Carbon isotopic composition of diamonds from the Archangelsk diamond province

The first data are reported on the carbon isotopic composition of diamond crystals from the Grib pipe kimberlite deposit of the Archangelsk diamond province (ADP). The δ¹³C value of the crystals ranges from ?2.79 to ?9.61‰. The isotopic composition of carbon was determined in three zoned crystals (δ¹³C of ?5.8 ?6.96 ‰, ?5.64/ ?5.85 ‰, and ?5.94/ ?5.69 ‰), two “diamond in diamond” samples (diamond inclusion with δ¹³C of ?4.05 and ?6.34 ‰ in host diamond crystals with δ¹³C of ?8.05 and ?7.54 ‰, respectively), and two samples of coated diamonds (cores with δ¹³C of ?6.98 and ?6.78‰ and coats with δ¹³C of ?7.51 and ?8.01 ‰, respectively). δ¹³C values were obtained for individual diamond crystals from bort-type aggregates (δ¹³C of ?4.24/ ?4.05 ‰, ?6.58/ ?7.48 ‰, and ?5.48/ ?6.08 ‰). Correlations were examined between the carbon isotopic composition of diamonds and their crystal morphology; the color; the concentration of nitrogen, hydrogen, and platelet defects; and mineral inclusions content. It was supposed that the observed δ¹³C variations in the crystals are most likely related to the fractionation of carbon isotopes rather than to the heterogeneity of carbon sources involved in diamond formation. The isotopic characteristics of diamonds from the Grib pipe were compared with those of previously investigated diamonds from the Lomonosov deposit. It was found that diamonds from these relatively closely spaced kimberlite fields are different; this also indicates the existence of spatially localized peculiarities of isotope fractionation in processes accompanying diamond formation.     

Carbon and Nitrogen Isotopic,and Mineral Inclusion Studies on the Diamonds from the Pozanti‐Karsanti Chromitite,Turkey

He Pozanti‐Karsanti ophiolite (PKO) is one of the largest oceanic remnants in the Tauride belt, Turkey. Micro‐diamonds were recovered from the podiform chromitites, and these were investigated based on morphology, color, cathodoluminescence, nitrogen content, carbon and nitrogen isotopes, internal structure and inclusions. The diamonds recovered from the PKO are mainly mixed‐habit diamonds with sectors of different brightness under the cathodoluminescence images. The total δ¹³C range of the PKO diamonds ranges between ?18.8 ‰ and ?28.4 ‰, with a principle δ¹³C mode at ?25 ‰. Nitrogen contents of the diamonds range from 7 to 541 μg/g with a mean value of 171 μg/g, and the δ¹⁵N values range from ?19.1 ‰ to 16.6 ‰, with a δ¹⁵N mode of ?9 ‰. Stacking faults and partial dislocations are commonly observed in the Transmission Electron Microscopy foils whereas inclusions are rather rare. Combinations of (Ca_0.81Mn_0.19)SiO₃, NiMnCo‐alloy and nano‐size, quenched fluid phases were observed as inclusions in the PKO diamonds, confirming a natural origin of these diamonds. We believe that the δ¹³C‐depleted carbon signature of the PKO diamonds is a remnant of previously subducted crustal matter. These diamonds may have crystallized in metal‐rich melts in the asthenospheric mantle at depth below 250 km which were subsequently carried rapidly upward by asthenospheric melts/fliuds. We concluded that diamond‐bearing asthenospheric melts were likely involved in the formation of the Pozanti‐Karsanti podiform chromitite.     

