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Crystallographic relations between four diamonds from the Yubileinaya pipe (Yakutia) and inclusions of eight olivine crystals in them are first studied by the EBSD method. Crystallographic coincidence between the olivine and diamond has been revealed in 15 samples, though we failed to make an unambiguous conclusion about the sequence of the mineral crystallization. It is confirmed that the new approach is promising for elucidation of the regularities of the mutual orientation of diamond and inclusion. However, more samples are required to establish whether the olivines formed earlier than the diamonds (protogenetic inclusions) or synchronously with them (syngenetic inclusions). © 2015, V.S. Sobolev IGM, Siberian Branch of the RAS. Published by Elsevier B.V. All rights reserved.

Subduction tectonics imposes an important role in the evolution of the interior of the Earth and its global carbon cycle; however, the mechanism of the mantle-slab interaction remains unclear. Here, we demonstrate the results of high-pressure redox-gradient experiments on the interactions between Mg-Ca-carbonate and metallic iron, modeling the processes at the mantle-slab boundary; thereby, we present mechanisms of diamond formation both ahead of and behind the redox front. It is determined that, at oxidized conditions, a low-temperature Ca-rich carbonate melt is generated. This melt acts as both the carbon source and crystallization medium for diamond, whereas at reduced conditions, diamond crystallizes only from the Fe-C melt. The redox mechanism revealed in this study is used to explain the contrasting heterogeneity of natural diamonds, as seen in the composition of inclusions, carbon isotopic composition, and nitrogen impurity content.

Oxygen fugacity ( $$ f_{{{\text{O}}_{ 2} }} $$ ) is a fundamental but little known intensive variable in mantle processes. It influences the P/T position of a mantle solidus and the composition of mantle-derived melts and fluids and constrains mantle-core equilibria and a number of geophysical properties of the mantle. An important source of information on oxidation states is the ferric–ferrous iron ratio in mantle spinels. Since the magnetite component is low in mantle spinels, normal analytical errors translate into considerable $$ f_{{{\text{O}}_{ 2} }} $$ uncertainties. In this study, we analyzed the Fe3+–Fetot ratio of chromites present as inclusions in diamond and other mantle-related occurrences by point-source Mossbauer spectroscopy using single-crystal absorbers as well as conventional Mossbauer spectroscopy using powder absorbers. The studied spinels have been previously analyzed by single-crystal X-ray diffraction and electron microprobe. The ferric–ferrous ratios found are normally similar to the different techniques apart from some samples where a large number of grains have been used for the analyses (powder absorbers). The general agreement between the different techniques allows us to conclude that the studied chromites are stoichiometric. However, conventional Mossbauer spectroscopy on powder absorbers should be conducted with great care, since the method requires a relatively large amount of sample material. Spinel frequently occurs as small grains, and the large number of crystals required may possess different degrees of oxidation/alteration and, consequently, different ferric–ferrous ratio leading to possible errors in the interpretation of the results.

After the discovery of metamorphic coesite in crustal rocks from the Western Alps (Italy) and the Western gneiss region (Norway) in the mid 1980s of the last century, metamorphic diamond was observed only a few years later “in situ” in the Kokchetav Massif (Kazakhstan). Findings of such coesite- and diamond-bearing ultrahigh pressure metamorphic (UHP) rocks with protoliths formed or embedded in crustal levels and subsequently experienced PT-conditions within or even higher than the coesite stability field have dramatically changed our geodynamic view of orogenetic processes. These occurrences provide evidence that crustal rocks were subducted into mantle depths and exhumed to the surface. Recent studies even suggest continental subduction to depths exceeding 300 km. These rocks have been extensively studied and many new and important observations have been made. Thus far, more than 350 papers have been published on various aspects of Kokchetav UHP rocks. The Kokchetav Massif of northern Kazakhstan is part of one of the largest suture zones in Central Asia and contains slices of HP and UHP metamorphic rocks. Classical UHP rocks mainly occur in the Kumdy Kol, Barchi Kol and Kulet areas, and include a large variety of lithologies such as calcsilicate rocks, eclogite, gneisses, schists, marbles of various compositions, garnet–pyroxene–quartz rocks, and garnet peridotite. Most of them contain microdiamonds; some of which reach a grain size of 200 μm. Most diamond grains show cuboid shapes but in rare cases, diamonds within clinozoisite gneiss from Barchi Kol occur as octahhedral form. Microdiamonds contain highly potassic fluid inclusions, as well as solid inclusions like carbonates, silicates and metal sulfides, which favour the idea of diamond formation from a C–O–H bearing fluid. Nitrogen isotope data and negative δ13C values of Kokchetav diamonds indicate a metasedimentary origin. PT-estimates of Kokchetav UHP rocks yield peak metamorphic conditions of at least 43 kbar at temperatures of about 950–1000 °C. Some zircon separates show inherited Proterozoic cores and 537–530 Ma UHP metamorphic mantle zones. Several Ar–Ar-ages on micas scatter around 529–528 and 521–517 Ma and reflect different stages of the exhumation history. Migmatization occurred during exhumation at about 526–520 Ma. Isotopic studies on calcsilicate rocks confirm a metasedimentary origin: δ18O values of garnet and clinopyroxene of a layered calcsilicate rock rule out the possibility having a primitive mantle protolith. Similar studies on eclogites indicate their basaltic protolith having experienced water–rock interaction prior to UHP metamorphism. A number of unique mineralogical findings have been made on Kokchetav UHP rocks. K-feldspar exsolutions in clinopyroxene demonstrate that potassium can be incorporated into the cpx-structure under upper mantle pressures. Other significant observations are coesite exsolutions in titanite, quartz-rods in cpx, the discovery of K-tourmaline as well as new minerals like kokchetavite, a hexagonal polymorph of K-feldspar and kumdykolite, an orthorhombic polymorph of albite. The Kokchetav UHP rocks represent a unique and challenging stomping ground for geoscientists of various disciplines. From crystallography, petrology and geochemistry to geophysics and geodynamics/geotectonics – it concerns all who are interested in the diverse metamorphic processes under upper mantle conditions.

Introduction Earth’s carbon, derived from planetesimals in the 1 AU region during accretion of the Solar System, still retains similarities to carbon found in meteorites (Marty et al. 2013) even after 4.57 billion years of geological processing. The range in isotopic composition of carbon on Earth versus meteorites is nearly identical and, for both, diamond is a common, if volumetrically minor, carbon mineral (Haggerty 1999). Diamond is one of the three native carbon minerals on Earth (the other two being graphite and lonsdaleite). It can crystallize throughout the mantle below about 150 km and can occur metastably in the crust. Diamond is a rare mineral, occurring at the part-per-billion level even within the most diamondiferous volcanic host rock although some rare eclogites have been known to contain 10–15% diamond. As a trace mineral it is unevenly distributed and, except for occurrences in metamorphosed crustal rocks, it is a xenocrystic phase within the series of volcanic rocks (kimberlites, lamproites, ultramafic lamprohyres), which bring it to the surface and host it. The occurrence of diamond on Earth’s surface results from its unique resistance to alteration/dissolution and the sometimes accidental circumstances of its sampling by the volcanic host rock. Diamonds are usually the chief minerals left from their depth of formation, because intact diamondiferous mantle xenoliths are rare. Diamond has been intensively studied over the last 40 years to provide extraordinary information on our planet’s interior. For example, from the study of its inclusions, diamond is recognized as the only material sampling the “very deep” mantle to depths exceeding 800 km (Harte et al. 1999; McCammon 2001; Stachel and Harris 2009; Harte 2010) although most crystals (~95%) derive from shallower depths (150 to 250 km). Diamonds are less useful in determining carbon fluxes on Earth because they provide only a small, …

article i nfo The world's largest diamondiferous eclogite (8.8 kg, UD-111/02) from the Udachnaya kimberlite, Siberia, is the subject of this investigation. High-resolution X-ray computed tomography (HRXCT), chemistry of host minerals and diamond inclusions, stratigraphy of the diamonds (cathodoluminescence zoning), and carbon isotopes have been obtained. HRXCT images, 3-d models, and subsequent detailed dissection of this Group B eclogite revealed linear distributions of diamonds along alteration zones. Both unusual multiple-diamond clusters with dodecahedral morphologies, and distinctive internal zoning recorded by cathodoluminescence analyses are indicative of multiple stages of diamond growth and resorption in UD-111-02. Carbon-isotope ratios (δ 13 C) of 16 diamonds have a total range of ~7‰ (−2.0 to −9.2‰), with the majority at −5.4‰.

