Fluid regime and diamond formation in the reduced mantle: Experimental constraints

The composition and potential diamond productivity of C–O–H fluids that could exist in the reduced regions of the Earth’s upper mantle and in the mantles of Uranus and Neptune were studied in experiments at 6.3 GPa and 1400–1600 °C and durations of 15–48 h. Hydrogen fugacity in the fluid phase was controlled by the Mo–MoO₂ or Fe–FeO buffers, using a specially modified double-capsule method. The oxygen fugacity in the samples was controlled by adding different amounts of water, stearic acid, anthracene, and docosane to a graphite charge. At high P–T conditions, the degree of decomposition of the heavy hydrocarbons added to the charge was 99.9%. The composition of the fluids coexisting with graphite/diamond in the buffered experiments varied from H₂O  H₂ > CH₄ (at fO₂ somewhat lower than the “water maximum”) to H₂ > CH₄ > (C₂H₄ + C₂H₆)>C₃H₈ (in C–H system). In the C–H system the maximum concentrations of major species in the synthesized fluid were: H₂ = 79 mol.% and CH₄ = 21 mol.%. The composition of the H₂-rich fluids, which were synthesized at 6.3 GPa and 1400–1600 °C for the first time, differs considerably from that of the ultra-reduced CH₄-rich fluids stable at 2.0–3.5 GPa and 1000–1300 °C. Thermodynamic calculations of the reduced C–O–H fluids at the P–T conditions of the experiments revealed CH₄-rich compositions (CH₄  H₂ > (C₂H₄ + C₂H₆)>C₃H₈), which however drastically differed from the synthesized compositions. The rates of diamond nucleation and growth in the experiments depended on the fluid composition. Diamond crystallization had a maximum intensity in the pure aqueous fluids, while in the H₂-rich fluids no diamond formation was observed. Only metastable graphite precipitated from the ultra-reduced fluids. The type of the initial hydrocarbon used for the fluid generation did not affect this process.     

A comparative study of melilite and fassaite in Types B1 and B2 refractory inclusions

Most of the petrologic data available for Type B inclusions comes from Type B1s. Relatively little comes from the B2s, and there has not been a systematic comparison of the properties of their two most abundant minerals. In this work, we document the compositions and zoning patterns of melilite and fassaite in Type B2 inclusions, and compare and contrast them with the features of their counterparts in Type B1 inclusions. We find that melilite compositions in Type B2 inclusions are similar to those of Type B1s, with maximum Åk contents of ∼75 mol % and a positive correlation between Åk and Na₂O contents. Asymmetrically zoned melilite is common in Type B2s as are melilite grains with reversely zoned regions, and the reversely zoned portions of crystals are thicker than in B1s. In B2s, like B1s, fassaite is zoned with decreasing Ti, Sc, and V oxide contents from cores to rims of grains. Approximately half of the Ti is trivalent, but unlike that in B1s, within fassaite grains in B2s the Ti³⁺/(Ti³⁺ + Ti⁴⁺) ratio does not decrease from core to rim, and sharp enrichments (“spikes”) in Ti³⁺ and V are not observed. Sector-zoned fassaite is much more common in B2s than in B1s. The differences we observed can be accounted for by the differences in bulk compositions between B1s and B2s. Type B2 inclusions tend to have higher SiO₂ contents, hence higher An/Ge component ratios, than Type B1s. Phase equilibria show that, compared to B1s, in B2s less melilite should crystallize prior to the appearance of fassaite, so that in B2s a higher proportion of melilite cocrystallizes with fassaite, causing more of the crystals to be reversely zoned; more melilite crystallizes while adjacent to other crystals, leading to asymmetrical zoning; and with more liquid available, transport of components to growing fassaite occurs more readily than in B1s, facilitating crystal growth and giving rise to sector zoning. The lack of zoning with respect to Ti³⁺/Ti^tot and the absence of Ti³⁺-, V-rich spikes suggest that Type B2 melts maintained equilibrium with the nebular gas throughout crystallization, while the interiors of B1s were probably isolated from the gas, perhaps by their melilite mantles. This makes the similarity of Na-Åk relationships in B1 and B2 melilite difficult to understand, but apparently enclosure by melilite mantles was not necessary for the retention of Na₂O during crystallization of Type B refractory inclusions.     