Formation of mosaic diamonds from the Zarnitsa kimberlite

Mosaic diamonds from the Zarnitsa kimberlite (Daldyn field, Yakutian diamondiferous province) are morphologicaly and structurally similar to dark gray mosaic diamonds of varieties V and VII found frequently in placers of the northeastern Siberian craton. However, although being similar in microstructure, the two groups of diamonds differ in formation mechanism: splitting of crystals in the case of placer diamonds (V and VII) and growth by geometric selection in the Zarnitsa kimberlite diamonds. Selective growth on originally polycrystalline substrates in the latter has produced radial micro structures with grains coarsening rimward from distinctly polycrystalline cores. Besides the formation mechanisms, diamonds of the two groups differ in origin of mineral inclusions, distribution of defects and nitrogen impurity, and carbon isotope composition. Unlike the placer diamonds of varieties V and VII, the analyzed crystals from the Zarnitsa kimberlite enclose peridotitic minerals (olivines and subcalcic Cr-bearing pyropes) and have total nitrogen contents common to natural kimberlitic diamonds (0 to 1761 ppm) and typical mantle carbon isotope compositions (-1.9 to -6.2%c 5¹³C; -4.2%c on average). The distribution of defect centers in the Zarnitsa diamond samples fits the annealing model implying that nitrogen aggregation decreases from core to rim.     

Syngenetic phlogopite inclusions in kimberlite-hosted diamonds: implications for role of volatiles in diamond formation

We discuss the chemistry of exceptionally rare phlogopite inclusions coexisting with ultramafic (peridotitic) and eclogitic minerals in kimberlite-hosted diamonds of Yakutia, Arkhangelsk, and Venezuela provinces. Phlogopite inclusions in diamonds are octahedral negative crystals following the diamond faceting in all 34 samples (including polymineralic inclusions). On this basis phlogopite inclusions have been interpreted as syngenetic and in equilibrium with the associated minerals. In ultramafic diamonds phlogopites coexist with subcalcic high-Cr₂O₃ pyrope and/or chromite, olivine and enstatite (dunite/harzburgite (H) paragenesis) or with clinopyroxene, enstatite, and/or olivine and pyrope (lherzolite (L) paragenesis). Ultramafic phlogopites have high Mg# [100?Mg/(Mg+Fe)] from 92.4 to 95.2 and Cr₂O₃ higher than TiO₂ in H-phlogopites (1.5–2.5 wt.% versus 0.1–0.4 wt.%, respectively) but lower in L-phlogopites (0.15–0.5 wt.% versus 1.3–3.5 wt.%, respectively). Eclogitic (E) phlogopites show Mg# from 47.4 to 85.3 inclusive, and very broad ranges of TiO₂ up to 12 wt.%. The primary syngenetic origin of phlogopite is indicated, besides other factors, by its compositional consistency with the associated minerals. The analyzed phlogopites are depleted in BaO (0.10–0.79 wt.%), and their F and Cl contents are highly variable reaching 1.29 and 0.49 wt.%, respectively. The latter is in line with high Cl enrichment in some unaltered kimberlites and in nanometric fluid inclusions from diamonds. The presence of syngenetic phlogopite in kimberlite-hosted diamonds provides important evidence that volatiles participated in diamond formation and that at least a part of diamonds may have been related to early stages of kimberlites formation.     

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.     

Coesite inclusions in diamonds of Yakutia

The results of the study of diamonds with inclusions of high-pressure modification of SiO₂ (coesite) by Raman spectroscopy are reported. It is established that the octahedral crystal from the Zapolyarnaya pipe is characterized by the highest residual pressure (2.7 ± 0.07 GPa). An intermediate value of this parameter (2.1 ± 0.07 GPa) was obtained for a crystal of transitional habit from the Maiskaya pipe. The minimal Raman shift was registered for coesite in diamond from the Komsomol’skaya–Magnitnaya pipe and provided a calculated residual pressure of 1.8 ± 0.03 GPa. The residual pressures for crystals from the placer deposits of the Kuoika and Bol’shaya Kuonamka rivers are 2.7 ± 0.07 and 3.1 ± 0.1 GPa, respectively. Octahedral crystals were formed in the mantle at a higher pressure than rhombododecahedral diamonds.     

Diamonds and Their Mineral Inclusions,and What They Tell Us: A Detailed “Pull-Apart” of a Diamondiferous Eclogite

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, whose compositions are extremely homogeneous. Some Cpx inclusions possess +Eu anomalies, probably inherited from their crustal source rocks. The only consistent feature for the Cpx crystals in the inclusions is that they have higher K₂O than the Cpx grains in the host.

