Oxidation states of the upper mantle recorded by megacryst ilmenite in kimberlite and type A and B spinel lherzolites

The intrinsic oxygen fugacities of homogeneous, inclusion-free, megacryst ilmenites from the Frank Smith, Excelsior, Sekameng and Mukorob kimberlite pipes in southern Africa, and the alnöitic breccia in the Solomon Islands have been determined. Similar measurements have been made of the type A and B spinel peridotites from San Carlos in Arizona. The type A peridotites are characterised by oxygen fugacities close to the iron-wüstite buffer, similar to those of equivalent peridotite specimens from other continental and island arc environments. In strong contrast, the type B peridotites and all of the ilmenite megacrysts range between the oxygen fugacities defined by the nickelnickel oxide and fayalite-magnetite-quartz buffers. A close relationship between type B peridotites, oxidized metasomatizing fluids in the upper mantle and oxidized, silicaundersaturated magma types is suggested. It is unlikely that a solid elemental carbon phase can be an equilibrium crystallization product of kimberlite magmas if the ilmenite megacrysts represent the redox state of kimberlite melts. The ultimate source of the oxidizing fluids and the development of such a wide dispersion (>4 orders of magnitude) in oxygen fugacities of the upper mantle is not clear, but may involve recycled lithosphere, fluids from the lower mantle or result from the relatively rapid diffusion of H₂, compared with other potential volatile species, in the mantle.     

The oxidation state of subcontinental mantle: oxygen thermobarometry of mantle xenoliths from central Asia

The oxygen fugacities of 48 mantle xenoliths from 5 localities in southern Siberia (USSR) and Mongolia have been determined. Ferric iron contents of spinels were measured by ⁵⁷Fe Mössbauer spectroscopy and oxygen fugacities calculated from spinel-olivineorthopyroxene equilibrium. The samples studied represent the major types of upper mantle lithologies including spinel and garnet peridotites and pyroxenites, fertile and depleted peridotites and anhydrous and metasomatized samples which come from diverse tectonic settings. Extensive geochemical and isotope data are also available for these samples. Oxygen fugacity values for most central Asian xenoliths fall within the range observed in peridotite xenoliths from other continental regions at or slightly below the FMQ buffer. However, xenoliths from the Baikal rift zone are the most reduced among xenoliths for which Mössbauer data on spinels are available. They yield fO₂ values similar to those in oceanic peridotites and MORBs, while xenoliths in other occurrences have higher fO₂s. In general, the continental lithosperic mantle is more oxidized than MORB-like oceanic mantle. This difference seems to be due to incorporation of oxidized material into some parts of the subcontinental mantle as a result of subduction of oceanic crust. Garnet- and garnet-spinel lherzolites from the Baikal rift area have slightly higher oxygen fugacities than shallower spinel lherzolites. Oxygen fugacity does not appear to be correlated with the degree of depletion of peridotites, and its values in peridotites and pyroxenites are very much alike, suggesting that partial melting (at least at moderate degrees) takes place at essentially the same fO₂s that are now recorded by the residual material. Modally (amphibole- and phlogopitebearing) and cryptically metasomatized xenoliths from the Baikal rift zone give the same fO₂ values as depleted anhydrous peridotites, suggesting that solid-melt-fluid reactions in the continental rift mantle also take place without substantial change in redox state. This is in contrast to other tectonic environments where metasomatism appears to be associated with oxidation.     

The characterisation and origin of graphite in cratonic lithospheric mantle: a petrological carbon isotope and Raman spectroscopic study