Trace element partitioning between type B CAI melts and melilite and spinel: Implications for trace element distribution during CAI formation

Calcium- and aluminum-rich inclusions (CAIs), occurring in chondritic meteorites and considered the oldest materials in the solar system, can provide critical information about the environment and time scale of creation of planetary materials. However, interpretation of the trace element and isotope compositions of CAIs, particularly the light elements Li, Be, and B, is hampered by the lack of constraint on melilite-melt and spinel-melt partition coefficients. We determined melilite-melt and spinel-melt partition coefficients for 21 elements by performing controlled cooling rate (2 °C/h) experiments at 1 atmosphere pressure in sealed platinum capsules using a synthetic type B CAI melt. Trace element concentrations were measured by secondary ion mass spectrometry (SIMS) and/or laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Melilites vary only slightly in composition, ranging from Åk_31-43. Results for the partitioning of trace elements between melilite and melt in three experiments and between spinel and melt in two experiments show that partition coefficients are independent of trace element concentration, are in good agreement for different analytical techniques (SIMS and LA-ICP-MS), and are in agreement with previous measurements in the literature. Partition coefficients between intermediate composition melilites and CAI melt are the following: Li, 0.5; Be, 1.0; B, 0.22; Rb, 0.012; Sr, 0.68; Zr, 0.004; Nb, 0.003; Cs, 0.002; Ba, 0.018; La, 0.056; Nd, 0.065; Sm, 0.073; Eu, 0.67; Er, 0.037; Yb, 0.018; Hf, 0.001; Ta, 0.003; Pb, 0.15; U, 0.001; Th, 0.002. Site size energetics analysis is used to assess isovalent partitioning into the different cation sites. The Young’s modulus deduced from +2 cations partitioning into the melilite X site agrees well with the bulk modulus of melilite based on X-ray diffraction methods. The changes in light element partitioning as melilite composition varies are predicted and used in several models of fractional crystallization to evaluate if the observed Li, Be, and B systematics in Allende CAI 3529-41 are consistent with crystallization from a melt. Models of crystallization agree reasonably well with observed light element variations in areas previously interpreted to be unperturbed by secondary processes [Chaussidon, M., Robert, F., McKeegan, K.D., 2006. Li and B isotopic variations in an Allende CAI: Evidence for the in situ decay of short-lived ¹⁰Be and for the possible presence of the short-lived nuclide ⁷Be in the early solar system. Geochim. Cosmochim. Acta70, 224-245], indicating that the trends of light elements could reflect fractional crystallization of a melt. In contrast, areas interpreted to have been affected by alteration processes are not consistent with crystallization models.     

Cosmogenic effects on Li/Li, B/B, and W/W in CAIs from carbonaceous chondrites

This study focuses on cosmogenic effects on lithium, boron, and tungsten isotopes in CAIs from carbonaceous chondrites. The results for lithium isotopes have been used to properly correct experimental data obtained by Chaussidon et al. (2006a) for Allende CAI 3529-41 for cosmogenic contributions. After proper correction, the new inferred ratios slightly but systematically differ from the original ones, indicating that the original study slightly overestimated the cosmogenic corrections. A statistical interpretation of the data indicates that there is a non-linear correlation between ⁷Li/⁶Li and ⁹Be/⁶Li that might be interpreted as a disturbed isochron. For boron isotopes, the data obtained here confirm that cosmogenic corrections on the ¹⁰Be-¹⁰B dating system are indeed very minor and can in most cases be neglected. However, a statistical interpretation of the data demonstrates that the type of the fitting procedure used can significantly change the results. It is demonstrated that a fitting procedure using the uncertainties as weights gives a slope about 50% shallower compared to the slope obtained using a non-weighted fitting procedure (for the same data). Such a difference can be wrongly interpreted as an age difference of about one half-life. The modeled results for tungsten isotopes clearly demonstrate that cosmic-ray effects might be of importance for samples having high Ta/W ratios due to thermal neutron capture on ¹⁸¹Ta to form ¹⁸²W. This effect does not increase the scatter of the data around the isochron but increases the slope of the isochron and therefore gives too old formation ages for the studied CAIs. Consequently, a proper handling of cosmic-ray induced shifts is necessary for high precision ¹⁸²Hf-¹⁸²W dating studies.     

