between metal and silicate at conditions relevant to core formation. For δ³⁰Si_BSE-δ³⁰Si_CHUR = 0.035 ± 0.035, the concentration of oxidized Fe in the mantle during the first 90% of accretion could be as low as ∼1%. However, at δ³⁰Si_BSE-δ³⁰Si_CHUR = 0, the Si isotope data do not require any change in the mantle concentration of oxidized Fe during accretion from the present day value of 6.26%.     

Origin, timing, and temperature of secondary calcite-silica mineral formation at Yucca Mountain, Nevada

The origin of secondary calcite-silica minerals in primary and secondary porosity of the host Miocene tuffs at Yucca Mountain has been hotly debated during the last decade. Proponents of a high-level nuclear waste repository beneath Yucca Mountain have interpreted the secondary minerals to have formed from cool, descending meteoric fluids in the vadose zone; critics, citing the presence of two-phase fluid inclusions, argued that the minerals could only have formed in the phreatic zone from ascending hydrothermal fluids. Understanding the origin, temperature, and timing of these minerals is critical in characterizing geologically recent fluid flux at the site, and has significant implications to whether waste should be stored at Yucca Mountain.Petrographic and paragenetic studies of 155 samples collected from the Exploratory Studies Facility (ESF) and repository block cross drift (ECRB) tunnels indicate that heterogeneously distributed calcite with lesser chalcedony, quartz, opal, and fluorite comprise the oldest secondary minerals. These are typically overgrown by intermediate-aged calcite, often exhibiting distinctive bladed habits. The youngest event recorded across the site is the deposition of Mg-enriched (up to ∼1 wt%) and depleted, growth-zoned calcite intergrown with U-enriched opal. The cyclical variation in Mg enrichment and depletion is probably related to climate changes that have occurred during the last few million years. The distribution of secondary minerals is consistent with precipitation in the vadose zone.Fluid inclusion petrography of sections from the 155 samples determined that 96% of the fluid inclusion assemblages (FIAs) contained liquid-only inclusions that formed at ambient temperatures (<35°C). However, 50% of the samples (n = 78) contained relatively rare FIA that contain both liquid-only and liquid plus vapor inclusions (herein termed two-phase FIAs) that formed at temperatures above 35°C. Virtually all of these two-phase FIAs occur in paragenetically old calcite; rare two-phase inclusion assemblages were also observed in early fluorite and quartz, and early-intermediate calcite. Homogenization temperatures (≡ trapping temperatures) across Yucca Mountain are generally 45 to 60°C, but higher temperatures reaching 83°C were recorded in calcite from the north portal and ramp of the ESF. Cooler temperatures of ∼35 to 45°C were recorded in the intensely fractured zone. Multiple populations of two-phase FIAs from lithophysal cavities in the ESF and ECRB cross drift indicate early fluid cooling with time from temperatures >45°C in early calcite, to <35 to 45°C in paragenetically younger calcite. Freezing point depressions range from −0.2 to −1.6°C, indicating trapping of a low salinity fluid. The majority of intermediate calcite and all outermost Mg-enriched calcite contains rare all-liquid inclusions and formed from ambient temperature (<35°C) fluids.Carbon and oxygen isotope data reveal a consistent trend of decreasing δ¹³C (from 9.5 to −8.5‰) and increasing δ¹⁸O (from 5.2 to 22.1‰) values from paragenetically early calcite to Mg-enriched growth-zoned calcite. Depleted δD values (−131 to −90‰) of inclusion fluids from intermediate and the youngest Mg-enriched calcite indicate derivation from surface meteoric fluids. Recalculation of δ¹⁸O_H2O values of −12 to −10‰ is consistent with derivation from paleometeoric fluids.Results of integrated U-Pb dating (opal and chalcedony) and fluid inclusion microthermometry indicate that two-phase FIAs that trapped fluids of >50°C are older than 6.29 ± 0.30 Ma. Two-phase FIAs in paragenetically later calcite, which formed from fluids of 35 to 45°C, are older than 5.32 ± 0.02 Ma. There is no evidence for trapping of fluids with elevated temperatures during the past 5.32 my. The youngest Mg-enriched calcite intergrown with opal began to precipitate between about 1.9 to 2.9 Ma and has continued to precipitate within the past half million years. The presence of liquid-only inclusions and the consistent occurrence of Mg-enriched calcite and opal as the youngest event indicate a minor, but chemically distinct, ambient temperature (<35°C) fluid flux during the past 2 to 3 my.     