Graphite-bearing peridotites, pyroxenites and eclogite xenoliths from the Kaapvaal craton of southern Africa and the Siberian craton, Russia, have been studied with the aim of: 1) better characterising the abundance and distribution of elemental carbon in the shallow continental lithospheric mantle; (2) determining the isotopic composition of the graphite; (3) testing for significant metastability of graphite in mantle rocks using mineral thermobarometry. Graphite crystals in peridotie, pyroxenite and eclogite xenoliths have X-ray diffraction patterns and Raman spectra characteristic of highly crystalline graphite of high-temperature origin and are interpreted to have crystallised within the mantle. Thermobarometry on the graphite-peridotite assemblages using a variety of element partitions and formulations yield estimated equilibration conditions that plot at lower temperatures and pressures than diamondiferous assemblages. Moreover, estimated pressures and temperatures for the graphite-peridotites fall almost exclusively within the experimentally determined graphite stability field and thus we find no evidence for substantial graphite metastability. The carbon isotopic composition of graphite in peridotites from this and other studies varies from δ¹³ C_PDB = ? 12.3 to ? ?3.8%o with a mean of-6.7‰, σ=2.1 (n=22) and a mode between-7 and-6‰. This mean is within one standard deviation of the-4‰ mean displayed by diamonds from peridotite xenoliths, and is identical to that of diamonds containing peridotite-suite inclusions. The carbon isotope range of graphite and diamonds in peridotites is more restricted than that observed for either phase in eclogites or pyroxenites. The isotopic range displayed by peridotite-suite graphite and diamond encompasses the carbon isotope range observed in mid-ocean-ridge-basalt (MORB) glasses and ocean-island basalts (OIB). Similarity between the isotopic compositions of carbon associated with cratonic peridotites and the carbon (as CO₂) in oceanic magmas (MORB/OIB) indicates that the source of the fluids that deposited carbon, as graphite or diamond, in catonic peridotites lies within the convecting mantle, below the lithosphere. Textural observations provide evidence that some of graphite in cratonic peridotites is of sub-solidus metasomatic origin, probably deposited from a cooling C-H-O fluid phase permeating the lithosphere along fractures. Macrocrystalline graphite of primary appearance has not been found in mantle xenoliths from kimberlitic or basaltic rocks erupted away from cratonic areas. Hence, graphite in mantle-derived xenoliths appears to be restricted to Archaean cratons and occurs exclusively in low-temperature, coarse peridotites thought to be characteristic of the lithospheric mantle. The tectonic association of graphite within the mantle is very similar to that of diamond. It is unlikely that this restricted occurrence is due solely to unique conditions of oxygen fugacity in the cratonic lithospheric mantle because some peridotite xenoliths from off-craton localities are as reduced as those from within cratons. Radiogenic isotope systematics of peridotite-suite diamond inclusions suggest that diamond crystallisation was not directly related to the melting events that formed lithospheric peridotites. However, some diamond (and graphite?) crystallisation in southern Africa occurred within the time span associated with the stabilisation of the lithospheric mantle (Pearson et al. 1993). The nature of the process causing localisation of carbon in cratonic mantle roots is not yet clearly understood.     

Kimberlite-hosted diamond deposits of southern Africa: A review

Following the discovery of diamonds in river deposits in central South Africa in the mid nineteenth century, it was at Kimberley where the volcanic origin of diamonds was first recognized. These volcanic rocks, that were named “kimberlite”, were to become the corner stone of the economic and industrial development of southern Africa. Following the discoveries at Kimberley, even more valuable deposits were discovered in South Africa and Botswana in particular, but also in Lesotho, Swaziland and Zimbabwe.A century of study of kimberlites, and the diamonds and other mantle-derived rocks they contain, has furthered the understanding of the processes that occurred within the sub-continental lithosphere and in particular the formation of diamonds. The formation of kimberlite-hosted diamond deposits is a long-lived and complex series of processes that first involved the growth of diamonds in the mantle, and later their removal and transport to the earth's surface by kimberlite magmas. Dating of inclusions in diamonds showed that diamond growth occurred several times over geological time. Many diamonds are of Archaean age and many of these are peridotitic in character, but suites of younger Proterozoic diamonds have also been recognized in various southern African mines. These younger ages correspond with ages of major tectono-thermal events that are recognized in crustal rocks of the sub-continent. Most of these diamonds had eclogitic, websteritic or lherzolitic protoliths.In southern Africa, kimberlite eruptions occurred as discrete events several times during the geological record, including the Early and Middle Proterozoic, the Cambrian, the Permian, the Jurassic and the Cretaceous. Apart from the Early Proterozoic (Kuruman) kimberlites, all of the other events have produced deposits that have been mined. It should however be noted that only about 1% of the kimberlites that have been discovered have been successfully exploited.In this paper, 34 kimberlite mines are reviewed with regard to their geology, mantle xenolith, xenocryst and diamond characteristics and production statistics. These mines vary greatly in size, grade and diamond-value, as well as in the proportions and types of mantle mineral suites that they contain. They include some of the world's richest mines, such as Jwaneng in Botswana, to mines that are both small and marginal, such as the Frank Smith Mine in South Africa. They include large diatremes such as Orapa and small dykes such as those mined at Bellsbank, Swartruggens and near Theunissen. These mines are all located on the Archaean Kalahari Craton, and it is apparent that the craton and its associated sub-continental lithosphere played an important role in providing the right environment for diamond growth and for the formation of the kimberlite magmas that were to transport them to the surface.     