Clinopyroxene and orthopyroxene are generally rare in kimberlites, and believed to originate from disintegrated mantle and crustal xenoliths. We report occurrence of inclusions of low-Ca and high-Ca pyroxenes in the olivine phenocrysts in the Udachnaya-East hypabyssal kimberlite (Yakutia, Russia), and make inferences on their relationships to the kimberlite magma. Pyroxenes are only found as either resorbed macrocrysts or small inclusions in olivine; both types are being very rare and volumetrically insignificant. All clinopyroxene and majority of orthopyroxene inclusions are hosted in the olivine cores (Fo86-92) that are compositionally similar to olivine macrocrysts. Major and trace element compositions of clinopyroxene inclusions in olivine phenocrysts and macrocrysts are similar, and resemble compositions of clinopyroxene from lherzolite xenoliths hosted in the Udachnaya-East kimberlite. Their high Na2O and Cr2O3 abundances (0.65-2.55 and 0.6-2.8 wt%, respectively) suggest deep mantle origin (>4.5 GPa). The majority of clinopyroxene inclusions have convex-upward trace element patterns that imply kimberlite-like compositions for the hypothetical equilibrium melts. Re-equilibration of clinopyroxene inclusions with the host kimberlite liquid through micro-cracks in olivine is our preferred explanation in this case, however, we cannot exclude their high-pressure crystallisation from the protokimberlite melt. Orthopyroxene inclusions show significant compositional overlap with the low-Al orthopyroxene from the Udachnaya peridotite nodules. Where such inclusions occur in olivine fragments and contact with the kimberlite groundmass, they are strongly resorbed and partially replaced by monticellite. The mantle origin of orthopyroxene and its host olivine and disequilibrium relationships with the kimberlite melt is most likely. Both clinopyroxene and orthopyroxene are completely absent in the kimberlite groundmass. We conclude that the parental melt of the Udachnaya-East kimberlite was not saturated in either clinopyroxene or orthopyroxene at low pressure. This argues against a perceived mafic-ultramafic lineage of the kimberlite primary melt, and provides further support for its essentially carbonate-chloride composition.

Article history:Received 23 January 2008Accepted 29 June 2008Available online 10 July 2008Keywords:SHRIMP dataU/PbZirconKokchetavUHP metamorphismpartial melting The Kokchetav Massif of northern Kazakhstan is the best-known metamorphic diamond locality amongnumerous ultrahigh-pressure (UHP) terranes in the world. At the Kumdy-Kol deposit, diamondiferous rocksare interbedded with granitic gneisses, and biotite gneisses; some have been migmatized. Some granitegneisses and migmatites were formed by partial melting of diamondiferous rocks. To verify such suggestion,sensitive high resolution ion microprobe (SHRIMP) U–Pb dating of zoned zircons from migmatites at theKumdy-Kol regionwas performed to constrain the age of partial melting of the Kokchetav UHP metamorphicrocks. Most age data from core and rim domains of zircon separates are concordant. The apparent 206 Pb/ 238 Uages for core and rim domains of zirconsare nearly identical within analytical error. All SHRIMP analyses ofzircons from four samples fall in the range 508–538 Mawith the weighted mean age for all zircon domains at526±2.1 (MSWD=1.7). Our data show that migmatization of UHP pelites occurred later than the peakmetamorphism (537±9 Ma) and the decompression partial melting took place during exhumation ofdiamondiferous rocks from mantle depths to amphibolite-facies conditions at mid-crustal levels (507±8 Ma).© 2008 Elsevier B.V. All rights reserved.

The geochemistry of mineral inclusions in diamonds is an important source of information on the composition of continental lithospheric mantle at depths exceeding 120-150 km. At these depths two main types of geological environment support diamond formation: they are ultramafic (or peridotitic) (U-type) and eclogitic (E-type) environments as shown by minerals that occur as inclusions in diamonds and compose xenoliths of diamondiferous peridotites and eclogites in kimberlites. In primary, diamond-bearing kimberlite and lamproite rocks the ratio of diamonds from these two geological environments varies widely between localities. However, U-type diamonds dominate in the overwhelming majority of diamond occurrences worldwide. Olivine is the most typical inclusion in U-type diamonds and coexists both as touching or non touching inclusions with enstatite, pyrope, chromite in harzburgitic or dunitic (without enstatite) assemblages and Cr-rich diopside (lherzolitic and wehrlitic assem- blages). More than 260 olivine inclusions sometimes associated with enstatite, Cr-rich diopside, pyrope and chromite were studied from diamonds of major Siberian mines, including Aikhal, Yubileinaya, Internatsionalnaya, Komsomolskaya, Sytykanskaya and alluvials from the north-eastern part of the Siberian Craton. Most olivine inclusions were prepared for analysis on a single polished surface with diamond. Olivine from diamonds of the Snap Lake dyke system (Canada) were studied for comparison. The olivine composition in eight xenoliths of diamondiferous peridotites from Udachnaya pipe, representing the rarest mantle samples, was also re-examined. Inclusions were analyzed for major and minor elements with an electron microprobe so as to obtain high precision and accuracy, especially for Ni, Ca, Mn, Cr, Co and Al. Minor-element abundances of the overwhelming majority of analyzed olivine vary within the following ranges in wt.% (NiO 0.320-0.408; CaO 0.005-0.045; MnO 0.079-0.131; Cr2O3 0.013-0.115; CoO 0.009-0.022 and Al2O3 0.007-0.039). About 70 % of all studied olivines demonstrate very low CaO (< 0.02 wt.%), which reflects a relatively low temperature of equilibration for the lherzolitic paragenesis, or lack of clinopyroxene associated with olivine. Some olivines of anomalous composition are detected in microdiamonds only. They contain relatively low forsterite (Fo) (100 Mg/(Mg+Fe)) along with very low MnO and unusually high NiO (86.6-90.0; 0.063-0.076 wt.% and 0.461-0.556 wt.%, respectively). The grain of such composition located in the inner diamond growth zone is associated with an olivine grain of "normal" composition in the outer zone of one microdiamond sample. Such a difference in olivine compositions may indicate an enrichment of the diamond growing source in garnet at the initial stages of diamond growth. The high-precision approach to trace elements by electron probe opens new possibilities for more accurate estimation of olivine assemblages, the temperature and pressure of diamond formation, and identification of clearly anomalous olivine compositions which may represent a crustal signature.