Supercontinent formation from stochastic collision and mantle convection models

The large-scale tectonics in the last billion years (Ga) are predominated by the assembly and breakup of supercontinents Rodinia and Pangea. The mechanisms controlling the assembly of supercontinents are not clear. Here, we investigate the assembly of a supercontinent with 1) stochastic models of randomly-moving continental blocks and 2) 3-D spherical models of mantle convection with continental blocks. For the stochastic models, we determined the time required for all the blocks to assemble into a single supercontinent on a spherical surface. We found that the assembly time from our stochastic models is significantly longer than inferred for Pangea and Rodinia. However, our study also suggests that the assembly time from stochastic models is sensitive to the rules for randomly assigning continental motion in the models. In our dynamic models of mantle convection, continental blocks are modeled as deformable and compositionally distinct materials from the mantle. We found that mantle convective planform has significant effects on supercontinent assembly. For models with moderately strong lithosphere and the lower mantle relative to the upper mantle that lead to degree-1 mantle convection, continental blocks always assemble to a supercontinent in  250 million years (Ma) and this assembly time is consistent with inferred for Pangea and Rodinia. However, for models with intrinsically small-scale mantle flows, we found that even when continental blocks merge to form a supercontinent, the assembly times are too long and the convective structures outside of supercontinent regions are of too small wavelengths, compared with observed.     

Crystallization of Cr-poor and Cr-rich megacryst suites from the host kimberlite magma: implications for mantle structure and the generation of kimberlite magmas

Cr-poor and Cr-rich megacryst suites, both comprising of varying proportions of megacrysts of orthopyroxene, clinopyroxene, garnet, olivine, ilmenite and a number of subordinate phases, coexist in many kimberlites, with wide geographic distribution. In rare instances, the two suites occur together on the scale of individual megacryst hand specimens. Deformation textures are common to both suites, suggesting an origin related to the formation of the sheared peridotites that also occur in kimberlites. Textures and compositions of the latter are interpreted to reflect deformation and metasomatism within the thermal aureole surrounding the kimberlite magma in the mantle. The megacrysts crystallized in this thermal aureole in pegmatitic veins representing small volumes of liquids derived from the host kimberlite magma, which were injected into a surrounding fracture network prior to kimberlite eruption. Close similarities between compositions of Cr-rich megacryst phases and those in granular lherzolites are consistent with early crystallization from a primitive kimberlite liquid. The low-Cr megacryst suite subsequently crystallized from residual Cr-depleted liquids. However, the Cr-poor suite also reflects the imprint of contamination by liquids formed by melting of inhomogeneously distributed mantle phases with low melting temperatures, such as calcite and phlogopite, present within the thermal aureole surrounding the kimberlite magma reservoir. Such carbonate-rich melts migrated into, and mixed with some, but not all, of the kimberlite liquids injected into the mantle fracture network. Contamination by the carbonate-rich melts changed the Ca–Mg and Mg–Fe crystal–liquid distribution coefficient, resulting in the crystallization of relatively Fe-rich and Ca-poor phases. The implied higher crystal-melt Mg–Fe distribution coefficient for carbonate-rich magmas accounts for the generation of small volumes of Mg-rich liquids that are highly enriched in incompatible elements (i.e. primary kimberlite magmas). The inferred metasomatic origin for the sheared peridotites implies that this suite provides little or no information regarding vertical changes in the thermal, chemical and mechanical characteristics of the mantle.     

Type I eclogites from Roberts Victor kimberlites: Products of extensive mantle metasomatism

Type I and Type II eclogite xenoliths from the Roberts Victor kimberlite (South Africa) show marked differences in terms of microstructures, mineralogy, major- and trace-element compositions and oxygen-isotope compositions. The unequilibrated microstructures of Type I eclogites, their typical accessory assemblages (phologopite, diamond, sulphides, fluid inclusions) and the ubiquitous presence of “melt pockets” in garnets provide strong evidence of metasomatism. Type II eclogites systematically lack such features and are microstructurally more equilibrated. Type I eclogites are more magnesium-rich than most Type II (mean Mg# = 0.56 vs. 0.46), while Type II eclogites are generally more Ca-rich (mean CaO = 9 vs. 12 wt%) and Fe-rich (mean FeO = 10 vs. 12 wt%). Type I eclogites are systematically enriched in LREE, Sr, Ba, alkali elements, HFSE, Th and U compared to the more depleted Type II eclogites. Calculated trace-element patterns of fluids in equilibrium with Type I eclogites are closely similar to those of volatile-rich small-volume mantle melts in the carbonatite-kimberlite spectrum commonly inferred to be responsible for mantle metasomatism. Although oxygen isotopes are often used to argue for a subduction origin of mantle eclogites, correlations between δ¹⁸O of garnet and typical metasomatic tracers suggest that the metasomatic process also has shifted the oxygen-isotope compositions of the Type I eclogites toward heavier values. Roberts Victor Type I eclogites thus carry the imprint of a metasomatic process that strongly modified their major-element, trace-element and isotopic compositions, while the more pristine Type II eclogites escaped this modification. Therefore, attempts to constrain the origin of Roberts Victor eclogites should not be based on the much more abundant Type I eclogites, which retain little geochemical memory of their protoliths. The most suitable materials for such investigations may be the less metasomatised, but more rare, Type II eclogites.     