Trace elements in garnets and chromites: Diamond formation in the Siberian lithosphere

Proton-microprobe analyses of trace elements in garnet and chromite inclusions in diamonds (DI) from the Mir, Udachnaya, Aikhal and Sytykanskaya kimberlites in Yakutia, CIS, provide new insights into the processes that form diamond. Equivalent data on garnet and chromite concentrates from these pipes yield information on the thermal state and chemical stratification of the Siberian lithosphere. Peridotite-suite diamonds from Yakutia have formed over a temperature interval of ca. 600°C, as measured by Ni and Zn thermometry on garnet and chromite inclusions in diamonds. Individual diamonds contain inclusions recording temperature intervals of >400°C; ranges of >100°C are common. Diamond formation followed a severe depletion event(s), and a separate enrichment in Sr. Comparison of temperatures on DI garnet and spinel with temperatures derived from diamondiferous harzburgites, exposed inclusions in boart and concentrate minerals suggests that the diamond-containing part of the lithosphere has cooled significantly since the Siberian diamonds crystallized. The peridotite-suite diamonds probably formed mainly in response to one or more relatively short-lived thermal events, related to magmatic intrusion. The northern part of the Daldyn-Alakit district may have had a typical cratonic geotherm at the time of diamond formation, and during kimberlite intrusion. The southern part of the district, and the Malo-Botuobiya kimberlite field, probably had a relatively low geotherm (ca. 35 mW/m²). The vertical distribution of garnet and chromite types indicates that the mantle above 120 km depth is dominated by lherzolites, whereas the deeper parts of the lithosphere are a mixture of lherzolites and more depleted harzburgites and dunites.     

Mantle Redox State Evolution in Eastern China and Its Implications

Using the secondary spinel standard, the authors have precisely measured the Fe3+/∑ Fe values of spinels in mantle xenoliths from Cenozoic basalts in eastern China, and estimated the oxygen fugacities recorded by 63 mantle xenoliths through olivine-orthopyroxene-spinel oxygen barometry. The results indicate that the oxygen fugacities of the lithospheric mantle in eastern China are higher in the south than in the north. Among them, the oxygen fugacity of the North China craton lithospheric mantle is the lowest, similar to that of the oceanic mantle, while that of Northeast and South China are the same as that of the global continental mantle. The variations of mantle redox state in eastern China are mainly controlled by the C-O-H fluids derived from the asthenospheric mantle. According to the mantle oxidation state, it can be concluded that the C-O-H fluids in the lithospheric mantle of eastern China consist mainly of CO2 and minor H2O, but CH4-rich fluids should come from the asthenosphere where the ox     

Diamond potential versus oxygen regime of carbonatites

Physicochemical conditions of graphite and diamond formation in the carbonate-rich melts were estimated. A large body of analytical data was obtained for compositions of coexisting minerals in the studied objects (Chernigovka Massif, Ukraine, and Chagatai carbonatite complex, Uzbekistan). The carbon isotopic composition of the coexisting carbonates and graphite from these carbonatites was analyzed. New thermodynamic methods were proposed to estimate the oxygen potential in graphite- and diamond-bearing carbonatites. Oxygen fugacity in the graphite-bearing carbonatites is slightly below the quartz-fayalite-magnetite buffer. It was proved that diamond is generated in the course of reduction of carbonate components arriving from plume material into the lower subcontinental lithosphere rather than owing to partial oxidation of methane fluids. As follows from the study of olivine and nominally anhydrous minerals in kimberlites, the limited role of methane in deep mantle is determined by low water activity. Methane is generated in mantle under special conditions such as extremely low oxygen fugacity (for instance, at the base of continental lithosphere) and elevated water activity. These conditions may occur during crystallization differentiation in deep-level chambers of kimberlite and proto-kimberlite magmas.     