Nanometer-size P/K-rich silica glass (former melt) inclusions were identified within metamorphic microdiamonds from garnets of ultrahigh-pressure (UHP) gneisses of the Kokchetav and the Erzgebirge massifs by analytical electron microscopy (AEM). The chemical characteristics of these inclusions within microdiamonds are surprisingly similar among various gneissic rocks from both Kokchetav and Erzgebirge, but are significantly different from the Si-poor ultrapotassic fluid inclusions within microdiamonds from garnets of the Kokchetav UHP marble. These contrasting findings not only provide constraints on the characteristics/compositions of the formation media of metamorphic microdiamonds, but also imply that the formation media must have been buffered by the hosting rocks, resulting in the observed diversities as reported here. In addition, depending on the rock types and thus on the nature of the formation media from which metamorphic microdiamonds were formed, the respective characteristic morphologies of the microdiamonds differ. The P/K-rich silica melt tends to form octahedral or cubo-octahedral microdiamonds within garnet in gneissic rocks, whereas the Si-poor ultrapotassic fluid tends to form spheroids/cuboid microdiamonds with rugged surfaces within garnet in marble. Consequently, the buffered media in hosting rocks played a decisive role in determining the different morphologies and growth rates/mechanisms of metamorphic microdiamonds in general.

Komsomolskaya high-Cr, harzburgitic-garnet, multiple diamond inclusions exhibit extremely variable and unusual LREE patterns. The high Cr2O3 contents of these diamond inclusions are exceptional, and indicate a possible genesis intermediate between that of harzburgitic and lherzolitic garnets. Both the major- and trace-element compositions of the garnet inclusions within a single diamond are unique, illustrating that each diamond has experienced a distinctly different chemical environment during its formation, in some cases even varying significantly during different episodes of growth within one diamond. Results of this study emphasize that such diamonds have been subjected to extreme changes in P-T-X conditions during their complex growth histories.

We have performed dissections of two diamondiferous eclogites (UX-1 and U33/1) from the Udachnaya kimberlite, Yakutia in order to understand the nature of diamond formation and the relationship between the diamonds, their mineral inclusions, and host eclogite minerals. Diamonds were carefully recovered from each xenolith, based upon high-resolution X-ray tomography images and three-dimensional models. The nature and physical properties of minerals, in direct contact with diamonds, were investigated at the time of diamond extraction. Polished sections of the eclogites were made, containing the mould areas of the diamonds, to further investigate the chemical compositions of the host minerals and the phases that were in contact with diamonds. Major- and minor-element compositions of silicate and sulfide mineral inclusions in diamonds show variations among each other, and from those in the host eclogites. Oxygen isotope compositions of one garnet and five clinopyroxene inclusions in diamonds from another Udachnaya eclogite (U51) span the entire range recorded for eclogite xenoliths from Udachnaya. In addition, the reported compositions of almost all clinopyroxene inclusions in U51 diamonds exhibit positive Eu anomaly. This feature, together with the oxygen isotopic characteristics, is consistent with the well-established hypothesis of subduction origin for Udachnaya eclogite xenoliths. It is intuitive to expect that all eclogite xenoliths in a particular kimberlite should have common heritage, at least with respect to their included diamonds. However, the variation in the composition of multiple inclusions within diamonds, and among diamonds, from the same eclogite indicates the involvement of complex processes in diamond genesis, at least in the eclogite xenoliths from Yakutia that we have studied.

Chemical compositions were determined on mineral inclusions recovered from 290 microdiamonds ( 1 mm) from the same sources, and worldwide data for olivines and chromites. Although there are general similarities, notable exceptions were detected in about 10% of the inclusions from microdiamonds. For each of the pipes, anomalous compositions occur between the micro- and macrodiamond inclusions, but in different proportions, sometimes as high as 50% of the inclusions. Our study has demonstrated that mineral inclusions in microdiamonds are considerably more variable in their compositions and parageneses compared with inclusions in macrodiamonds. Significant compositional anomalies in inclusions from microdiamonds include: (1) garnets containing pyroxene solid solution (majoritic component) both in U- and E-type microdiamonds from three pipes: Yubileynaya, Komsomolskaya and Krasnopresnenskaya. The moles of Si (pfu) in these garnets range from 3.07 to 3.13 and as high as 3.29, on the basis of 12 oxygens, along with a notable contents of Na 2 O in two eclogitic garnets (0.43 and 0.93 wt.%) and uniquely high Cr 2 O 3 and CaO contents in an ultramafic garnet of wehrlitic paragenesis; (2) coexisting wehrlitic garnets in a single microdiamond, one majoritic, the other normal, both with distinct +Eu anomalies, considered as signatures of crustal protoliths for the precursors to these garnets; (3) olivines with relatively low Fo (86–89) and high-NiO contents (0.46–0.64 wt.%), from Yubileynaya and Sytykanskaya microdiamonds; (4) chromites containing high-TiO 2 (up to 4.7 wt.%) and some extremely rich in MgO (Mg# 80). It is concluded that many of these compositional features observed may be related to a deeper origin for the microdiamond source region (>300 km), for at least a 10–30% portion of microdiamonds from each Yakutian pipe.

Multiple inclusions of minerals in diamonds from the Snap Lake/King Lake kimberlites of the southeastern Slave craton in Canada have been analyzed for trace elements to elucidate the petrogenetic history of these inclusions, and of their host diamonds. As observed worldwide, the harzburgitic-garnet diamond inclusions (DIs) possess sinusoidal REE patterns that indicate an early depletion event, followed by metasomatism by LREE-enriched, HREE-depleted fluids. Furthermore, these fluids appear to contain appreciable concentrations of LILE and HFSE, based on the increasing abundances of these elements in the olivine inclusion that occurs at the outer portion of a diamond compared to that near the core. The compositions of these fluids are probably a mixture of hydrous-silicic melt, carbonatitic melt, and brine, similar to the compositions of micro-inclusions in diamonds reported by Navon et al. (2003). Comparison between the compositions of majoritic and normal harzburgitic garnets shows that the former are more depleted in terms of major/minor elements (higher Cr#) but significantly more enriched in the REE (up to ∼10×). This characteristic may indicate the higher susceptibility for metasomatic enrichment of previously more depleted garnets. Garnets of eclogitic paragenesis show strong LREE-depleted patterns, whereas the coexisting omphacite inclusion has relatively flat light- and middle-REE but depleted HREE. Whole-rock reconstruction from coexisting garnet and omphacite inclusions indicates that the protolith of these inclusions was probably the extrusive section of an oceanic crust, subducted beneath the Slave craton.

