Redox state of eclogites and peridotites from sub-cratonic upper mantle and a connection with diamond genesis

Pressure–Temperature- conditions and fluid compositions estimated for mineral parageneses from inclusions in diamonds, diamond-bearing and diamond-free xenoliths using a garnet–clinopyroxene–silica oxygen barometer data indicate that the upper mantle is zoned, with a relatively oxidized lithosphere and a reduced asthenosphere. Calculations in the C–O–H system indicate that eclogite inclusions within diamonds and xenoliths have formed mainly in equilibrium with water-rich fluids.     

金刚石成因之谜

叙述了金刚石的四种成因说,研究了各种成因的可能性,并对金刚石成因作为初步评述。     

Primary Ca-rich carbonatite magma and carbonate-silicate-sulphide liquid immiscibility in the upper mantle

A primary carbonate phase with Ca/(Ca+Mg) in the range 0.85–0.95 has been identified in a metasomatized, depleted harzburgite nodule from Montana Clara Island, Canary Islands; textural relations show that this carbonate represents a quenched liquid. Although magnesian carbonate melts have been described from upper mantle peridotites, this is the first reported occurrence of a primary magma within peridotite nodules which has the composition of calciocarbonatite, by far the most common carbonatite type occurring in crustal complexes. The carbonate in the Montana Clara harzburgite host is restricted to wehrlitic alteration zones and is intimately associated with a second generation of minerals, mainly olivine, clinopyroxene and spinel, with glass of syenitic composition, and with Fe−Cu-rich sulphides. The metasomatic assemblage was formed by reaction of a sodiumbearing dolomitic melt, derived from a somewhat deeper level in the upper mantle, with the harzburgite mineral assemblage at a pressure of 15 kbars, or lower. As a result of the reaction the residual carbonatite melt became more enriched in calcium. The calciocarbonatite and sulphide phases almost invariably form globules in the silicate glass, indicating the existence of three immiscible liquids under upper mantle conditions. Several alkaline complexes contain carbonatites occurring with syenitic rock types and its seems feasible that the formation of such close associations might have been influenced by processes of liquid immiscibility which took place under upper mantle conditions. Editorial responsibility: I. Parsons     

The brevity of carbonatite sources in the mantle: evidence from Hf isotopes

Hf, Zr and Ti in carbonatites primarily reside in their non-carbonate fraction while the carbonate fraction dominates the Nd and Sr elemental budget of the whole rock. A detailed investigation of the Hf, Nd and Sr isotopic compositions shows frequent isotopic disequilibrium between the carbonate and non-carbonate fractions. We suggest that the trace element and isotopic composition of the carbonate fraction better represents that of the carbonatite magma, which in turn better reflects the composition of the carbonatitic source. Experimental partitioning data between carbonatite melt and peridotitic mineralogy suggest that the Lu/Hf ratio of the carbonatite source will be equal to or greater than the Lu/Hf ratio of the carbonatite. This, combined with the Hf isotope systematics of carbonatites, suggests that, if carbonatites are primary mantle melts, then their sources must be short-lived features in the mantle (maximum age of 10–30 Ma), otherwise they would develop extremely radiogenic Hf compositions. Alternatively, if carbonatites are products of extreme crystal fractionation or liquid immiscibility then the lack of radiogenic initial Hf isotope compositions also suggests that their sources do not have long-lived Hf depletions. We present a model in which the carbonatite source is created in the sublithospheric mantle by the crystallization of earlier carbonatitic melts from a mantle plume. This new source melts shortly after its formation by the excess heat provided by the approaching hotter center of the plume and/or the subsequent ascending silicate melts. This model explains the HIMU-EMI isotope characteristics of the East African carbonatites, their high LREE/HREE ratios as well as the rarity of carbonatites in the oceanic lithosphere.     