Physicochemical parameters of the material of mantle plumes: Evidence from the thermodynamic analysis of mineral inclusions in sublithospheric diamond

Thermodynamic analysis of equilibria involving minerals of the lower mantle of pyrolite composition and crystalline carbon-bearing compounds indicates that the range of oxygen fugacity values at which diamond can be formed is separated from the region in which Fe-rich metallic alloy is generated by a field in which Fe carbides are stable. This implies that diamond can be formed in the lower mantle under more oxidizing conditions than those thought to be dominant in this geosphere. The absence of a metallic phase from the lower-mantle diamond-bearing mineral assemblage is consistent with the high (approximately 1%) Ni concentration in the ferropericlase found as inclusions in diamonds (Fe-rich metallic alloy is able to intensely extract Ni). An elevated redox potential also follows from the occurrence of carbonate phases found among mineral inclusions in lower-mantle diamonds. The main reason for a local increase in oxygen fugacity in the lower mantle may be shifts of redox equilibria toward a decrease in the amount, and then the disappearance of the Fe-Ni alloy with increasing temperature. An important role in the formation of diamond may be played by the generation of carbonate-phosphate and silicate melts in high-temperature zones and the migration of these melts and their interaction with wall rocks.     

博茨瓦纳奥拉帕金刚石矿床成矿地质特征

博茨瓦纳是世界上金刚石资源最为丰富的国家之一。奥拉帕金刚石矿床是该国最大的金刚石矿,矿床的金伯利岩为Ⅰ型,其中的包体可以分为2种:橄榄岩型和榴辉岩型;金刚石可以分为3类:橄榄岩型、榴辉岩型及两者的过渡类型-二辉岩型。其中,橄榄岩型和部分榴辉岩型金刚石来自于地幔结晶堆晶体,而榴辉岩型则与板块俯冲的构造-热事件有关。金伯利岩的形成时代主要为白垩纪,而金刚石则主要形成于元古宙和太古宙,金伯利岩和金刚石为不同时期的产物,金刚石为金伯利岩侵位期间捕获的上地幔物理破碎产物。其中年龄为900~1000Ma的金刚石为板块构造-热事件的产物,并对早期金刚石进行了改造破坏。     

Mineral inclusions in diamonds from the Sputnik kimberlite pipe, Yakutia

The Sputnik kimberlite pipe is a small “satellite” of the larger Mir pipe in central Yakutia (Sakha), Russia. Study of 38 large diamonds (0.7-4.9 carats) showed that nine contain inclusions of the eclogitic paragenesis, while the remainder contain inclusions of the peridotitic paragenesis, or of uncertain paragenesis. The peridotitic inclusion suite comprises olivine, enstatite, Cr-diopside, chromite, Cr-pyrope garnet (both lherzolitic and harzburgitic), ilmenite, Ni-rich sulfide and a Ti-Cr-Fe-Mg-Sr-K phase of the lindsleyite-mathiasite (LIMA) series. The eclogitic inclusion suite comprises omphacite, garnet, Ni-poor sulfide, phlogopite and rutile. Peridotitic ilmenite inclusions have high Mg, Cr and Ni contents and high Nb/Zr ratios; they may be related to metasomatic ilmenites known from peridotite xenoliths in kimberlite. Eclogitic phlogopite is intergrown with omphacite, coexists with garnet, and has an unusually high TiO₂ content. Comparison with inclusions in diamonds from Mir shows general similarities, but differences in details of trace-element patterns. Large compositional variations among inclusions of one phase (olivine, garnet, chromite) within single diamonds indicate that the chemical environment of diamond crystallisation changed rapidly relative to diamond growth rates in many cases. P-T conditions of formation were calculated from multiphase inclusions and from trace element geothermobarometry of single inclusions. The geotherm at the time of diamond formation was near a 35 mW/m² conductive model; that is indistinguishable from the Paleozoic geotherm derived by studies of xenoliths and concentrate minerals from Mir. A range of Ni temperatures between garnet inclusions in single diamonds from both Mir and Sputnik suggests that many of the diamonds grew during thermal events affecting a relatively narrow depth range of the lithosphere, within the diamond stability field. The minor differences between inclusions in Mir and Sputnik may reflect lateral heterogeneity in the upper mantle.     