Thin sections of ultrahigh pressure (UHP) metamorphic rocks from the Dora Maira Massif (Italy) and the Kokchetav Massif (Kazakhstan) were investigated using the hot cathode cathodoluminescence (CL) technique. Coloured images of important, but otherwise invisible growth features could be easily identified with this tool within seconds. These features are in excellent correlation with chemical variations of minerals revealed by electron microprobe (EMP). Generally, CL is induced by activator-elements (e.g. Mn and REE) and lattice defects whereas so-called quencher-elements like Fe may reduce or even extinct luminescence. Since X-ray-intensity mapping images (MAPS) of minerals can take up to 50 hours, the CL-method represents an ideal and rapid approach prior to chemical characterization. In addition to typical carbonates such as calcite, Mg-bearing calcite and dolomite, a number of rock forming and accessory minerals including Mg- and Mg-Ca-garnets, diopsidic and jadeitic pyroxenes, kyanite, K-feldspar, quartz, coesite, diamond, zircon, apatite, and bearthite were examined. Features observed in garnets include small-scale oscillatory zoning patterns, changes in morphology during growth as well as different crack generations which were partly annealed. SiO2 phases (coesite, quartz, chalcedony) as well as exsolution textures of dolomite and Mg-bearing calcite are easy to distinguish due to their different CL-colours. Pyroxene displays complex zonation patterns and -to some extent- exsolution-textures of K-feldspar. Kyanite reveals distinct growth zones; in combination with mineral inclusion studies it is possible to discriminate between different kyanite-forming reactions. The different crystallographical orientation of twinned kyanite crystals leads to various luminescence colours, thus, the suture of the twin plane is well defined. Prior to SHRIMP analyses, knowledge of the internal structures of zircon is indispensable. Even very tiny coesite crystals are easy to distinguish from quartz or chalcedony by their disparate luminescence colours. Accessory luminescent minerals like diamond, apatite, bearthite are easy to identify in thin section even if they occur in very small abundance within the matrix or as inclusions. The CL method presented here for UHP-metamorphic rocks is recommended as a pathfinder for the discovery of internal structures of minerals prior to their chemical characterization using EMP.

The primary garnet (pyrope-almandine)-omphacite (Cpx 1, 6.5–7 wt% Na2O)-sulfide (Fe-Ni-Co mss) assemblage of the two diamondiferous eclogite xenoliths studied (U33/1 and UX/1) experienced two mantle metasomatic events. The metasomatic event I is recorded by the formation of platy phlogopite (~ 10 wt% K2O), prior to incorporation of the xenoliths in the kimberlite. The bulk of the metasomatic alteration, consisting of spongy-textured clinopyroxene (Cpx 2A, 1–3 wt% Na2O), coarser-grained clinopyroxene (Cpx 2B, 2–5 wt% Na2O), pargasitic amphibole (~ 0.8 wt% K2O; 3–3.5 wt% Na2O), kelyphite (Cpx 3, mostly

Large diamonds (10–200 carats) from Udachnaya, Mir, and Aikhal kimberlite pipes of Yakutia contain variable mineral inclusions typical of diamonds of smaller size. Among these inclusions, extracted from outer portions of these diamonds, the majority are garnets of harzburgitic paragenesis, with a small number of inclusions belonging to lherzolitic and eclogitic groups, in addition to chromite diamond inclusions (DIs). The most striking feature of the garnet DIs is the sinusoidal rareearth elements (REE) patterns observed for all harzburgitic, and some lherzolitic garnets, whereas eclogitic garnets form normal LREE-depleted patterns. These sinusoidal REE patterns are indicative of a complex petrogenesis for the garnets, involving partial-melting, followed by metasomatic enrichment, particularly of the LREEs/MREEs. The metasomatic agents were probably not those of carbonatitic fluids, but rather C-O-H-N-S fluids, as indicated by the negative anomalies of Ba and Sr in the garnets. The general axiom among investigators that most, if not all, DIs are syngenetic with their diamonds is seriously questioned. The petrogenetic history of the harzburgitic garnet DIs involved complex processing prior to their diamond encapsulation. That is, the garnet DIs retained a signature of their earlier, pre-diamond encapsulation history. This result is taken as proof that basically all harzburgitic garnet DIs are non-syngenetic (i.e., protogenetic) with their host diamonds.

For the first time, three-dimensional, high-resolution X-ray computed tomography (HRXCT) of an eclogite xenolith from Yakutia has successfully imaged diamonds and their textural relationships with coexisting minerals. Thirty (30) macrodiamonds (≥1 mm), with a total weight of just over 3 carats, for an ore grade of some 27,000 ct/ton, were found in a small (4 × 5 × 6 cm) eclogite, U51/3, from Udachnaya. Based upon 3-D imaging, the diamonds appear to be associated with zones of secondary alteration of clinopyroxene (Cpx) in the xenolith. The presence of diamonds with secondary minerals strongly suggests that the diamonds formed after the eclogite, in conjunction with meta-somatic input(s) of carbon-rich fluids. Metasomatic processes are also indicated by the non-systematic variations in Cpx inclusion chemistry in the several diamonds. The inclusions in the diamonds vary considerably in major- and trace-element chemistry within and between diamonds, and do not correspond to the minerals of the host eclogite,...

Mineral inclusions in diamonds provide an important source of information about the composition of the continental lithosphere at depths exceeding 120–150 km, i.e., within the diamond stability field. Fossilized high pressures in coesite inclusions from a Venezuela diamond have been identified and measured by using laser Raman and synchrotron x-ray microanalytical techniques. Micro-Raman measurements on an intact inclusion of remnant vibrational band shifts give a high confining pressure of 3.62 (±0.18) GPa. Synchrotron single-crystal diffraction measurements of the volume compression are in accord with the Raman results and also revealed direct structural information on the state of the inclusion. In contrast to olivine and garnet inclusions, the thermoelasticity of coesite favors accurate identification of pressure preservation. Owing to the unique combination of physical properties of coesite and diamond, this “coesite-in-diamond” geobarometer is virtually independent of temperature, allowing an estimation of the initial pressure of Venezuela diamond formation of 5.5 (±0.5) GPa.

Isotopic and geochemical data of the Zerenda series metamorphic rocks from the Kokchetav massif are reported. Some of these rocks contain microdiamond inclusions in garnets and other indicators of ultrahigh pressure metamorphism (P > 40 kbar, T = 900–1000 °C). The diamond-bearing rocks exhibit distinctive geochemical characteristics compared to typical crustal rocks. The REE patterns range from LREE depleted to slightly LREE enriched [chondrite normalized (La/Yb)N– 0.1–5.4] with a negative Eu anomaly. They are depleted in incompatible elements (e.g. Sr, Ba, U, Th) with respect to the upper crust. In contrast non-diamondiferous rocks of the Zerenda series exhibit normal crustal geochemistry. All rocks of the Zerenda series have very radiogenic lead isotopes. The measured μ values (238U/204Pb) compared with those calculated for the interval between crust formation and ultrahigh pressure (UHP) metamorphism suggest a decrease by factors of up to 200 during the UHP metamorphism. The Sm-Nd mineral isochrons from the diamond-bearing rocks and other rock types of the Zerenda series give a Middle Cambrian (524–535 Ma) age of metamorphism. The Nd model ages show that crust formation occurred about 2.3 Ga ago. Significant fractionation of Sm and Nd and loss of incompatible elements may be due to partial melting of the protoliths. The Ar-Ar age determinations of secondary biotite and muscovite from the diamond-bearing rocks yield an age of 517 ± 5 Ma. This cooling age requires a short time interval between UHP metamorphism and uplift to a crustal level. Ultrahigh pressure metamorphism might be a significant source of Pb for the mantle. We propose that the radiogenic Pb of the oceanic array is the contamination traces of numerous UHP events. Beside the geological aspect we demonstrate a method of dating a high grade metamorphic terrain using Nd isotopes. We compare whole rock isochrons and mineral isochrons and in this way get some insight into the behaviour of the Sm-Nd system during very high grade metamorphic events.