The δ¹³C compositions are relatively constant at ?5% both within and between diamonds, whereas δ¹⁵N values vary from ?2.8% to ?15.8%. Within a diamond, the total N varies considerably from 15 to 285 ppm in one diamond to 103 to 1250 ppm in another. Cathodoluminescent imaging reveals extremely contorted zonations and complex growth histories in the diamonds, indicating large variations in growth environments for each diamond.

This study directly bears on the concept of diamond inclusions as time capsules for investigating the mantle of the Earth. If diamonds and their inclusions can vary so much within this one small xenolith, the significance of their compositions is a serious question that must be addressed in all diamond-inclusion endeavors.     

Diamondiferous Archean rocks of the Olondo greenstone belt (western Aldan–Stanovoy shield)

Diamond from metaultramafic rocks of the Mesoarchean (2.96–3.0 Ga) Olondo greenstone belt, located in the western Aldan–Stanovoy shield, has been studied. Diamonds occur in lenses of olivine–serpentine–talc rocks within metaultramafic rocks of intrusive habit, whose composition corresponds to peridotite komatiites. All diamonds from the metaultramafic rocks are crystal fragments 0.3 to 0.5 mm in size. Morphological examination has revealed laminar octahedra, their transitional forms to dodecahedroids, crystals with polycentric faces, and spinel twins. The crystals vary in photoluminescence color: dark blue, green, yellow, red, or albescent. Characteristic absorption bands in crystals point to nitrogen impurities in the form of A and B1 defects and tabular B2 defects. The crystals studied belong to the IaA/B type, common among natural diamonds. The overall nitrogen content varies from < 100 to 3800 ppm. The relative content of nitrogen in B1 centers varies from 0 to 94%, pointing to long stay in the mantle. The carbon isotope ratio in the diamonds, ¹³C = ? 26‰, is indicative of involvement of subducted crust matter in diamond formation in the Archean.     

Diamonds in the Attawapiskat area of the Superior craton (Canada): evidence for a major diamond-forming event younger than 1.1 Ga

Here, we compare nitrogen aggregation characteristics and carbon isotopic compositions in diamonds from Mesoproterozoic (T1) and Jurassic (U2) kimberlites in the Attawapiskat area—the first diamond-producing area on the Superior craton. The T1 kimberlite sampled diamonds from the lithospheric mantle at 1.1 Ga, at the same time as the major Midcontinent Rift event. These diamonds have a narrow range in δ¹³C (mode of ?3.4 ‰), with compositions that overlap other diamond localities on the Superior craton. Some diamond destruction must have occurred during the Mesoproterozoic in response to the thermal impact of the Midcontinent Rift—the associated elevated geotherm caused a narrow diamond window (<30 km) close to the base of the lithosphere, compared to a wide diamond window of ~85 km following thermal relaxation (sampled by Jurassic kimberlites, such as U2). T1 diamonds have highly aggregated nitrogen, possibly due to the thermal effect of the rift. Diamond-favourable conditions were re-established in the lithospheric mantle after the thermal impact of the Midcontinent Rift dissipated. The poorly aggregated nature of nitrogen in U2 diamonds—compared to highly aggregated nitrogen in diamonds from T1—indicates that renewed diamond formation must have occurred only after the thermal impact of the Midcontinent Rift at 1.1 Ga had subsided and that these newly formed diamonds were subsequently sampled by Jurassic kimberlites. The overall δ¹³C distribution for U2 diamonds is distinct to T1 and other Superior diamonds, further suggesting that U2 diamonds are not related to the older pre-rift diamonds.     

Oxygen isotope composition of syngenetic inclusions in diamond from the Finsch Mine,RSA