贵州镇远马坪金伯利岩及其捕虏晶对金刚石成矿条件的指示意义

贵州镇远是中国金刚石原生矿找矿的重点区域之一。镇远地区马坪D1号岩体是1965年中国首次发现的含原生金刚石金伯利岩。该岩体岩石具典型的金伯利岩结构和组成特征,其中的锆石捕虏晶U–Pb年代学和Hf同位素分析结果表明,该地区存在未暴露的太古宙基底物质残余。基于壳幔耦合性规律,可能对应有古老的岩石圈地幔,这种古老的克拉通属性是金刚石形成的有利因素。但另一方面,马坪金伯利岩普遍含有伴生矿物含铬镁铝榴石,其CaO含量较高,多数属于G9(二辉橄榄岩)类型,不是全球富含金刚石的方辉橄榄岩原岩类型(G10),暗示当时的岩石圈发生了部分改造而可能不利于高品质金刚石的形成。需要注意的是,在金刚石找矿过程中,应该以详细的野外工作与岩石学对比研究为基础,同时依赖于金伯利岩及其相关的岩浆活动所携带的捕虏体/捕虏晶的研究,配合以岩浆成分来反演地幔源区特征,才能较全面地揭示古老大陆岩石圈的形成年龄与演化历史、物质组成与精细结构,以及大陆岩石圈根的厚度、热状态、氧逸度、流体作用等,进而为寻找金刚石提供重要的依据。     

地幔氧逸度的时空变化

地幔氧逸度是反映地幔氧化还原程度的参量,由温度、压力、岩石化学成分、矿物结构等共同作用控制.目前对上地幔氧逸度的研究主要针对镁橄榄石-磁铁矿-石英体系、含角闪石的橄榄岩体系和玄武岩(熔体)体系,通过实验岩石学方法进行.地幔氧逸度在垂直深度上随深度增加而减小受到普遍认可.天然样品和理论研究认为,岩石圈地幔底部的软流圈氧逸...     

Effect of oxygen fugacity and water on phase equilibria of a hydrous tholeiitic basalt

The influence of oxygen fugacity and water on phase equilibria and the link between redox conditions and water activity were investigated experimentally using a primitive tholeiitic basalt composition relevant to the ocean crust. The crystallization experiments were performed in internally heated pressure vessels at 200 MPa in the temperature range 940–1,220°C. The oxygen fugacity was measured using the H₂-membrane technique. To study the effect of oxygen fugacity, three sets of experiments with different hydrogen fugacities were performed, showing systematic effects on the phase relations and compositions. In each experimental series, the water content of the system was varied from nominally dry to water-saturated conditions, causing a range of oxygen fugacities varying by ~3 log units per series. The range in oxygen fugacity investigated spans ~7 log units. Systematic effects of oxygen fugacity on the stability and composition of the mafic silicate phases, Cr–spinel and Fe–Ti oxides, under varying water contents were recorded. The Mg# of the melt, and therefore also the Mg# of olivine and clinopyroxene, changed systematically as a function of oxygen fugacity. An example of the link between oxygen fugacity and water activity under hydrogen-buffered conditions is the change in the crystallization sequence (olivine and Cr–spinel) due to a change in the oxygen fugacity caused by an increase in the water activity. The stability of magnetite is restricted to highly oxidizing conditions. The absence of magnetite in most of the experiments allows the determination of differentiation trends as a function of oxygen fugacity and water content, demonstrating that in an oxide-free crystallization sequence, water systematically affects the differentiation trend, while oxygen fugacity seems to have a negligible effect.     