球粒陨石中富Ca、Al包体成因研究进展与演化模式

富Ca、Al包体(简称CAI)形成于太阳星云演化的最初始阶段,其成因模式主要包括:气—固凝聚、熔融结晶和部分熔融以及高温蒸发作用等。最近,通过对不同球粒陨石化学群中的CAI进行岩石学特征对比研究,发现不同化学群中的CAI具有相似的大小和类型分布特征,表明不同球粒陨石化学群中的CAI极可能具有相似的起源。该结果,与前人的氧同位素、Al—Mg同位素体系以及稀土元素等研究得到的结论一致。不同球粒陨石化学群中的CAI具有相似的成因,并很可能形成于太阳星云的相同区域,随后迁移到不同球粒陨石群的吸积区域。     

Physicochemical conditions and timing of rodingite formation: evidence from rodingite-hosted fluid inclusions in the JM Asbestos mine,Asbestos, Québec

Fluid inclusions and geological relationships indicate that rodingite formation in the Asbestos ophiolite, Québec, occurred in two, or possibly three, separate episodes during thrusting of the ophiolite onto the Laurentian margin, and that it involved three fluids. The first episode of rodingitization, which affected diorite, occurred at temperatures of between 290 and 360°C and pressures of 2.5 to 4.5 kbar, and the second episode, which affected granite and slate, occurred at temperatures of between 325 and 400°C and pressures less than 3 kbar. The fluids responsible for these episodes of alteration were moderately to strongly saline (~1.5 to 6.3 m eq. NaCl), rich in divalent cations and contained appreciable methane. A possible third episode of alteration is suggested by primary fluid inclusions in vesuvianite-rich bodies and secondary inclusions in other types of rodingite, with significantly lower trapping temperatures, salinity and methane content. The association of the aqueous fluids with hydrocarbon-rich fluids containing CH₄ and higher order alkanes, but no CO₂, suggests strongly that the former originated from the serpentinites. The similarities in the composition of the fluids in all rock types indicate that the ophiolite had already been thrust onto the slates when rodingitization occurred.     

Windows to early solar system processes: Refractory inclusions in the CV and CM chondrites

The refractory element-enriched inclusions found in the carbonaceous meteorites give cosmochemists a fascinating glimpse at processes which occurred near the birth of the solar system. Although many complications must still be unravelled, the weight of the available evidence indicates that many of these objects condensed directly from the solar nebula, and have remained relatively unaltered up to the present. Their mineralogical and chemical compositions therefore reflect conditions at the time of their formation. The most thoroughly studied of the inclusions are those from the Allende CV meteorite. These, in general, have mineral assemblages similar to those which would be predicted for nebular condensation. The mineralogical agreement is not strict, however, and also the bulk chemical compositions sometimes deviate markedly from expected trends. More work is required to understand these differences. A range of isotopic anomalies in many elements has been found, in these inclusions. Some of these suggest an extra-solar system origin for a part of the material in the inclusions. Although much less work has been done on the inclusions in the CM meteorites, current data indicate that they will prove to be at least as valuable as those from Allende. Chemical data show that some inclusions in the Murchison meteorite are more refractory than the most refractory Allende inclusions. Isotopic anomalies, including²⁵Mg excesses and oxygen-16 enriched oxygen, indicate that, in spite of chemical and mineralogical differences, the Murchison and Allende inclusions contain common isotopic components, and are probably contemporaneous.     

Hf-W isotope systematics of chondrites, eucrites, and martian meteorites: Chronology of core formation and early mantle differentiation in Vesta and Mars