Oxygen isotope data have been obtained for silicate inclusions in diamonds, and similar associated minerals in peridotitic and eclogitic xenoliths from the Finsch kimberlite by laser-fluorination. Oxygen isotope analyses of syngenetic inclusions weighing 20–400 μg have been obtained by laser heating in the presence of ClF₃. ¹⁸O/¹⁶O ratios are determined on oxygen converted to CO₂ over hot graphite and, for samples weighing less than 750 μg (producing <12 μmoles O₂) enhanced CO production in the graphite reactor causes a systematic shift in both δ¹³C and δ¹⁸O that varies as a function of sample weight. A “pressure effect” correction procedure, based on the magnitude of δ¹³C (CO₂) depletion relative to δ¹³C (graphite), is used to obtain corrected δ¹⁸O values for inclusions with an accuracy estimated to be ±0.3‰ for samples weighing 40 μg.Syngenetic inclusions in host diamonds with similar δ¹³C values (−8.4‰ to −2.7‰) have oxygen isotope compositions that vary significantly, with a clear distinction between inclusions of peridotitic (+4.6‰ to +5.6‰) and eclogitic paragenesis (+5.7‰ to +8.0‰). The mean δ¹⁸O composition of olivine inclusions is indistinguishable from that of typical peridotitic mantle (5.25 ± 0.22‰) whereas syngenetic purple garnet inclusions possess relatively low δ¹⁸O values (5.00 ± 0.33‰). Reversed oxygen isotope fractionation between olivine and garnet in both diamond inclusions and diamondiferous peridotite xenoliths suggests that garnet preserves subtle isotopic disequilibrium related to genesis of Cr-rich garnet and/or exchange with the diamond-forming fluid. Garnet in eclogite xenoliths in kimberlite show a range of δ¹⁸O values from +2.3‰ to +7.3‰ but garnets in diamondiferous eclogites and as inclusions in diamond all have values >4.7‰.     

FTIR Spectroscopy Data and Carbon Isotope Characteristics of the Ophiolite‐hosted Diamonds

We report new δ¹³C ‐values data and N‐content and N‐aggregation state values for microdiamonds recovered from peridotites and chromitites of the Luobusa ophiolite (Tibet) and chromitites of the Ray‐Iz ophiolite in the Polar Urals (Russia). All analyzed microdiamonds contain significant nitrogen contents (from 108 up to 589 ± 20% atomic ppm) with a consistently low aggregation state, show identical IR spectra dominated by strong absorption between 1130 cm^?1 and 1344 cm^?1, and hence characterize Type Ib diamond. Microdiamonds from the Luobusa peridotites have δ¹³C ‐PDB‐values ranging from ‐28.7‰ to ‐16.9‰, and N‐contents from 151 to 589 atomic ppm. The δ¹³C and N‐content values for diamonds from the Luobusa chromitites are ‐29‰ to ‐15.5‰ and 152 to 428 atomic ppm, respectively. Microdiamonds from the Ray‐Iz chromitites show values varying from ‐27.6 ‰ to ‐21.6 ‰ in δ¹³C and from 108 to 499 atomic ppm in N. The carbon isotopes values bear similar features with previously analyzed metamorphic diamonds from other worldwide localities, but the samples are characterized by lower N‐contents. In every respect, they are different from diamonds occurring in kimberlites and impact craters. Our samples also differ from the few synthetic diamonds; we also analyzed showing enhanced δ¹³C ‐variability and less advanced aggregation state than synthetic diamonds. Our newly obtained N‐aggregation state and N‐content data are consistent with diamond formation over a narrow and rather cold temperature range (i.e. <950°C), and in a short residence time (i.e. within several million years) at high temperatures in the deep mantle.     

Kimberlitic sources of super-deep diamonds in the Juina area,Mato Grosso State,Brazil

The Juina diamond field, in the 1970–80s, was producing up to 5–6 million carats per year from rich placer deposits, but no economic primary deposits had been found in the area. In 2006–2007, Diagem Inc. discovered a group of diamondiferous kimberlitic pipes within the Chapadão Plateau (Chapadão, or Pandrea cluster), at the head of a drainage system which has produced most of the alluvial diamonds mined in the Juina area. Diamonds from placer deposits and newly discovered kimberlites are identical; they have super-deep origins from the upper-mantle and transition zone. Field observations and petrographic studies have identified crater-facies kimberlitic material at seven separate localities. Kimberlitic material is represented by tuffs, tuffisites and various epiclastic sediments containing chrome spinel, picroilmenite, manganoan ilmenite, zircon and diamond. The diamond grade varies from 0.2–1.8 ct/m³. Chrome spinel has 30–61 wt.% Cr₂O₃. Picroilmenite contains 6–14 wt.% MgO and 0.2–4 wt.% Cr₂O₃. Manganoan ilmenite has less than 3 wt.% MgO and 0.38–1.41 wt.% MnO. The ¹⁷⁶Hf/¹⁷⁷Hf ratio in kimberlitic zircons is 0.028288–0.28295 with ε_Hf = 5.9–8.3, and lies on the average kimberlite trend between depleted mantle and CHUR. The previously known barren and weakly diamondiferous kimberlites in the Juina area have ages of 79–80 Ma. In contrast, zircons from the newly discovered Chapadão kimberlites have a mean ²⁰⁶Pb/²³⁸U age of 93.6 ± 0.4 Ma, corresponding to a time of magmatic activity related to the opening of the southern part of the Atlantic Ocean. The most likely mechanism of the origin of kimberlitic magma is super-deep subduction process that initiated partial melting of zones in lower mantle with subsequent ascent of proto-kimberlitic magma.     