Oxygen isotopic compositions of Allende Type C CAIs: Evidence for isotopic exchange during nebular melting and asteroidal metamorphism

In situ oxygen isotopic measurements of primary and secondary minerals in Type C CAIs from the Allende CV3 chondrite reveal that the pattern of relative enrichments and depletions of ¹⁶O in the primary minerals within each individual CAI are similar to the patterns observed in Types A and B CAIs from the same meteorite. Spinel is consistently the most ¹⁶O-rich (Δ¹⁷O = −25‰ to −15‰), followed by Al,Ti-dioside (Δ¹⁷O = −20‰ to −5‰) and anorthite (Δ¹⁷O = −15‰ to 0‰). Melilite is the most ¹⁶O-depleted primary mineral (Δ¹⁷O = −5‰ to −3‰). We conclude that the original melting event that formed Type C CAIs occurred in a ¹⁶O-rich (Δ¹⁷O  −20‰) nebular gas and they subsequently experienced oxygen isotopic exchange in a ¹⁶O-poor reservoir. At least three of these (ABC, TS26F1 and 93) experienced remelting at the time and place where chondrules were forming, trapping and partially assimilating ¹⁶O-poor chondrule fragments. The observation that the pyroxene is ¹⁶O-rich relative to the feldspar, even though the feldspar preceded it in the igneous crystallization sequence, disproves the class of CAI isotopic exchange models in which partial melting of a ¹⁶O-rich solid in a ¹⁶O-poor gas is followed by slow crystallization in that gas. For the typical (not associated with chondrule materials) Type C CAIs as well for as the Types A and B CAIs, the exchange that produced internal isotopic heterogeneity within each CAI must have occurred largely in the solid state. The secondary phases grossular, monticellite and forsterite commonly have similar oxygen isotopic compositions to the melilite and anorthite they replace, but in one case (CAI 160) grossular is ¹⁶O-enriched (Δ¹⁷O = −10‰ to −6‰) relative to melilite (Δ¹⁷O = −5‰ to −3‰), meaning that the melilite and anorthite must have exchanged its oxygen subsequent to secondary alteration. This isotopic exchange in melilite and anorthite likely occurred on the CV parent asteroid, possibly during fluid-assisted thermal metamorphism.     

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.     

汉诺坝玄武岩及幔源包体对大陆地幔不均一性的指示

了解大陆地幔的不均一性对于理解地壳成分再循环、壳-幔相互作用等过程至关重要。本文通过对华北克拉通北缘汉诺坝地区来自不同地幔深度幔源岩石（玄武岩及橄榄岩和辉石岩包体）的研究进行综述,探讨了地幔在垂向上成分的不均一性特征。汉诺坝玄武岩的研究揭示了汉诺坝地区软流圈顶部存在再循环的碳酸盐化榴辉岩以及岩石圈底部具有富集的古老洋壳和沉积物成分。另外,玄武岩携带的橄榄岩和多类型辉石岩包体记录了不同来源（蚀变洋壳、沉积碳酸盐岩、碎屑沉积物、拆沉下地壳、软流圈）且不同成分（硅酸盐、碳酸盐）的熔/流体活动。富集地壳来源的熔/流体加入明显影响了汉诺坝地区陆下地幔成分的均质性,使得陆下地幔在微米至千米尺度存在明显的成分不均一特征。汉诺坝地区陆下地幔不均一性的认识为了解地壳物质再循环提供了绝佳的窗口。

     

Chalcophile element partitioning between sulfide phases and hydrous mantle melt: Applications to mantle melting and the formation of ore deposits