In mantle xenoliths, metasomatism is recorded by compositional variations within and between minerals, and by the introduction of secondary minerals. However, metasomatism has not been quantitatively evaluated as a process with respect to the fluid composition involved. Diamondiferous eclogites from the Udachnaya kimberlite provide a unique suite of samples that allow a semiquantitative estimation of metasomatic fluid composition. The basis of our analysis involves comparison of reconstructed whole-rock compositions with measured whole-rock analyses. Primary minerals in these samples are relatively homogeneous, and permit the use of modal analyses and mineral chemistry for reconstruction of “pristine” whole-rock compositions. The metasomatic overprint, which is similiar in all samples studied, has produced depletions in SiO2, Na2O, and FeO and enrichments in TiO2, K2O, MgO, and LREE. Secondary minerals from the samples are interpreted as the direct result of metasomatism (i.e., typical metasomatic mineral...

Eclogitic (E-type) and related parageneses of natural diamonds are represented by suites of diamond inclusions and xenoliths of diamondiferous eclogites. Major-element data are presented for 32 coexisting minerals forming 19 bimineralic and trimineralic inclusions from diamonds, including omphacite-orthopyroxene (1 sample), garnet-omphacite (5 samples), garnet-coesite (5 samples), omphacite-coesite (2 samples), garnet-picroilmenite (2 samples), garnet-kyanite (1 sample), omphacite-phlogopite (2 samples), and garnel-omphacite-phlogopite (1 sample). Major-element variations of coexisting minerals are typical of corresponding eclogites. Omphacite with 5.02 wt% Na2O, inter-grown with orthopyroxene with Mg# 83.7, represents the first example of a diamondiferous websterite paragenesis including Na-clinopyroxene. This indicates a broader range in mineral compositions of E-type-related websteritepyroxenite-associated diamonds than known previously. This unique websterite-pyroxenitic mineral assemblage represents ...

For estimations of P-T conditions of igneous and metamorphic rocks, Fe 31 in coexisting minerals is either assumed to be zero or is calculated from electron microprobe analyses (EMPA) based upon stoichiometry and charge balance. Geothermobarometers that involve Fe 21 -Mg 21 exchange can be significantly affected by either neglecting Fe 31 or using incorrect values. Ratios of Fe 31

Primary (syn-growth) fluid inclusions in synthetic diamonds, produced within the field of their thermodynamic stability in a high-pressure split-sphere apparatus using the temperature gradient method, have been studied by optical microscopy and Raman spectroscopy. Inclusions in tabular diamond crystals contain CH 4 +other higher-molecular hydrocarbons, whereas inclusions in octahedral and dodecahedral diamonds contain only CH 4 . All inclusions in octahedral and dodecahedral diamonds contain graphite, which covers the walls of vacuoles as an opaque film. The formation of this film is most likely associated with precipitation of carbon from fluid on cooling. The obtained results emphasize the possible role of hydrocarbons in the process of diamond crystallization.

Bulk compositions and mineral analyses for forty-one, large, garnet- and spinel-facies peridotite xenoliths from the Udachnaya kimberlite in the central Siberian platform have many similarities to those of well-studied peridotites from the Kaapvaal craton in southern Africa. Coarse Mg-rich lherzolites and harzburgites with equilibration temperatures below 1000 °C are abundant and are believed to form the principal rock type in the Siberian lithosphere. The low-temperature Udachnaya peridotites have an average mg number [Mg/(Mg+Fe)] of 92.6 with a wide dispersion in modal enstatite, ranging to over 40 wt%. High-temperature peridotites are relatively richer in Fe and Ti and are commonly deformed, with porphyroclastic or mosaic-porphyroclastic textures, some of the latter having fluidized enstatite. The Udachnaya peridotites have experienced late-stage metasomatism before, during and after eruption. Garnets and pyroxenes in many of the high-temperature rocks are zoned, probably by reaction with melt prior to eruption. Virtually all the peridotites contain secondary diopside, inhomogeneous on a micron scale, that mantles primary orthopyroxene. It is believed to have crystallized along with lesser amounts of intergranular calcite and monticellite during eruption. Bulk analyses for total Fe in many specimens are higher than whole-rock Fe calculated from the electron probe analyses and the modes. The magnitude of the difference between the two measurements of total Fe correlates with loss-on-ignition, suggesting that Fe has been introduced during serpentinization following eruption. These late metasomatic processes have thus affected some major as well minor and trace element compositions. The similarities in bulk composition of peridotites from Udachnaya and the Kaapvaal are evidence of a common origin. Low-temperature cratonic peridotites differ from oceanic peridotites in having higher mg numbers (>92) and in having relatively high but wide-ranging modal enstatite (Mg/Si = 1.06–1.49 weight fraction). The Udachnaya low-temperature peridotites have an inverse correlation between FeO (calculated from the probe analyses and modes) and SiO2. This correlation is also present in the Kaapvaal data but is complicated by a greater range in fertility that produces a positive variation of Fe with Si. A negative trend for Fe/Si can be seen within a portion of the Kaapvaal data, that for low-Ca harzburgites, in which the variation in fertility is restricted. The negative trends for Fe/Si can be interpreted as a consequence of either segregation of olivine and orthopyroxene by metamorphic differentiation or partial sorting during cumulate formation.

Representative diamond-bearing gneisses and dolomitic marble, eclogite and Ti-clinohumite-bearing garnet peridotite from Unit I at Kumdy Kol and whiteschist from Unit II at Kulet, eastern Kokchetav Massif, northern Kazakhstan, were studied. Diamond-bearing gneisses contain variable assemblages, including Grt+Bt+Qtz±Pl±Kfs±Zo±Chl±Tur±Cal and minor Ap, Rt and Zrn; abundant inclusions of diamond, graphite+chlorite (or calcite), phengite, clinopyroxene, K-feldspar, biotite, rutile, titanite, calcite and zircon occur in garnet. Diamond-bearing dolomitic marbles consist of Dol+Di±Grt+Phl; inclusions of diamond, dolomite±graphite, biotite, and clinopyroxene were identified in garnet. Whiteschists carry the assemblage Ky+Tlc+Grt+Rt; garnet shows compositional zoning, and contains abundant inclusions of talc, kyanite and rutile with minor phlogopite, chlorite, margarite and zoisite. Inclusions and zoning patterns of garnet delineate the prograde P–T path. Inclusions of quartz pseudomorphs after coesite were identified in garnet from both eclogite and gneiss. Other ultrahigh-pressure (UHP) indicators include Na-bearing garnet (up to 0.14 wt% Na2O) with omphacitic Cpx in eclogite, occurrence of high-K diopside (up to 1.56 wt% K2O) and phlogopite in diamond-bearing dolomitic marble, and Cr-bearing kyanite in whiteschist. These UHP rocks exhibit at least three stages of metamorphic recrystallization. The Fe-Mg partitioning between clinopyroxene and garnet yields a peak temperature of 800–1000 °C at P >40 kbar for diamond-bearing rocks, and about 740–780 °C at >28–35 kbar for eclogite, whiteschist and Ti-bearing garnet peridotite. The formation of symplectitic plagioclase+amphibole after clinopyroxene, and replacement of garnet by biotite, amphibole, or plagioclase mark retrograde amphibolite facies recrystallization at 650–680 °C and pressure less than about 10 kbar. The exsolution of calcite from dolomite, and development of matrix chlorite and actinolite imply an even lower grade greenschist facies overprint at c. 420 °C and 2–3 kbar. A clockwise P–T path suggests that supracrustal sediments together with basaltic and ultramafic lenses apparently were subjected to UHP subduction-zone metamorphism within the diamond stability field. Tectonic mixing may have occurred prior to UHP metamorphism at mantle depths. During subsequent exhumation and juxtaposition of many other tectonic units, intense deformation chaotically mixed and mylonitized these lithotectonic assemblages.