The Origins of Yakutian Eclogite Xenoliths

Owing to the association with diamonds, eclogite xenoliths havereceived disproportionate attention given their low abundancein kimberlites. Several hypotheses have been advanced for theorigin of eclogite xenoliths, from the subduction and high-pressuremelting of oceanic crust, to cumulates and liquids derived fromthe upper mantle. We have amassed a comprehensive data set,including major- and trace-element mineral chemistry, carbonisotopes in diamonds, and Rb–Sr, Sm–Nd, Re–Os,and oxygen isotopes in ultrapure mineral and whole-rock splitsfrom eclogites of the Udachnaya kimberlite pipe, Yakutia, Russia.Furthermore, eclogites from two other Yakutian kimberlite pipes,Mir and Obnazhennaya, have been studied in detail and offercontrasting images of eclogite protoliths. Relative to eclogitesfrom southern Africa and other Yakutian localities, Udachnayaeclogites are notable in the absence of chemical zoning in mineralgrains, as well as the degree of light rare earth element (LREE)depletion and unradiogenic Sr; lack of significant oxygen, sulfur,and carbon isotopic variation relative to the mantle; and intermineralradiogenic isotopic equilibration. Several of these eclogitescould be derived from ancient, recycled, oceanic crust, butmany others exhibit no evidence for an oceanic crustal protolith.The apparent lack of stable-isotope variation in the Udachnayaeclogites could be due to the antiquity of the samples and consequentlack of deep oceanic and biogenically diverse environments atthat time. Those eclogites that are interpreted to be non-recycledhave compositions characteristic of Group A eclogites from otherlocalities that also have been interpreted as being directlyfrom the mantle. At least two separate and diverse isotopicreservoirs are suggested by Nd isotopic whole-rock reconstructions.Most samples were derived from typical depleted mantle. However,two groups of three samples each indicate both enriched mantleand possible ultra-depleted mantle present beneath Yakutia duringthe late Archean and early Proterozoic. The vast majority ofeclogites studied from the Obnazhennaya pipe also exhibit characteristicsof Group A eclogites and are probably derived directly fromthe mantle. However, the eclogites from the Mir kimberlite aremore typical of other eclogites world-wide and show convincingevidence of a recycled, oceanic crustal affinity. We concurwith the late Ted Ringwood that eclogites can be formed in avariety of ways, both within the mantle and from oceanic crustalresidues. KEY WORDS: diamonds; eclogite xenoliths; isotopic composition; REE; Yakutia     

The redox states of basic and silicic magmas: a reflection of their source regions?

At present the best estimates of the oxygen fugacity of spinel-lherzolites that could be the source material of basic magmas is about five log units below the Ni–NiO buffer to one above it. However partially glassy basic lavas, ranging from MORBs to minettes, all with olivine on their liquidus, cover a wider range, and may have oxygen fugacities that extend to four log units above NNO. Surprisingly the range of oxygen fugacities observed in silicic lavas and ashflows with quartz phenocrysts is smaller, despite a crustal dominated evolution. The peralkaline silicic lava type pantellerite is the most reduced, equivalent to MORBs, whereas the large volume ashflows with phenocrysts of hornblende and/or sphene are the most oxidised. As the concentration of water in the basic lavas is correlated with increase in their redox state, it would seem that water could be the agent of this increase. That this is unlikely is seen in the behavior of silicic ashflows and lavas, particularly those of Yellowstone. Here the silicic magmas of the last 2Ma contain about 2 wt% FeO_(total), and typically phenocrysts of fayalite, quartz and Fe–Ti oxides. Despite extensive exchange of the ¹⁸O of the magma with meteoric water after caldera collapse (Hildreth et al. 1984), there is no displacement of the redox equilibria. Thus the thermal dissociation of molecular H₂O to H₂, and its subsequent diffusive loss to cause oxidation must have been minimal. This could only be so if the activity of water was small, as it would be if H₂O reacted with the silicate liquid to form OH groups (Stolper 1982). The conclusion is that silicic magmas with small amounts of iron and large amounts of water do not have their redox states reset, which in turn presumably reflect their generation. By analogy basic magmas with large amounts of iron and far less water are even less likely to have their redox equilibria disturbed, so that their oxygen fugacities will also reflect their source regions. The effect of pressure on the ferric-ferrous equilibrium in basic magmas can be calculated from experimental measurements of the partial molar volumes of FeO and Fe₂O₃, and their pressure derivatives V/P, in silicate liquids. The effect of pressure is found to be about the same on the liquid as it is for various solid oxygen buffers. Accordingly there should be mantle source regions covering the same range of oxygen fugacity as that found in basic lavas, but so far samples of spinel-lherzolite of equivalent oxygen fugacity to minettes or other potassic lavas have not been found. Whether or not the redox state of phlogopite-pyroxenites is equivalent to these potassic lavas cannot be established without experiment.     