Hf-Pb isotope and trace element constraints on the origin of the Jacupiranga Complex (Brazil): Insights into carbonatite genesis and multi-stage metasomatism of the lithospheric mantle

The Lower Cretaceous Jacupiranga complex, in the central-southeastern portion of the South American Platform, includes carbonatites in close association with silicate rocks (i.e. strongly and mildly silica-undersaturated series). Here we document the first hafnium isotope data on the Jacupiranga complex, together with new trace element and Pb isotope compositions. Even though liquid immiscibility from a carbonated silicate melt has been proposed for the genesis of several Brazilian carbonatites, isotopic and geochemical (e.g., Ba/La ratios, lack of pronounced Zr-Hf and Nb-Ta decoupling) information argues against a petrogenetic relationship between Jacupiranga carbonatites and their associated silicate rocks. Thus, an origin by direct partial melting of the mantle is considered. The isotopic compositions of the investigated silicate samples are coherent with a heterogeneously enriched subcontinental lithospheric mantle (SCLM) source of rather complex evolution. At least two metasomatic processes are constrained: (1) a first enrichment event, presumably derived from slab-related fluids introduced into the SCLM during Neoproterozoic times, as indicated by consistently old T_DM ages and lamprophyre trace signatures, and (2) a Mesozoic carbonatite metasomatism episode of sub-lithospheric origin, as suggested by εNd-εHf values inside the width of the terrestrial array. The Jacupiranga parental magmas might thus derive by partial melting of distinct generations of metasomatic vein assemblages that were hybridized with garnet peridotite wall-rocks.     

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.     

Partitioning of rare earth elements between phosphate-rich carbonatite melts and mantle peridotites

Summary Near solidus equilibria in the system mantle peridotite-carbonate-phosphate doped with Ce and Yb have been studied at 20 kbar and 950°C. Carbonatitic melts in this system may be quenched into homogeneous glasses. Such melts intensely extract REE from rock-forming mantle minerals, and their migration may cause processes of mantle metasomatism.

---

Verteilung von Seltenen Erden zwischen phosphatreichen karbonatitischen Schmelzen und Mantel-Peridotiten

Zusammenfassung Gleichgewichte nahe dem Solidus im System Mantel-Peridotit-Karbonat-Phosphat, das mit Ce und Yb dotiert wurde, wurden bei 20 kbar und 950°C untersucht. Karbonatitische Schmelzen in diesem System können zu homogenen Gläsern abgeschreckt werden. Solche Schmelzen extrahieren SEE aus gesteinsbildenden Mantelmineralen und ihre Migration könnte für Vorgänge der Mantel-Metasomatose verantwortlich sein.

---

---

With 2 figures     

Garnet inclusions in diamond and the state of the upper mantle

Temperature and pressure estimates for Earth's upper mantle generally are based on indirect information derived from phase equilibria studies and the measurement of temperature and pressure dependent physical and chemical properties for relevant mantle materials. This paper describes an alternative approach, based on solid-inclusion piezothermometry, which utilizes the thermoelastic properties of direct mantle derived mineral samples. In particular, this study provides the theoretical development, based on the Murnaghan equation of state for solids, for a simple method of calculating isomeke lines for host and inclusion minerals of cubic symmetry which may be extrapolated accurately to upper mantle pressure and temperature conditions. The method is demonstrated for the particular case of garnet inclusions in diamond, for which adequate laboratory thermoelastic data are available. A specific application is made in the evaluation of the depth of formation of the D1 garnet-diamond inclusion system described by Harris et al. (1970). The pressure and temperature conditions of inclusion formation lie along the calculated isomeke line within the range constrained by recent graphite-diamond phase equilibria data. However, because the isomeke line for the garnet-diamond system and the graphite-diamond phase transition are very similar in slope, a further constraint is required. Assuming, therefore, that temperature in the upper mantle is bounded by the “Oceanic” and “Shield” geotherms of Clark and Ringwood (1964), the present results indicate that the D1 garnet-diamond system formed within the depth range 138 to 155 km (about 45 to 53 kbar pressure). This result, which relates to the genesis of kimberlite xenoliths, is generally consistent with the results of other studies which utilize phase equilibria data.     