The carbon isotopic composition of diamonds: relationship to diamond shape,color, occurrence and vapor composition

Three hundred and thirty new ¹³C analyses of diamonds are presented, indicating, in conjunction with earlier published work, a range of about 30%. in the carbon isotopic composition of diamonds. The frequency distribution of diamond δ¹³C analyses shows a very pronounced mode at ?5 to ?6%.vs PDB, a large negative skewness, and a sharp boundary at about ?1%.. Analyses of diamonds from the Premier and Dan Carl mines, South Africa, demonstrate that: (1) differences in ¹³C content that can be related to diamond color and shape are smaller than 1%.; (2) the mean ¹³C content of kimberlite carbonates is 1–2%. lower than that of associated diamonds; (3) significant differences in ¹³C content exist between the mean isotopic compositions of diamonds from these two pipes; (4) the variability in δ¹³C differs from one mine to the other.Computations were carried out evaluating the effect on the ¹³C content of diamonds of: (i) various precipitation processes; (ii) the abundance of the species H₂, H₂O, CH₄, CO, CO₂ and O₂ in the vapor; (iii) the initial isotopic composition variability of the source carbon; (iv) variations of the carbon isotope effects resulting from changes in pressure and temperature and (v) reservoir effects (Rayleigh fractionation). Fifty-eight genetic models were investigated for compatibility with the ¹³C distribution in diamonds and associated carbonate. The modeling does not permit an unambiguous answer to the question whether or not a vapor participated in diamond formation, although the presence of methane during diamond formation is compatible with the carbon isotopic composition data, possible oxygen fugacities in the mantle and with the composition of gases liberated from diamonds. In all probability carbon isotope effects in the diamond formation process were small, and the very large range in δ¹³C observed was inherited from the source carbon.     

Relationships between textural and photoluminescence spectral features of carbonado (natural polycrystalline diamond) and implications for its origin

Field Emission SEM (FESEM) textural observations, crystal size distribution (CSD) analyses, UV-excited luminescence imaging, and photoluminescence (PL) microspectroscopy excited by 488 nm laser were conducted on two texturally contrasting samples of carbonado, a kind of natural polycrystalline diamond from the Central African Republic (CAR). The investigated carbonado samples A and B show extremely different textures: sample A is made up of faceted crystals accompanied by abundant, small rectangular pores, whereas sample B has a granular texture with coarser crystals and scarce, large pores. Diamond crystals smaller than 2–3 µm are enriched in sample A but depleted in sample B. These textural features indicate that sample B diamonds were annealed under thermodynamically stable P–T conditions. The pore characteristics indicate that fluid permeability was higher for sample A than sample B. Photoluminescence (PL) spectra indicate that samples A and B correspond to Group A and B carbonados in the classification of Kagi et al. (1994), respectively, so that sample A reveals emissions from the H3 center without any N–V⁰ derived emission at 575 nm, whereas sample B shows emissions from the 3H center and the N–V⁰ defect. In addition, UV-excited luminescence images and photoluminescence spectra for sample B indicate that the rims of diamond crystals within several microns of a pore show luminescence features similar to those of Group AB carbonados (Kagi et al., 1994), indicating that this Group AB material was formed from Group B by irradiation from pore-filling, radioactive-element-bearing materials at a low temperature. The extent of the low-temperature irradiation is considered to depend on fluid permeability, and the Group A material was strongly irradiated due to its permeable texture whereas the Group B material was not significantly irradiated due to its less permeable granular texture. These results indicate that Group B carbonados have retained their original PL spectral features produced under high pressures and temperatures at mantle depths.     