Understanding the geochemical behavior of chalcophile elements in magmatic processes is hindered by the limited partition coefficients between sulfide phases and silicate melt, in particular at conditions relevant to partial melting of the hydrated, metasomatized upper mantle. In this study, the partitioning of elements Co, Ni, Cu, Zn, As, Mo, Ag, and Pb between sulfide liquid, monosulfide solid solution (MSS), and hydrous mantle melt has been investigated at 1200 °C/1.5 GPa and oxygen fugacity ranging from FMQ−2 to FMQ+1 in a piston-cylinder apparatus. The determined partition coefficients between sulfide liquid and hydrous mantle melt are: 750–1500 for Cu; 600–1200 for Ni; 35–42 for Co; 35–53 for Pb; and 1–2 for Zn, As, and Mo. The partition coefficients between MSS and hydrous mantle melt are: 380–500 for Cu; 520–750 for Ni; ∼50 for Co; <0.5 for Zn; 0.3–6 for Pb; 0.1–2 for As; 1–2 for Mo; and >34 for Ag. The variation of the data is primarily due to differences in oxygen fugacity. These partitioning data in conjunction with previous data are applied to partial melting of the upper mantle and the formation of magmatic-hydrothermal Cu–Au deposits and magmatic sulfide deposits.I show that the metasomatized arc mantle may no longer contain sulfide after >10–14% melt extraction but is still capable of producing the Cu concentrations in the primitive arc basalts, and that the comparable Cu concentrations in primitive arc basalts and in MORB do not necessarily imply similar oxidation states in their source regions.Previous models proposed for producing Cu- and/or Au-rich magmas have been reassessed, with the conclusions summarized as follows. (1) Partial melting of the oxidized (fO₂ > FMQ), metasomatized arc mantle with sulfide exhaustion at degrees >10–14% may not generate Cu-rich, primitive arc basalts. (2) Partial melting of sulfide-bearing cumulates in the root of thickened lower continental crust or lithospheric mantle does not typically generate Cu- and/or Au-rich magmas, but they do have equivalent potential as normal arc magmas in forming magmatic-hydrothermal Cu–Au deposits in terms of their Cu–Au contents. (3) It is not clear whether partial melting of subducting metabasalts generates Cu-rich adakitic magmas, however adakitic magmas may extract Cu and Au via interaction with mantle peridotite. Furthermore, partial melting of sulfide-bearing cumulates in the deep oceanic crust may be able to generate Cu- and Au-rich magmas. (4) The stabilization of MSS during partial melting may explain the genetic link between Au-Cu mineralization and the metasomatized lithospheric mantle.The chalcophile element tonnage, ratio, and distribution in magmatic sulfide deposits depend on a series of factors. This study reveals that oxygen fugacity also plays an important role in controlling Cu and Ni tonnage and Cu/Ni ratio in magmatic sulfide deposits. Cobalt, Zn, As, Sn, Sb, Mo, Ag, Pb, and Bi concentrations and their ratios in sulfide, due to their different partitioning behavior between sulfide liquid and MSS, can be useful indices for the distribution of platinum-group elements and Au in magmatic sulfide deposits.     

Oxygen potential of diamond formation in the lower mantle

Thermodynamic calculations have shown that when a metallic phase arising due to ferroan ion disproportionation is contained in lower-mantle rocks, carbon occurs as iron carbide and the oxygen fugacity corresponds to the equilibrium of ferropericlase with Fe-Ni alloy. The typical values of oxygen fugacity in zones of diamond formation in the lower mantle lie between the iron-wüstite buffer and six logarithmic units above this level. The processes that proceed in the lower mantle give rise to variation of $f_{O_2 }$ within several orders of magnitude above the elevated $f_{O_2 }$ values, which are necessary for the formation of diamond, as compared with a common level typical of the lower mantle. The mechanisms responsible for redox differentiation in the lower mantle comprise the subduction of oxidized crustal material, mechanical separation of metallic phase and silicate-oxide mineral assemblage enriched in ferric ions, as well as transfer of fused silicate material presumably enriched in Fe³⁺ through the mantle.     

On mantle drag force for the formation of a next supercontinent as estimated from a numerical simulation model of global mantle convection

Three‐dimensional spherical mantle convection was simulated to predict future continental motion and investigate the driving force of continental motion. Results show that both the time required (≥300 Ma from the present) and the process for the next supercontinent formation are sensitive to the choice of critical rheological parameters for mantle dynamics, such as a viscosity contrast between the upper and lower mantles and a yield strength of the lithosphere. From all the numerical models studied herein, mantle drag force by horizontal mantle flow beneath the continents may mostly act as a resistance force for the continental motion in the process of forming a new supercontinent. The maximum absolute magnitude of the tensional and compressional stress acting at the base of the moving continents is in the order of 100 MPa, which is comparable to a typical value of the slab pull force.     