Mapping the mantle lithosphere for diamond potential using teleseismic methods

Recent developments in seismic, magnetotelluric and geochemical analytical techniques have significantly increased our capacity to explore the mantle lithosphere to depths of several hundred kilometres, to map its structures, and through geological interpretations, to assess its potential as a diamond reservoir. Several independent teleseismic techniques provide a synergistic approach in which one technique compensates for inadequacies in another. Shear wave anisotropy and discontinuity studies using single seismic stations define vertical mantle stratigraphic columns. For example, beneath the central Slave craton seismic discontinuities at depths of 38, 110, 140 and 190 km appear to bound two distinct anisotropic layers. Tomographic (3-D) inversions of seismic wave travel-times and 2-D inversions of surface or scattered waves use arrays of stations and provide lateral coverage. In combination, and by correlation with electrical conductivity and xenolith petrology studies, these techniques provide maps of key physical properties within parts of the cratons known to host diamonds. Beneath the Slave craton, the discontinuity at 38 km is the base of the crust; the boundaries at 110 and 140 km appear to bound a layer of depleted harzburgite that is interpreted to contain graphite. To date, only some of these techniques have been applied to the Slave and Kaapvaal cratons so that the origin and geological history of the currently mapped mantle structures are not, as yet, generally agreed.     

Fenitization at the Alnö carbonatite complex,Sweden; distribution,mineralogy and genesis

Re-mapping of the Alnö complex has radically reduced the area identified as fenite, in comparison with the classic work of Eckermann (1948). A marginal fenite zone, generally 500–600 m wide, is present around the complex, and the petrography and mineralogy of six selected key areas have been investigated in detail. Fenitization of the country rock migmatitic gneiss led to replacement of quartz, feldspars, biotite and chlorite by alkali pyroxene and amphibole, new generations of feldspars, calcite, titanite, fluorite and apatite. In some areas, however, a distinctive narrow band of fenitization, referred to as contact fenite, adjacent to large sövite dykes, contains mineral assemblages that include phlogopite, nepheline, melanite and wollastonite. Amphiboles in the fenites are richterite, katophorite, arfvedsonite and eckermannite. There is a very wide variation in the composition of pyroxenes which vary between diopside, aergirine-augite and aergirine. Although trends from aergirine to aegirine-augite and aegirine-augite to diopside have been defined, which are similar to those of other fenite localities, distinctive trends for the eastern part of the aureole have been identified that converge on aegirine, and approximate trends in some series of alkaline igneous rocks. Analyses of mica, garnet, wollastonite and feldspar are also presented and discussed. The mineralogical data are used to estimate the conditions of temperature, oxidation state, and activity of CO₂, H₂O and silica pertaining during the fenitization process. The fluids with which the fenites equilibrated were apparently different in composition in different parts of the aureole, and varied with time, implying more than one magmatic source. The various evolutionary trends identified in the pyroxenes and amphiboles, in particular, are explained in terms of two main fluid types, which emanated from ijolitic and carbonatitic magma sources.     

Deep carbon cycle and geodynamics: the role of the core and carbonatite melts in the lower mantle

Carbon, though being abundant in the Solar system, barely exceeds 0.01 wt.% in the silicate mantle, whereas it is ~ 3.6 wt.% in primitive chondritic meteorites that most likely formed our planet. This deficit may be due to redistribution of carbon in the liquid metal phase and then in the core at the stage of magma ocean fractionation, because carbon is much more soluble in Fe–Ni ± S melt than in silicate melts. The terrestrial heat and mass transfer are controlled mainly by layered convection and periodic peaks of plume activity as fast mantle jets that rise from the core. Plumes carry significant amounts of CO₂, H₂O, and K₂O (most probably in the form of carbonatite or hydrous carbonatite melts) released by the degassing core on its interaction with oxidized silicate material. There are two mechanisms that may maintain fast plume ascent: (1) local melting at the plume front as a result of doping with volatiles (H₂O, CO₂) as in a gas burner (rise rate 60–110 cm/yr) or (2) flow controlled by diffusion transport of silicate components in carbonatite melt (rise rate ~ 100 cm/yr).     