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 TiO 2 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/m 2 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.

Owing to the association with diamonds, eclogite xenoliths have samples were derived from typical depleted mantle. However, two groups of three samples each indicate both enriched mantle and received disproportionate attention given their low abundance in kimberlites. Several hypotheses have been advanced for the origin of possible ultra-depleted mantle present beneath Yakutia during the late Archean and early Proterozoic. The vast majority of eclogites eclogite xenoliths, from the subduction and high-pressure melting of oceanic crust, to cumulates and liquids derived from the upper studied from the Obnazhennaya pipe also exhibit characteristics of mantle. We have amassed a comprehensive data set, including Group A eclogites and are probably derived directly from the mantle. majorand trace-element mineral chemistry, carbon isotopes in However, the eclogites from the Mir kimberlite are more typical of diamonds, and Rb–Sr, Sm–Nd, Re–Os, and oxygen isotopes in other eclogites world-wide and show convincing evidence of a recycled, ultrapure mineral and whole-rock splits from eclogites of the Udoceanic crustal affinity. We concur with the late Ted Ringwood achnaya kimberlite pipe, Yakutia, Russia. Furthermore, eclogites that eclogites can be formed in a variety of ways, both within the from two other Yakutian kimberlite pipes, Mir and Obnazhennaya, mantle and from oceanic crustal residues. have been studied in detail and offer contrasting images of eclogite protoliths. Relative to eclogites from southern Africa and other Yakutian localities, Udachnaya eclogites are notable in the absence of chemical zoning in mineral grains, as well as the degree of light

Garnet xenocrysts (n = 386) and associated mineral inclusions and intergrowths from the diamond-free Zagadochnaya kimberlite (Daldyn field, Yakutia) were studied to provide new insights into mantle processes beneath the central Siberian Craton. Electron microprobe analyses indicate that the great majority of the garnets follow the 'lherzolitic' trend in the CaO vs Cr2O3 diagram (Cr2O3 = 0 center dot 5-9 center dot 3 wt %, CaO = 3 center dot 2-10 center dot 3 wt %), with < 10% falling in the wehrlitic field and < 3% falling in a transitional region between the lherzolitic and harzburgitic fields. A representative subset of the garnets (n = 28) was further analysed for trace elements by laser ablation inductively coupled plasma mass spectrometry. Based on both major and trace element data, three main compositional groups are distinguished: Group A garnets (Cr2O3 = 1 center dot 3-5 center dot 2 wt %) may contain inclusions of chromian diopside and are characterized by progressively increasing, chondrite (CI)-normalized rare earth element (REE) abundances from La to Lu; Group B garnets (Cr2O3 = 5 center dot 4-8 center dot 6 wt %) are less depleted in light REE (LREE) and show nearly flat patterns from Sm to Lu; Group C garnets (Cr2O3 = 7 center dot 3-8 center dot 4 wt %) are characterized by humped to strongly sinusoidal REE patterns, with Yb between 0 center dot 5 and 3 center dot 0 x CI. Numerical simulations of melt-rock interactions show that the wide spectrum of garnet REE compositions can be produced by a unique episode of melt injection and percolation through a refractory mantle column, whereby the melt progressively changes its composition owing to chromatographic ion exchange, fractional crystallization, and assimilation of peridotitic minerals, under decreasing melt/rock ratios. The calculated composition of the metasomatizing melt has a kimberlitic affinity, but is distinct from the composition of the host Zagadochnaya kimberlite. Most of the Group B and C garnets show replacement by a secondary mineral assemblage of (Ca, Cr)-poor garnet, chromian diopside, and chromite (+/- phlogopite +/- amphibole). The (Ca, Cr)-poor garnets are enriched in almost all incompatible trace elements, and often show humped CI-normalized REE patterns. The textures and mineralogy of these secondary mineral assemblages, the calculated compositions of the melts in equilibrium with the secondary garnets and clinopyroxenes, and Ca concentration profiles across garnet zoning indicate deep-seated (100-130 km) pervasive reaction with melts related to the host kimberlite. The lack of mantle materials from depths greater than 130 km, the absence of diamond, the abundance of secondary mineral assemblages, and the high-Mg composition of the kimberlite are consistent with a relatively slow ascent of the melts to intermediate and shallow mantle depths (< 130 km) and extensive melt-mantle interactions before eruption.

The first ion-probe trace element analyses of clinopyroxene-garnet pairs both included within diamonds and from the eclogite host xenoliths are reported; these diamondiferous eclogites are from the Udachnaya and Mir kimberlite pipes, Yakutia, Russia. The major and trace element analyses of these diamond-inclusion and host-rock pairs are compared in order to determine the relative ages of the diamonds, confirm or deny genetic relationships between the diamonds and the eclogites, evaluate models of eclogite petrogenesis, and model igneous processes in the mantle before, during, and after diamond formation. The most striking aspect of the chemical compositions of the diamond inclusions is the diversity of relationships with their eclogite hosts. No single distinct pattern of variation from diamond inclusion minerals to host minerals is found for all four samples. Garnet and clinopyroxene inclusions in the diamonds from two samples (U-65/3 and U-66/3) have lower Mg#s, lower Mg, and higher Fe contents, and lower LREE than those in the host eclogite. We interpret such variations as due to metasomatism of the host eclogite after diamond formation. One sample, U-41/3 shows enrichment in diamond-inclusion MREE enrichment relative to the eclogite host and may indicate a metasomatic event prior to, or during, diamond formation. Bulanova [2] found striking differences between inclusions taken from within different portions of the very same diamond. Clinopyroxene inclusions taken from the central (early) portions of Yakutian diamonds were lower in Mg# and Mg contents (by up to 25%) than those later inclusions at the rims of diamonds. These trends are parallel to those between diamond inclusions and host eclogites determined for four of the five samples from the present study and may merely represent changing magmatic and/or P-T conditions in the mantle. Garnet trace element compositions are similar in relative proportions, but variable in abundances, between diamond inclusions and host eclogites. This is probably due to the rapid diffusion of trace elements in garnet under mantle temperatures and consequent alteration of the garnet, and not due to juvenile diamonds ‘locking in’ source heterogeneities (c.f., [3]). Trace element compositions of clinopyroxenes included in diamonds are generally similar to those in the host eclogite. However, one host clinopyroxene does show enrichment in the LREE compared to that in the inclusion and may be attributed to mantle metasomatism, not related to kimberlite transport. In another eclogite, M-46, the host clinopyroxene is depleted in the LREE and Fe, and enriched in the HREE and Mg, relative to the inclusion and is consistent with partial melting of the eclogite subsequent to diamond formation. SmNd ratios in clinopyroxenes appear to be little affected by these processes for most samples, allowing SmNd isotopic studies to yield important information about ancient protoliths. Eclogitic mineral inclusions in Yakutian diamonds appear consanguineous with the diamonds, a contention supported by the observations of Bulanova [2]. Therefore, ReOs whole-rock and SmNd clinopyroxene age determinations of the Udachnaya eclogites also yield the time of diamond formation, approximately 2.9 Ga [32,33].