Search for extinct Cl: Vigarano CAIs, the Pink Angel from Allende, and a Ningqiang chondrule

We have searched for excesses of ³⁶S derived from the decay of extinct ³⁶Cl in sodalite, a secondary Cl-rich mineral, in Ca-Al-rich inclusions (CAIs) from the Vigarano and Allende CV3 chondrites and in a chondrule from the Ningqiang carbonaceous chondrite. The presence of sodalite in two CAIs from Vigarano and its absence from surrounding CAI fragments suggests sodalite formation after CAI fragmentation. As for sodalite in the Allende Pink Angel CAI, oxygen isotopic compositions have been interpreted as indicative of high temperature interactions, thus suggesting formation prior to accretion to the parent body, probably in a nebular setting. Sodalite in the Ningqiang chondrule is considered to have formed via alkali-Ca exchange, which is believed to have occurred before accretion to the parent body.Sodalites in the Vigarano CAIs and in the Ningqiang chondrule show no clear evidence for the presence of radiogenic ³⁶S. The inferred 2σ upper limits for ³⁶Cl/³⁵Cl at the time of sodalite formation are 1.6 × 10⁻⁶ (Vigarano CAIs) and 3.3 × 10⁻⁶ (Ningqiang chondrule), respectively. In the Pink Angel CAI sodalite exhibits small ³⁶S excesses which weakly correlate with ³⁵Cl/³⁴S ratios. The inferred ³⁶Cl/³⁵Cl ratio of (1.8 ± 2.2) × 10⁻⁶ (2σ error) is lower than that found by Hsu et al. [Hsu, W., Guan, Y., Leshin, L. A., Ushikubo, T. and Wasserburg, G. J. (2006) A late episode of irradiation in the early solar system: Evidence from extinct ³⁶Cl and ²⁶Al in meteorites. Astrophys. J. 640, 525-529], thus indicative of heterogeneous distribution of ³⁶Cl in this CAI. Spallation reactions induced by energetic particles from the young Sun are suggested for the origin of ³⁶Cl, similar to the case of ¹⁰Be. While ¹⁰Be appears to be present in roughly equal abundance in all studied CAIs, our study indicates the level of ³⁶Cl abundances to be variable so that there seems to be no simple relationship between ¹⁰Be and ³⁶Cl. This would be expected if trapped cosmic rays rather than Early Solar System spallation were the dominant source of ¹⁰Be in the Early Solar System, since their contribution to ³⁶Cl would have been tiny.If the variability of ³⁶Cl abundances is caused by temporal differences in the alteration that formed sodalite, sodalite in the Vigarano CAIs and in the Ningqiang chondrule may have formed ?0.5 and ?0.2 Ma after formation of the sodalite in the Ningqiang CAI analyzed by Lin et al. [Lin, Y., Guan, Y., Leshin, L. A., Ouyang, Z. and Wang, D. (2005) Short-lived chlorine-36 in a Ca- and Al-rich inclusion from the Ningqiang carbonaceous chondrite. Proc. Natl. Acad. Sci. USA 102, 1306-1311]. The Pink Angel sodalite that we analyzed may have formed ∼0.3 Ma after formation of the sodalite in the Pink Angel analyzed by Hsu et al. [Hsu, W., Guan, Y., Leshin, L. A., Ushikubo, T. and Wasserburg G. J. (2006) A late episode of irradiation in the early solar system: Evidence from extinct ³⁶Cl and ²⁶Al in meteorites. Astrophys. J. 640, 525-529]. The estimated temporal differences suggest that alteration extended over at least 0.5 Ma. If previous works showing very low initial ³⁶Cl/³⁵Cl in the Allende CAIs and a H3 chondrite CAI are also considered, then alteration processes may have been more than 1.7 Ma.     

Depleted and enriched matter in the upper mantle of Spitsbergen: Evidence from the study of mantle xenoliths

Doklady Earth Sciences -     

Mineralogy of the upper mantle: A review of the minerals in mantle xenoliths from kimberlite