地球早期地幔化学不均一性及其成因机制

早期地球是地球科学前沿研究方向之一,涉及地-月形成、核幔分异、原始大气圈和水圈的形成等关键科学问题。地幔是硅酸盐地球的主要组成部分,也是地球上最大的化学储库,其早期演化为揭示早期地球增生、核-幔分异、壳-幔分异等重大地质事件提供重要制约。近年来,地球早期地幔不均一性逐渐被认知,本文在总结早期地幔不均一性的稀有气体同位素、钕同位素和钨同位素等证据基础上,探讨了早期地幔不均一性形成动力学机制,并指出发展高精度同位素分析技术,结合地球物理和实验岩石学,揭示核幔边界结构、核幔物质交换过程是深入研究早期地幔不均一的重要发展方向。

     

Basaltoids and carbonatite tuffs of Ambinsky volcano (Southwestern Primorye): Geology and genesis

Geological-petrological data were first obtained on the Early Miocene basaltoids and spinel-fassaite carbonatite tuffs of the Ambinsky volcanic structure in southwestern Primorye. The geological study of Ambinsky volcano allowed the reconstruction of stratigraphic sections across lava and pyroclastic basaltic rocks and stratified carbonatite tuffs. The chemical compositions of rocks and mineral phenocrysts from basalts and carbonatite tuffs are reported. The basaltoids are classed with undifferentiated moderately alkaline within-plate basalts. Evidence of carbonate-silicate immiscibility was found in the basaltoids and carbonatite tuffs. It was suggested that the formation of the carbonatite melt associated with simultaneous basification and abundant crystallization of spinel, fassaite, as well as oversaturation of the silicate system in Ca was caused by limestone assimilation, subsequent transformation of the melt, and liquid immiscibility. Thermal decomposition of carbonates with dissolution of released CaO in magma and accumulation of CO₂ in a closed magmatic chamber gave rise to the autoclave gas effect and, correspondingly, heavy explosive eruptions atypical of such volcanic rocks. The genesis of carbonatite tuffs of Ambinsky volcano can serve as a model example of exsolution of carbonate melt in the moderately alkaline nonagpaitic basaltic system.     

Nano-and micron-sized diamond genesis in nature: An overview

There are four main types of natural diamonds and related formation processes. The first type comprises the interstellar nanodiamond particles. The second group includes crustal nano-and micron-scale diamonds associated with coals, sediments and metamorphic rocks. The third one includes nanodiamonds and microndiamonds associated with secondary alteration and replacing of mafic and ultramafic rocks.The fourth one includes macro-, micron-and nano-sized mantle diamonds which are associated with kimberlites, mantle peridotites and eclogites. Each diamond type has its specific characteristics. Nanosized diamond particles of lowest nanometers in size crystallize from abiotic organic matter at lower pressures and temperatures in space during the stages of protoplanetary disk formation. Nano-sized diamonds are formed from organic matter at P-T exceeding conditions of catagenesis stage of lithogenesis. Micron-sized diamonds are formed from fluids at P-T exceeding supercritical water stability.Macrosized diamonds are formed from metal-carbon and silicate-carbonate melts and fluids at P-T exceeding 1150℃ and 4.5 GPa. Nitrogen and hydrocarbons play an important role in diamond formation.Their role in the formation processes increases from macro-sized to nano-sized diamond particles.Introduction of nitrogen atoms into the diamond structure leads to the stabilization of micron-and nanosized diamonds in the field of graphite stability.     

Constraints on diamond genesis from the study of the dependence of diamond properties on the composition of kimberlites and lamproites

It was shown that the crystal morphology, content, and size of diamonds depend on the concentrations of silica, magnesium, calcium, and carbon dioxide in the host kimberlites and lamproites. The character of this dependence suggests that the viscosity of the initial melts of these rocks was the main control of the morphology and properties of diamond crystals and indicates a magmatic genesis for this mineral. Two genetic varieties of diamond crystals were distinguished: larger residual grains coeval with the formation of the sources of kimberlite and lamproite magmas during the slow high-pressure fractionation of the near-bottom peridotite layer of the global magma ocean and smaller early magmatic grains, which crystallized during the decompression-friction transformation of kimberlite and lamproite protoliths into magmas.     