The Kokchetav Complex is a tectonic mega-melange consisting of seven pre-Ordovician units (units I-VII) of contrasting lithologies and P–T conditions of metamorphism, overlain and/or intruded by four post-recrystallization entities. Most of the constituent rock types display affinities with continental crust; paraschists and paragneisses, which carry biogenically produced carbon, clearly were laid down near the surface of the Earth. Microdiamond (and rare coesite) inclusions are contained in strong, refractory garnet, zircon, clinopyroxene, and kyanite, some of the constituent neoblastic phases of this metasedimentary unit. Systematic mineral parageneses and textural relationships support the hypothesis that the metamorphic assemblages represent a close approach to chemical equilibrium at the time of formation. Metamorphism of diamond-bearing paragneisses and schists transpired at 535 ± 5 Ma; physical conditions included minimum pressures of 40 kbar and temperatures exceeding 900 °C. Other associated units contain mineralogic evidence of somewhat lower to considerably lower pressures and temperatures: observed magnesite + diopside pairs, coesite, grossular-pyropic garnet, potassic clinopyroxene, Si-rich phengite, barroisite-crossite(?), aluminous titanite and/or Al-rutile, and the assemblage talc + kyanite + garnet all testify to relatively elevated pressures of formation. The metamorphosed lithotectonic units represent individual, discrete stages in what initially may have been a continuous P-T series, but intense post-metamorphic dislocation has resulted in the preservation of a chaotically mixed sequence rather than an unbroken gradation in preserved conditions of metamorphism. Only units I-III, and probably VIb may represent portions of a dismembered subduction zone lithologie assemblage. The uplift to mid-crustal levels and cooling of the mega-melange took place by about 515–517 Ma, at which time the complex was stabilized as a part of the Kazakhstan microcontinental collage. An hypothesized Late Vendian-Early Cambrian subduction of the Kazakhstan-North Tianshan(?) microcontinental salient to depths exceeding 125 km, followed by decoupling from the descending oceanic crust-capped lithospheric plate is held responsible for the ultrahigh-pressure metamorphism of the Kokchetav Complex. Inasmuch as vestiges of a calc-alkaline volcanic/plutonic arc of approximately Early Cambrian age are preserved as only scattered relics in the general region, the plate-tectonic setting may have involved an intra-oceanic, Marianas-type, incipient arc which was subsequently removed through transform faulting or erosion.

Data are presented for the O isotopic composition of clinopyroxene and garnet, the C isotopic composition of diamond, and the OH- content of garnet from eclogite xenoliths brought to the surface by the Udachnaya kimberlite pipe, Yakutia, Siberia. Radiogenic isotopic data suggest that the eclogites could have been derived from an ultradepleted mantle at approximately 2.9 Ga (Pearson et al., 1995; Snyder et al., in preparation). O isotopic compositions generally show equilibration between the eclogitic minerals (Δ_(cpx-Grt) = 0.11-0.41‰) and have δ^(18)O_(SMOW) for both garnet and clinopyroxene that lie near the range of accepted mantle values of 5.7±0.7‰. However, several eclogites indicate significant deviations from this range, at higher values of 6.8-7.0‰. Also, two eclogites lie at the lower end of the mantle range, at values of 4.8 and 5.0‰ (all in clinopyroxene). C isotopic compositions of diamonds all have δ^(13)C_(PDB) in the range of -1 to -7‰ and are centered at approximately -5‰, also within the range of accepted mantle values. The OH- contents of the garnet are generally between 0 and 22 ppm (as H_(2)0), although two samples exceed 70 ppm. This range of OH- is similar to eclogitic garnet from the Kaapvaal craton of southern Africa. The mantle C isotopic values of associated diamonds, the majority of O isotopic data, and the low OH- content of the minerals, although suggesting a general lack of crustal participation in the formation of the Udachnaya eclogites, do not rule out the participation of some ancient crustal material. That these eclogites include both ^(18)O-enriched and ^(18)O-depleted types suggests that the protoliths may have been overprinted by both low- and high-temperature hydrothermal events (cf. Jacob et aI., 1994). A positive correlation between δ^(18)O and ^(87)Sr/^(86)Sr allows the interpretation of these eclogites as representing a cross section of an Archean ophiolite. However, the lack of a single coherent grouping on a plot of δ^(18)O vs. ^(87)Sr/^(86)Sr suggests that, if the Udachnaya eclogites were derived from oceanic crust, they cannot be cogenetic and must represent at least two separate ophiolite sequences. Conversely, if the eclogites are found to be cogenetic, then a totally different process affected their formation and a probable metasomatic mechanism was operative. Because of the total lack of correlation of δ^(18)O with other geochemical parameters, we find no compelling evidence that all eclogites are derived ultimately from oceanic crust.

Garnet crystals from diamondiferous high-pressure metamorphic rocks of the Kokchetav Massiv, Kazakhstan, were studied by electron microprobe and single crystal microscope-spectrometry in the UV/VIS and IR spectral ranges. The crystals are quaternary solid solutions Gross 48 Pyr 33 Alm 16 Spess 2 , (I.) from garnet-pyroxene-carbonate rock K7, and Gross 21 Pyr 24 Alm 49 Spess 5 , (II.) from garnet-biotite-gneiss, both with small TiO 2 -contents (0.3 wt%). Their yellow (I.) or deep-red colour (II.) is caused by the position of the UV absorption edge and a broad Fe 2+[8] Ti 4+[6] charge-transfer band centered at 21 500 cm −1 . For comparison, a high-pressure garnet Py26, Py 70 Alm 17 Uv 13 (III.), from Liaoning-50 kimberlite, NE China, was included in the IR and microprobe study. All crystals studied contained defect OH − -groups, corresponding to those in synthetic OH − -bearing pyropes, giving rise to a single, relatively sharp absorption band (Δv 1/2 ≃ 100 cm −1 ) in the range 3560 to 3610 cm −1 . The exact energy position depends on the type and site fractions of ions in the OH − -coordinating metal sites, A [8] and B [6] . This hydroxyl «water» seems to be not uniformly distributed in the garnet crystals and ranges from 0.02 to 0.25 wt% (wt% calculated from integral intensities using e i,Gross ). In addition to ν OH , the IR spectra show a broad band at 3400 cm −1 , characteristic of (H 2 O) n -clusters. There seems to be a constant ratio α i,OH− /(α i,OH− + α i,H2O ) for the various spots on the different crystals I, II, and III

Nd and Sr isotopic data from diamond-bearing eclogites found in the Udachnaya kimberlite, Yakutia, Siberia, are interpreted as indicating an early (>1 4 Ga) differentiation event, whereby the mantle split into complementary depleted and enriched reservoirs. Reconstructed whole-rock 87Sr/S6Sr ratios (present-day) range from 0.70151 to 0.70315 and are consistent with a mantle origin for these rocks. The Nd isotopic evolution lines of four samples (U-5, U-37, U-41 and U-79) converge at 2.2-2.7 Ga. Sample U-5 is unique in exhibiting the most enriched signature of any of the samples yet analyzed (present-day end of --20), and this sample points unequivocally to an old, enriched component. A complementary depleted mantle component is suggested by two of the eclogite samples, U-86 and U-25, which yield ENd values (at 2.2 Ga) of + 13 and + 7, respectively. The two mantle reservoirs possibly formed prior to 4 Ga and evolved separately until 2.2-2.7 Ga. At that time, the reservoirs were melted forming eclogites both as residues (from the enriched reservoir) and as partial melts of peridotite (from the depleted reservoir), resulting in demonstrably different histories for eclogites from the same locality.