The importance of ultramafic and eclogitic xenoliths in kimberlite as representing the rocks and minerals of the upper mantle has been widely perceived during the last decade. Studies of the petrology and mineral chemistry of these mantle fragments as well as of inclusions in diamond, have led to significant progress in our understanding of the mineralogy and chemistry of the upper mantle. For example, it is now known that textural differences in the ultramafic xenoliths (lherzolite, harzburgite, pyroxenite and websterite) are partially reflected in chemical differences. Thus xenoliths that display a ‘fluidal’ texture, indicative of intense deformation are less depleted in Ca, Al, Na, Fe and Ti than those xenoliths in which granular textures are predominant. It is believed this relative depletion may indicate the sheared (fluidal texture) xenoliths are representative of primary, undifferentiated mantle. This material on partial melting would produce ‘basaltic-type’ material, and leave a residuum whose chemistry and mineralogy is reflected by the granular xenoliths.Also present in kimberlite are large single phase xenoliths that may be either one single crystal (xenocryst, megacryst) or an aggregate of several crystals of the same mineral (discrete xenolith, or discrete nodule). These large single phase samples consist of similar minerals to those occurring in the ultramafic xenoliths but chemically they are distinct in being generally more Fe-rich. The relation between these xenocrysts to their counterparts in the ultramafic xenoliths is unknown. Also unknown, at the present time, is the exact relation between diamond and kimberlite. Evidence obtained from study of the mineral inclusions in diamond suggests that diamond forms in at least two chemically distinct environments in the mantle; one eclogitic, the other, ultramafic. Interestingly, this suggestion is true for diamonds from worldwide localities.The mineral-chemical results of studies on xenoliths and inclusions in diamond have been convincingly interpreted in the light of experimental studies. It is now possible based on several different geothermometers and barometers to determine relatively reasonable physical conditions for the final genesis of many of these mantle rocks. For the most part the final equilibration temperatures range between 1000 and 1400°C and pressure in the region 100–200 km. These conditions are consistent with an upper mantle origin. Future studies will undoubtedly attempt to more concisely, and accurately, define these conditions, as well as understand better the chemical and spatial relationship of the rock-types in the mantle.     

The physicochemical conditions of diamond formation in the mantle matter: experimental studies

Experimental studies of diamond formation in the alkaline silicate-carbon system Na₂O–K₂O–MgO–CaO–Al₂O₃–SiO₂–C were carried out at 8.5 GPa. In accordance with the diamond nucleation criterion, a high diamond generation efficiency (spontaneous mass diamond crystallization) has been confirmed for the melts of the system Na₂SiO₃–carbon and has been first established for the melts of the systems CaSiO₃–carbon and (NaAlSi₃O₈)₈₀(Na₂SiO₃)₂₀–carbon. It is shown that in completely miscible carbonate-silicate melts oversaturated with dissolved diamond-related carbon, a concentration barrier of diamond nucleation (CBDN) arises at a particular ratio of carbonate and silicate components. Study of different systems (eclogite–K-Na-Mg-Ca-Fe-carbonatite–carbon, albite–K₂CO₃–carbon, etc.) has revealed a dependence of the barrier position on the chemical composition of the system and the inhibiting effect of silicate components on the nucleation density and rate of diamond crystal growth. In multicomponent eclogite-carbonatite solvent, the CBDN is within the range of carbonatite compositions (<50 wt.% silicates). Based on the experimental criterion for the syngenesis of diamond and growth inclusions in them, we studied the syngenesis diagram for the system melanocratic carbonatite–diamond and determined a set of the composition fields and physical parameters of the system that are responsible for the cogeneration of diamond and various mineral and melt parageneses. The experimental results were applied to substantiate a new physicochemical concept of carbonate-silicate (carbonatite) growth media for most of natural diamonds and to elaborate a genetic classification of growth mineral, melt, and fluid inclusions in natural diamonds of mantle genesis.     

The buffering capacity of lithospheric mantle: implications for diamond formation