Trace element partitioning between silicate minerals and carbonatite at 25 kbar and application to mantle metasomatism

Summary Experiments at 25 kbar and 1000°C, on a model trace element-enriched carbonatite-eridotite mix, produced augite + pargasite ± garnet ± dolomite coexisting with a carbonatite melt. Proton microprobe analysis of the phases showed that key trace elements (Rb, Ba, Sr, Nb, Ta, Zr, Y and REE) all partitioned strongly into the melt (with the exception of Y, Ho and Lu in garnet), verifying that carbonatite is potentially a highly effective metasomatizing agent. The data also indicate that carbonatitic metasomatism will impart higher Ba/Rb, Ba/Nb, Nb/Ta, Sr/Ta, La/Ta, and lower Zr/Y, with little change to Sr/Nb, in affected mantle.

---

Spurenelementverteilung zwischen Silikatmineralen und Karbonatit bei 25 kbar: Anwendung für die Mantel-Metasomatose

Zusammenfassung Experimente mit einer Modell-mischung von Karbonatit-Peridotit, angereichert mit Spurenelementen, produzierten bei 25 kbar und 1000°C Augit + Pargasit ± Granat ±Dolomit coexistierend mit einer Karbonatitschmelze. Protonmikrosonden-Analyse der Phasen zeigte, dass alle Schlüsselspurenelemente (Rb, Ba, Sr, Nb, Ta, Zr, Y and REE) stark in der Schmelze angereichert werden (mit der Ausnahme von Y, Ho und Lu in Granat), was beweist, dass Karbonatit potentiell ein sehr effektives Agens für Metasomatose ist. Die Daten zeigen weiterhin, dass karbonatitische Metasomatose in betroffenen Mantel höhere Ba/Rb, Ba/Nb, Nb/Ta, Sr/Ta, La/Ta und niedrigere Zr/Y produziert, mit geringen Äderungen für Sr/Nb.

---

---

With 1 Figure     

华北克拉通东部岩石圈破坏与幔柱的成因

华北克拉通东部是指大兴安岭—太行山重力梯度带以东的地区。该地区与东北及华南地区一样,也存在着岩石圈减薄和岩石圈破坏的现象。华北克拉通古生代与新生代的橄榄岩包体地热值分别为40mW/m~2和80mW/m~2,地热增高是岩石圈破坏的重要因素。中国东部—朝鲜半岛的GRACE卫星布格重力异常呈巨型环状展布,可能是地幔亚热柱所致。区内郯庐断裂带呈NNE向纵贯切割,最新的地震反射剖面成果反映,该断裂带以走滑为主,兼有逆冲和正断层,所组成的大型"花状"复杂断裂构造带,切穿地壳、莫霍面,直至岩石圈地幔,起到破坏岩石圈的作用。S波速成像结果证实,在苏鲁造山带下方,分布的碎块状波速扰动带延伸300km,应是中生代扬子板块走滑俯冲、断离、折返的产物;而在渤海湾盆地下方,下地幔也存在陡倾的破碎带,延伸300km,在岩石圈76km处及其深部,S波速降低,扰动很剧烈,可能是地幔柱头部呈粗大状的反映,故可认为渤海湾盆地是由蘑菇云状的地幔柱形成。再从华北克拉通的大陆根来看,东部为A型反时针pT轨迹麻粒岩分布,而中西部则为B型麻粒岩,这是因为东部新太古代绿岩带中赋存有科马提岩,其岩浆温度可高达1 600℃,如用幔柱构造模型解释成因最为合适。通过研究近年大量地震反射P波和S波层析资料,华北克拉通的东部在晚侏罗-早白垩世及新生代期间,受太平洋板块俯冲和地幔热柱上隆的相互作用,深部的地幔流体常沿构造破裂带运移,促使岩石圈拆沉,并发生热侵蚀作用,形成酸性大火成岩省(SLIP)、裂谷型盆地的广泛分布和成矿成藏作用的"大爆发"。由此认为,建立区域构造模型将有利于指导深部找矿工作。     

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.