Eclogite xenoliths from the mantle have experienced a wide variety of processes and P-T conditions, many of which are recorded in the mineral compositions and textures. Exsolution of garnet from clinopyroxene is one such texture, occurring in a minority of mantle eclogites. New analyses of clinopyroxene and garnet of eclogite xenoliths from kimberlites at Bellsbank (South Africa) and Obnazhennaya (Yakutia, Russia) are presented here, and these are combined with data from the literature. Exsolution of garnet from clinopyroxene is generally lamellar, although lens-shaped garnets are also present. Major- and trace-element characteristics show a wide range of compositions and include eclogite Groups A, B, and C. Rare-earth element (REE) concentrations of garnet and pyroxene were determined by SIMS, and the REE patterns are subtly different from those in “ordinary” eclogites. Differences include the absence of prominent Eu anomalies in samples of this study and differences in the slopes of chondrite-normalized REE patterns. It is possible that these “signatures” are unique to exsolved eclogites, a result of subsolidus elemental partitioning during exsolution. Some reconstructed whole-rock compositions are aluminuous; comparison with ordinary eclogites shows only minor differences, implying a similar origin. If the immediate precursor to the exsolved eclogites was a monomineralic pyroxenite, the excess aluminium was tied up in Tschermak's molecule, although the occasional presence of kyanite exsolution lamellae is indicative of a Ca-Eskola component. Reconstructed “pyroxenes” from kyanite- and corundum-rich samples contain unrealistic amounts of aluminium for mantle pyroxenes. A protolith (or parental pyroxene) “threshold” of ∼24% Al2O3 may exist, above which (as in a plagioclase cumulate) the final assemblage is kyanite- and/or corundum-bearing.

Major-element and REE compositions of 14 diamondiferous eclogites from the Udachnaya kimberlite in Yakutia, Siberia have been determined by electron microprobe and secondary ion mass spectrometer (SIMS). Based on previous clinopyroxene classification schemes (e.g., Taylor and Neal 1989), all of these eclogite xenoliths belong to Group B/C, although some of the garnet compositions and mineral REE abundances are inconsistent with the indicated groups. This demonstrates the inadequacy of the classification scheme based on African eclogites for application to Siberian samples. Because of the coarse grain size of the Udachnaya nodules, meaningful modal abundances could not be obtained. However, reconstructed REE compositions using various garnet: clinopyroxene ratios demonstrate relative insensitivity to changes in mode for common eclogitic assemblages. Many of these reconstructed REE compositions show LREE depletions. Some depletions are consistent with an origin (either directly or through partial melting) as “normal” or Type-I ocean floor basalt. Others, however, require material of eclogitic or pyroxenitic affinities to undergo partial melting; this facilitates the depletion of LREE while leaving the HREE at nearly original levels. Many of the eclogites of South Africa are consistent with a protolith of “anomalous” or Type II ocean floor basalt. This fundamental difference between the two regions is the likely cause of the inconsistencies with the chemicallybased classification.

The mineral eskolaite (Cr 2 O 3 ) has been discovered in association with natural diamond from the Udachnaya pipe in Yakutia, where it is intergrown with an octahedral diamond, mostly as an inclusion in the diamond, but also exposed at its surface. A detailed study was performed on fragments extracted from the outer surface of the diamond, using single-crystal X-ray diffraction (XRD), high-resolution electron microscopy (HRTEM), analytical electron microscopy (AEM), including line-scan and elemental-mapping, EMP, and SIMS. These applied techniques confirmed the nature of the eskolaite with 86.8 wt% Cr 2 O 3 and notable impurities of TiO 2 (3.99 wt%), Al 2 O 3 (2.00 wt%), Fe 2 O 3 (5.83 wt%), and MgO (1.11 wt%). Trace elements, including V (4900 ppm), Mn (129 ppm), Zr (56 ppm), and Nb (32 ppm) were also detected. The entire range of REE is just at or below the limits of detection. A small picrochromite inclusion (X Mg 81.2; Y Cr 94.7) was detected in the eskolaite; its chemistry is typical of chromite diamond inclusions. It also contains minute inclusions of perovskite, corundum, and an unidentified Ti-phase. Nano-sized cavities in picrochromite were determined to consist of carbonate and quench products, including Si, Mg, Ca, P, K, and Cl. This may represent relics of the diamond-forming metasomatic fluids. The eskolaite, containing a picrochromite inclusion, was formed at high pressure within the diamond stability field from C-O-H-bearing fluids containing Ca, K, Cl, P, and possibly even peridotitic (U-type) oxides and silicates.

Nanometre-sized isolated inclusions have been studied in four cloudy octahedral diamonds from the Internatsionalnaya and one from the Yubileynaya mines (Yakutia). Transmission electron microscopy (TEM) techniques such as electron diffraction, analytical electron microscopy (AEM), electron energy-loss spectroscopy (EELS) and high-resolution electron microscopy (HREM) were applied as well as line scan and elemental mapping of the samples. All crystals exhibit octahedral external habit with opaque central cuboid cores that contain numerous nano-inclusions. All nano-inclusions in the size range between 30 and 800 nm reflect the diamond habit and are considered primary, syngenetic to host diamond. They are composed of multi-phase assemblages, which include solid phases (silicates, oxides, carbonates), brines (halides), and fluid bubbles. These inclusions are relatively homogeneous in composition and contain distinguishable crystalline and fluid phases. Al-bearing high-Mg silicate, dolomite, Ba-Sr carbonate, phlogopite, ilmenite, ferropericlase, apatite, magnetite, K-Fe sulfides (djerfisherite?) and kyanite have been identified as crystalline mineral phases by electron diffraction patterns, except the Ba-Sr carbonate. Several phases, including CaF 2 and clinohumite-like phases, have never been reported as inclusions in diamond. The halide phase was KCl. Bubbles contained high K, Cl, O, P and less S, Ba, Si, Ti components. Carbonates were identified in TEM foils from all studied diamonds. They occur in all assemblages with silicates, oxides, and sulfides and show a general enrichment in incompatible elements such as Sr and Ba. Some elemental variations may be explained by fractional crystallization of fluid/melt or mixing of fluids with different compositions (carbonatitic, hydrous-silicic, brines).

DIAMONDS commonly occur in kimberlites, lamproites and alluvial sediments derived from these rocks. More recently, diamonds (or their graphite pseudomorphs) have been discovered in ultramafic massifs1 and picrites2. Here we report the occurrence of diamonds in situ in crustal rocks: highly retrograded high-pressure metamorphic garnet–pyroxene and pyroxene–carbonate–garnet rocks, biotite gneisses and schists from the Kokchetav massif, northern Kazakhstan, USSR. The diamonds are cubo-octahedral, averaging 12 μm in size, and occur in zircons, and with euhedral graphite as inclusions in unzoned garnets. We believe that the zircon and garnet matrices protected these diamonds from retrogressive transformation to graphite. Mica, rutile, titanite, clinopyroxene, kyanite and zircon also occur as inclusions in garnet, often intergrown with the diamonds. Equilibration relations of inclusions and host garnets indicate that both diamonds and graphite crystallized from a fluid phase under static conditions at pressures of ⩾40 kbar and temperatures >900–1,000 °C.

Kimberlite magmas, as the deepest probe into Earth's mantle (>150 km), can supply unique information about volatile components (hydrogen, carbon, chlorine, sulfur) in mantle-derived melts and fluids. All known kimberlite rocks are not suitable for studies of mantle volatiles because of their pervasive postmagmatic alteration; however, this study discusses an exceptionally fresh group I kimberlites (