Oxygen fugacity dependence of Ni,Co, Mn,Cr, V,and Si partitioning between liquid metal and magnesiowüstite at 9–18 GPa and 2200°C

The oxidation states of Ni, Co, Mn, Cr, V and Si in magnesiowüstite have been determined in metal-oxide distribution experiments using a multi anvil apparatus at 9 and 18 GPa and 2200°C as a function of oxygen fugacity. Despite limitations to control oxygen fugacity by applying conventional buffering methods in high pressure experiments, a wide range of redox-conditions (3 log bar units) has been imposed to the metal-oxide partitioning experiments by varying the Si/O ratio of the starting material. The oxygen fugacity was calculated according to the Fe-FeO equilibrium between the run products. The ability to impose different oxygen fugacities by varying the starting material is confirmed by the large variation of element partitioning coefficients obtained at constant pressure and temperature. The calculated valences at both pressures investigated are divalent for Co, Mn, V and 4+ for Si. The results for Cr (∼2.5+) and Ni (∼1.5+) indicate non-ideal mixing of Ni and Cr in at least one of the product phases. Because the application of 1 bar activity coefficients for Ni and Cr in metal alloys does not change these valences, non-ideal mixing in magnesiowüstite or significantly larger non-ideal mixing properties of Ni and Cr in metal alloys at high pressure are likely to be responsible for the apparent valences. Omitting such non-ideal mixing properties when extrapolating high-pressure element partitioning data may be significant. The elements Cr, V and Mn become siderophile (D_M^met/ox > 1) at 9–18 GPa and 2200°C at oxygen fugacities below IW-2.7 to IW-3.7. Considering, in addition, the influence of temperature, the depletion of Cr, Mn and V in the Earth’s mantle may be due, at least partly, to siderophile behavior at high pressure and temperature.     

Hydration of mantle olivine under variable water and oxygen fugacity conditions

The incorporation of H into olivine is influenced by a significant number of thermodynamic variables (pressure, temperature, oxygen fugacity, etc.). Given the strong influence that H has on the solidus temperature and rheological behavior of mantle peridotite, it is necessary to determine its solubility in olivine over the range of conditions found in the upper mantle. This study presents results from hydration experiments carried out to determine the effects of pressure, temperature, and the fugacities of H₂O and O₂ on H solubility in San Carlos olivine at upper mantle conditions. Experiments were carried out at 1–2 GPa and 1,200 °C using a piston-cylinder device. The fugacity of O₂ was controlled at the Fe⁰–FeO, FeO–Fe₃O₄, or Ni⁰–NiO buffer. Variable duration experiments indicate that equilibration is achieved within 6 h. Hydrogen contents of the experimental products were measured by secondary ion mass spectrometry, and relative changes to the point defect populations were investigated using Fourier transform infrared spectroscopy. Results from our experiments demonstrate that H solubility in San Carlos olivine is sensitive to pressure, the activity of SiO₂, and the fugacities of H₂O and O₂. Of these variables, the fugacity of H₂O has the strongest influence. The solubility of H in olivine increases with increasing SiO₂ activity, indicating incorporation into vacancies on octahedral lattice sites. The forsterite content of the olivine has no discernible effect on H solubility between 88.17 and 91.41, and there is no correlation between the concentrations of Ti and H. Further, in all but one of our experimentally hydrated olivines, the concentration of Ti is too low for H to be incorporated dominantly as a Ti-clinohumite-like defect. Our experimentally hydrated olivines are characterized by strong infrared absorption peaks at wavenumbers of 3,330, 3,356, 3,525, and 3,572 cm^?1. The heights of peaks at 3,330 and 3,356 cm^?1 correlate positively with O₂ fugacity, while those at 3,525 and 3,572 cm^?1 correlate with H₂O fugacity.     

The Olivine--Orthopyroxene--Spinel Oxygen Geobarometer, the Nickel Precipitation Curve, and the Oxygen Fugacity of the Earth's Upper Mantle