Current models for the formation of natural diamond involve either oxidation of a methane-bearing fluid by reaction with oxidized mantle, or reduction of a carbonate-bearing fluid (or melt) by reaction with reduced mantle. Implicit in both models is the ability of the mantle with which the fluid equilibrates to act as an oxidizing or reducing agent, or more simply, to act as a source or sink of O₂. If only redox reactions involving iron are operating, the ability of mantle peridotite to fulfill this role in diamond formation may not be sufficient for either model to be viable. Using the recent experimental recalibration of olivine–orthopyroxene–garnet oxybarometers of Stagno et al. (2013), we re-evaluated the global database of ~200 garnet peridotite samples for which the requisite Fe³⁺/Fe²⁺ data for garnet exist. Relative to the previous calibration of Gudmundsson and Wood (1995), the new calibration yields somewhat more oxidized values of Δlog fO₂ (FMQ), with the divergence increasing from <0.5 units of log fO₂ at ~3 GPa to as much as 1.5 units at 5–6.5 GPa. Globally, there is a range of ~4 log units fO₂ for samples from the diamond stability field at any given pressure. Most samples are sufficiently reduced such that diamond, rather than carbonate, would be stable, and CHO fluids at these conditions would be H₂O-rich (>60 mol%), with CH₄ being the next most abundant species. To ascertain the capacity for mantle peridotite to act as a source or sink of O₂, we developed a new model to calculate the fO₂ for a peridotite at a given P, T, and Fe³⁺/Fe²⁺. The results from this model predict 50 ppm or less O₂ is required to shift a depleted mantle peridotite the observed four log units of fO₂. Coupled with the observed distribution of samples at values of fO₂ intermediate between the most reduced (metal-saturated) and most oxidized (carbonate-saturated) possible values for diamond stability, these results demonstrate that peridotites are very poor sinks or sources of O₂ for possible redox reactions to form diamond. A corollary of the poor redox buffering capacity of cratonic peridotites is that they can be employed as faithful indicators of the redox state of the last metasomatic fluid that passed through them. We propose that diamond formation from CHO fluids is a predictable consequence either of isobaric cooling or of combined cooling and decompression of the fluid as it migrates upward in the lithosphere. This establishes a petrological basis for the observed close connection between subcalcic garnet and diamond: based on high solidus temperatures of harzburgite and dunite effectively precluding dilution of CHO fluids through incipient melts, such highly depleted cratonic peridotites are the preferred locus of diamond formation. Due to a rapid increase in solidus temperature with increasing CH₄ content of the fluid, diamond formation related to reduced CHO fluids may also occur in some cratonic lherzolites.     

Komatiites II: Experimental and Theoretical Investigations of Post-emplacement Cooling and Crystallization

When komatiite lavas are emplaced on the sea floor most of theheat transfer occurs through the upper lava-seawater boundary.We have investigated the cooling and crystallization of komatiitesusing a series of analogue laboratory experiments with aqueoussolutions and by theoretical analysis. In komatiites the viscosityis sufficiently low that convection occurs in the interior ofthe flow and these motions, due both to thermal and compositionalvariations, have an important influence on the characteristicfeatures of komatiites such as the strong compositional andtextural layering. The experiments have been conducted with crystallizing aqueoussolutions which display the same overall dynamical processesas solidifying komatiites. The solutions used are simple eutecticsystems having the property that crystallization from a solutionwhich is substantially more concentrated than the eutectic compositionleaves behind residual fluid which is less dense than the originalfluid. This models the decrease in density of komatiite meltson cooling, due to the crystallization of olivine. Such solutionshave been cooled strongly through the metal roof of an otherwiseinsulated container, using a typical fluid depth of 80 mm. Dendriticcrystals grew down vertically from the roof and released lightfluid, depleted in solute, which rose to form a zone of stagnantfluid at the top of the container, while the tips of the crystalsextended just below the bottom of this light layer. A layerof solid eutectic, with a horizontal front, grew more slowlyand filled in the space between the vertically oriented crystals. The growth of the crystals and the eutectic layer were monitoredvisually, and in some experiments the temperatures at the topand in the fluid were recorded, until solidification throughoutthe layer was complete. The solid block was sampled, and themelted products analysed to give vertical concentration profiles.Both the texture and composition are strongly influenced bythe fluid conditions during crystal growth. The top concentrationis that of the original solution, rapidly quenched against theroof, and the mean concentration through the region influencedby the stable fluid layer is also close to the original. Atthe bottom the concentration is high, reflecting the in situgrowth of close-packed crystals, and there is a sharp decreasein concentration at an intermediate level, between the upperand lower crystal layers. The experiments and associated theory shed new light on theconsolidation of komatiites and the development of their characteristictextures and compositions. Since the lava is convecting withinthe interior, the early stages of cooling are characterizedby a rapid decrease in temperature. Initial cooling rates of1 to 100 °C h^–1 are calculated. At this stage thecrust remains thin, but as the spinifex zone develops, convectionprogressively decreases in vigour and the cooling rate decreases.Spinifex texture is considered to form by constitutional supercoolingwhich is controlled by compositional convection. As the spinifextexture develops, the olivine dendrites form a layer of depletedfluid. The tips of the crystals extend beyond this differentiatedlayer into a convecting lower region and grow preferentiallyto produce the characteristic vertically oriented spinifex texture.The composition of spinifex zones is shown to be close, butnot identical, to the initial liquid composition. The compositionalprofiles of the solid products of the experiments are similarto those found in komatiites, with the most evolved rock compositionsbeing found just above the cumulate zone. The experiments alsosuggest an alternative explanation to crystal settling for thecumulate zone, in which growth of the spinifex zone by compositionalconvection concentrates crystals suspended within the turbulentlyconvecting lower layer.