The timescale of accretion and differentiation of asteroids and the terrestrial planets can be constrained using the extinct ¹⁸²Hf-¹⁸²W isotope system. We present new Hf-W data for seven carbonaceous chondrites, five eucrites, and three shergottites. The W isotope data for the carbonaceous chondrites agree with the previously revised ¹⁸²W/¹⁸⁴W of chondrites, and the combined chondrite data yield an improved ?_W value for chondrites of −1.9 ± 0.1 relative to the terrestrial standard. New Hf-W data for the eucrites, in combination with published results, indicate that mantle differentiation in the eucrite parent body (Vesta) occurred at 4563.2 ± 1.4 Ma and suggest that core formation took place 0.9 ± 0.3 Myr before mantle differentiation. Core formation in asteroids within the first ∼5 Myr of the solar system is consistent with the timescales deduced from W isotope data of iron meteorites. New W isotope data for the three basaltic shergottites EETA 79001, DaG 476, and SAU 051, in combination with published ¹⁸²W and ¹⁴²Nd data for Martian meteorites reveal the preservation of three early formed mantle reservoirs in Mars. One reservoir (Shergottite group), represented by Zagami, ALH77005, Shergotty, EETA 79001, and possibly SAU 051, is characterized by chondritic ¹⁴²Nd abundances and elevated ?_W values of ∼0.4. The ¹⁸²W excess of this mantle reservoir results from core formation. Another mantle reservoir (NC group) is sampled by Nakhla, Lafayette, and Chassigny and shows coupled ¹⁴²Nd-¹⁸²W excesses of 0.5-1 and 2-3 ? units, respectively. Formation of this mantle reservoir occurred 10-20 Myr after CAI condensation. Since the end of core formation is constrained to 7-15 Myr, a time difference between early silicate mantle differentiation and core formation is not resolvable for Mars. A third early formed mantle reservoir (DaG group) is represented by DaG 476 (and possibly SAU 051) and shows elevated ¹⁴²Nd/¹⁴⁴Nd ratios of 0.5-0.7 ? units and ?_W values that are indistinguishable from the Shergottite group. The time of separation of this third reservoir can be constrained to 50-150 Myr after the start of the solar system. Preservation of these early formed mantle reservoirs indicates limited convective mixing in the Martian mantle as early as ∼15 Myr after CAI condensation and suggests that since this time no giant impact occurred on Mars that could have led to mantle homogenization. Given that core formation in planetesimals was completed within the first ∼5 Myr of the solar system, it is most likely that Mars and Earth accreted from pre-differentiated planetesimals. The metal cores of Mars and Earth, however, cannot have formed by simply combining cores from these pre-differentiated planetesimals. The ¹⁸²W/¹⁸⁴W ratios of the Martian and terrestrial mantles require late effective removal of radiogenic ¹⁸²W, strongly suggesting the existence of magma oceans on both planets. Large impacts were probably the main heat source that generated magma oceans and led to the formation metallic cores in the terrestrial planets. In contrast, decay of short-lived ²⁶Al and ⁶⁰Fe were important heat sources for melting and core formation in asteroids.     

Geochemistry and mineralogy of the Al-rich shale from Baluti formation,Iraqi Kurdistan region: implications for weathering and provenance

The mineralogical and geochemical characteristics of the Upper Triassic Baluti shale from the Northern Thrust Zone (Sararu section) and High Folded Zone (Sarki section) Kurdistan Region, Iraq, have been investigated to constrain their paleoweathering, provenance, tectonic setting, and depositional redox conditions. The clay mineral assemblages are dominated by kaolinite, illite, mixed layers illite/smectite at Sararu section, and illite > smectite with traces of kaolinite at Sarki. Illite, to be noted, is within the zone of diagenesis. The non-clay minerals are dominated by calcite with minor amounts of quartz and muscovite in Sararu shale; and are dominated by dolomite with amounts of calcite and quartz in Sarki shale. Baluti shale is classified as Al-rich based on major and minor elements. The chemical index of alteration (CIA) is significantly higher in the Sararu than the Sarki shales, suggesting more intense weathering of the Sararu than the Sarki shales. The index of compositional variability (ICV) of the Sararu shale is less than 1 (suggesting it is compositionally mature and was deposited in a tectonically quiescent setting). More than 1 for Sarki shales (suggest it is less mature and deposited in a tectonically active setting). Most shale of the Baluti plot parallel and along the A-K line in A-CN-K plots suggest intense chemical weathering (high CIA) without any clear-cut evidence of K-metasomatism. Clay mineral data, Al enrichment, CIA values, and A-CN-K plot suggest that the source area experienced high degree of chemical weathering under warm and humid conditions, especially in Sararu. Elemental ratios critical of provenance (La/Sc, Th/Sc, Th/Cr, Th/Co, Ce/Ce*_PN, Eu/Eu*_PN, and Eu/Eu*_CN) shows slight difference between the Sararu and Sarki shales; and the ratios are similar to fine fractions derived from the weathering of mostly felsic rocks. The Eu/Eu^* _CN, Th/Sc, and low K₂O/Al₂O₃ ratios of most shales suggest weathering from mostly a granodiorite source rather than a granite source, consistent with a source from old upper continental crust. Discrimination diagrams based on major and trace element content point to a role of the felsic-intermediate sources for the deposition of Baluti Formation, and probably mixed with mafic source rocks at Sararu section. The chondrite-normalized rare earth elements (REE) patterns are similar to those of PAAS, with light REE enrichment, a negative Eu anomaly, and almost flat heavy REE pattern similar to those of a source rock with felsic components. The source of sediments for the Baluti Formation was likely the Rutba Uplift and/or the plutonic-metamorphic complexes of the Arabian Shield located to the southwest of the basin; whereas the Sararu shale was affected by the mafic rocks of the Bitlis-Avroman-Bisitoun Ridge to the northeast of Arabian Plate. The tectonic discrimination diagrams, as well as critical trace and REE characteristic parameters imply rift and active setting for the depositional basin of the shale of Baluti Formation. The geochemical parameters such as U/Th, V/Cr, V/Sc, and Cu/Zn ratios indicate that these shales were deposited under oxic environment and also show that Sarki shale was deposited under more oxic environment than Sararu.     