The common upper mantle assemblage olivine-orthopyroxene-spinelmay be used to calculate the oxygen fugacity at which mantle-derivedperidotites have equilibrated. The equilibrium has been calibratedusing the large amount of existing data on the thermodynamicproperties of each phase in this assemblage. A by-product ofthis procedure is a new calibration of the olivine-spinel Mg-Fe²⁺exchange geothermometer. Application of the equilibrium to avariety of peridotite xenoliths indicates that the oxygen fugacityof the upper mantle lies between the quartz-fayalite-magnetite(QFM) and w?stite-magnetite (WM) oxygen buffers; the few apparentexceptions to this rule may be due to analytical error, particularlyin the Fe³⁺ content of the spinet phase. In fact, the determinationof Fe³⁺ in spinet is at present the limiting factor in the accurateapplication of the method: within this limitation, the presentlyavailable evidence suggests that the oxygen fugacity of themantle may be laterally homogeneous over wide regions, but mayalso show small differences between these regions. The fluidspecies in the system C-H-O at such oxygen fugacities are predominantlyCO₂ and/or H₂O, and not CH₄/H₂ The minimum possible oxygen fugacity of the mantle is givenby the nickel content of olivine in equilibrium with orthopyroxene;for typical mantle compositions this minimum curve is virtuallycoincident with the iron-w?stite (IW) oxygen buffer.     

Peridotitic diamonds from the Slave and the Kaapvaal cratons—similarities and differences based on a preliminary data set

A comparison of the diamond productions from Panda (Ekati Mine) and Snap Lake with those from southern Africa shows significant differences: diamonds from the Slave typically are un-resorbed octahedrals or macles, often with opaque coats, and yellow colours are very rare. Diamonds from the Kaapvaal are dominated by resorbed, dodecahedral shapes, coats are absent and yellow colours are common. The first two features suggest exposure to oxidizing fluids/melts during mantle storage and/or transport to the Earth's surface, for the Kaapvaal diamond population.

Comparing peridotitic inclusions in diamonds from the central and southern Slave (Panda, DO27 and Snap Lake kimberlites) and the Kaapvaal indicates that the diamondiferous mantle lithosphere beneath the Slave is chemically less depleted. Most notable are the almost complete absence of garnet inclusions derived from low-Ca harzburgites and a generally lower Mg-number of Slave inclusions.

Geothermobarometric calculations suggest that Slave diamonds originally formed at very similar thermal conditions as observed beneath the Kaapvaal (geothermal gradients corresponding to 40–42 mW/m² surface heat flow), but the diamond source regions subsequently cooled by about 100–150 °C to fall on a 37–38 mW/m² (surface heat flow) conductive geotherm, as is evidenced from touching (re-equilibrated) inclusions in diamonds, and from xenocrysts and xenoliths. In the Kaapvaal, a similar thermal evolution has previously been recognized for diamonds from the De Beers Pool kimberlites. In part very low aggregation levels of nitrogen impurities in Slave diamonds imply that cooling occurred soon after diamond formation. This may relate elevated temperatures during diamond formation to short-lived magmatic perturbations.

Generally high Cr-contents of pyrope garnets (inside and outside of diamonds) indicate that the mantle lithosphere beneath the Slave originally formed as a residue of melt extraction at relatively low pressures (within the stability field of spinelperidotites), possibly during the extraction of oceanic crust. After emplacement of this depleted, oceanic mantle lithosphere into the Slave lithosphere during a subduction event, secondary metasomatic enrichment occurred leading to strong re-enrichment of the deeper (>140 km) lithosphere. Because of the extent of this event and the occurrence of lower mantle diamonds, this may be related to an upwelling plume, but it may equally just reflect a long term evolution with lower mantle diamonds being transported upwards in the course of “normal” mantle convection.     

Crystal forms and surface textures of alluvial diamonds from the Western Region of the Central African Republic

The most common crystal forms of the diamonds from the alluvial deposits in the Western Region of the Central African Republic were examined by scanning electron microscope (SEM) in an attempt to determine their geological history. The marks observed are related to two distinct periods in the geological history of the diamonds: the magmatic episode and their hydraulic transport. The effects of significant magmatic corrosion undergone by the diamonds during their ascent from the upper mantle are shown by the predominance of rhombododecahedral forms over octahedral forms and the frequent occurrence on the crystal faces of pyramidal depressions with triangular (111) or square (100) bases, as well as of V-shaped figures (111) or stepped figures (on the faces around the ternary axes). Some impact marks probably occurred during the explosive episode of kimberlite extrusion. Other impact marks, the marks of general wear, and the high proportion of gemstone-quality diamonds indicate the lengthy transport. They thus also indicate that the diamonds have undergone a prolonged geological history after the erosion of the kimberlite. This suggests that the kimberlite are separated from the Carnot Sandstone Formation by a considerable distance. The diamonds were stored in Albian-Maastrichtian rocks before they become concentrated in the Recent alluvium.