Magmatic fractionation of Hf and W: constraints on the timing of core formation and differentiation in the Moon and Mars

Excesses of ¹⁸²W have previously been measured in samples from the Moon and Mars, and can be derived from high Hf/W regions in their interiors during their early histories. Although planetary mantles will have superchondritic Hf/W after core formation, the extent to which high Hf/W regions could be generated by magmatic fractionation has not been evaluated. In order to address the latter possibility, we have carried out experiments from 100 MPa to 10.0 GPa, 1150 to 1850°C, at oxygen fugacities near the IW (iron-wüstite) buffer, and measured partition coefficients for W and Hf for plagioclase-liquid, olivine-liquid, orthopyroxene-liquid, clinopyroxene-liquid, garnet-liquid, and metal-liquid pairs. Clinopyroxene and garnet are both capable of fractionating Hf from W during magmatic crystallization or mantle melting, and minor variations in the measured D’s can be attributed to crystal chemical effects. Excesses of ¹⁸²W and ¹⁴²Nd in lunar samples can be explained by fractionation of Hf from W, and Sm from Nd (by ilmenite and clinopyroxene) during crystallization of the latest stages of a lunar magma ocean. Correlations of ε_W with ε_Nd in martian samples could be a result of early silicate fractionation in the martian mantle (clinopyroxene and/or garnet).     

Physicochemical formation parameters of hydrothermal mineral deposits: Evidence from fluid inclusions. II. Gold,silver, lead,and zink deposits

Information from a database, which was compiled and continuously updated by the authors of this paper and now includes information from 19500 publication on fluid and melt inclusions in minerals, is used to summarize results on the physicochemical formation parameters of hydrothermal Au, Ag, Pb, and Zn deposits. The database provides information on fluid inclusions in minerals from 970 Pb-Zn, 220 Au-Ag-Pb-Zn, and 825 Au-Ag deposits in various settings worldwide. Histograms for the homogenization temperatures of fluid inclusion are presented for the most typical minerals of the deposits. In sphalerite, most homogenization temperatures (1327 measurements) of fluid inclusions lie within the range of 50–200°C with a maximum at 100–200°C for this mineral from Pb-Zn deposits and within the range of 100–350°C (802 measurements) with a maximum at 200–300°C for this mineral from Au deposits. Data are presented on fluid pressures at Au (1495 measurements) and Pb-Zn (180 measurements) deposits. The pressure during the preore, ore-forming, and postore stages at these deposits ranged from 4–10 to 6000 bar. The reason for the high pressures during preore stages at the deposits is the relations of the fluids to acid magmatic and metamorphic processes. More than 70% of the fluid pressures values measured at Pb-Zn deposits lie within the range of 1–1500 bar. Au-Ag deposits are characterized by higher fluid pressures of 500–2000 bar (61% of the measurements). The overall ranges of the salinity and temperature of the mineral-forming fluid at Au-Ag (6778 measurements) and Pb-Zn (3395 measurements) deposits are 0.1–80 wt % equiv. NaCl and 20–800°C. Most measurements (～64%) for Au-Ag deposits yield fluid salinity <10 wt % equiv. NaCl and temperatures of 200–400°C (63%). Fluids at Pb-Zn deposits are typically more saline (10–25 wt % equiv. NaCl, 51% measurements) and lower temperature (100–300°C, 74% measurements). Several measurements of the fluid density fall within the range of 0.8–1.2 g/cm³. The average composition of volatile components of the fluids was evaluated by various techniques. The average composition of volatile components of fluid inclusions in minerals is calculated for hydrothermal W, Au, Ag, Sn, and Pb-Zn deposits, metamorphic rocks, and all geological objects. The Au, Ag, Pb, and Zn concentrations in magmatic melts and mineral-forming fluids is evaluated based on analyses of individual inclusions.