Raman spectra of polycrystalline microdiamond inclusions in zircons,and ultrahigh-pressure metamorphism of a quartzofeldspathic rock from the Erzgebirge terrane,Germany

ABSTRACT

Polycrystalline microdiamonds are rare in ultrahigh-pressure (UHP) rocks worldwide. Among samples collected at Erzgebirge, Germany, we found abundant polycrystalline microdiamonds as inclusions in zircons from a quartzofeldspathic rock. To illuminate their origin and forming age, we investigated morphologies and Raman spectra of 52 microdiamond inclusions, and dated the zircon host. The zircons have low Th/U values (0.03–0.07) and a concordia U/Pb age of 335.8 ± 1.9 Ma. Polycrystalline diamond (10–40 µm) consists of many fine-grained crystals (1.5–3 µm) with different orientations; discrete single diamonds (2–20 µm) are rare. All measured Raman spectra show an intense diamond band at 1332–1328 cm^?1 and have a negative correlation with full width at half maximum (FWHM) of 5.8–11.3 cm^?1. These data combined with previously reported diamond band data (1331–1337 cm^?1) are compatible with those of diamond inclusions in various host minerals from other UHP terranes, but are different from those of ureilite diamonds. The Erzgebirge microdiamonds in zircon do not display visible disordered sp³-carbon, but show downshifting of the Raman band from the ideal value (1332 cm^?1), and have a broader diamond band (FWHM >3 cm^?1) than those of well-ordered diamonds. These features may reflect imperfect ordering due to rapid nucleation/crystallization during UHP metamorphism and rapid exhumation of the UHP terrane. Graphite inclusions in zircon show a typical G-band at 1587 cm^?1. Our study together with previously reported C-isotopic compositions (δ¹³C, ?17 to ?27‰) of diamond and occurrences of fluid/melt inclusions in diamond and garnet indicates that Erzgebirge microdiamonds are metamorphic, have an organic carbon source, and crystallized from aqueous fluids. Limited long-range ordering suggested by the Raman spectra is a function of the P–T time of crystallization and subsequent thermal annealing on decompression. Combined with regional geology, our work further constrains the tectonic evolution of the Erzgebirge terrane.     

Diamonds from the Buffalo Head Hills,Alberta: Formation in a non-conventional setting

Kimberlite pipes K11, K91 and K252 in the Buffalo Head Hills, northern Alberta show an unusually large abundance (20%) of Type II (no detectable nitrogen) diamonds. Type I diamonds range in nitrogen content from 6 ppm to 3300 ppm and in aggregation states from low (IaA) to complete (IaB). The Type IaB diamonds extend to the lowest nitrogen concentrations yet observed at such high aggregation states, implying that mantle residence occurred at temperatures well above normal lithospheric conditions. Syngenetic mineral inclusions indicate lherzolitic, harzburgitic, wehrlitic and eclogitic sources. Pyropic garnet and forsteritic olivine characterize the peridotitic paragenesis from these pipes. One lherzolitic garnet inclusion has a moderately majoritic composition indicating a formation depth of ∼ 400 km. A wehrlitic paragenesis is documented by a Ca-rich, high-chromium garnet and very CaO-rich (0.11–0.14 wt.%) olivine. Omphacitic pyroxene and almandine-rich garnet are characteristic of the eclogitic paragenesis. A bimodal δ¹³C distribution with peaks at − 5‰ and − 17‰ is observed for diamonds from all three kimberlite pipes. A large proportion (∼ 40%) of isotopically light diamonds (δ¹³C < −10‰) indicates a predominantly eclogitic paragenesis.The Buffalo Head Terrane is of Lower Proterozoic metamorphic age (2.3–2.0 Ga) and hence an unconventional setting for diamond exploration. Buffalo Hills diamonds formed during multiple events in an atypical mantle setting. The presence of majorite and abundance of Type II and Type IaB diamonds suggests formation under sublithospheric conditions, possibly in a subducting slab and resulting megalith. Type IaA to IaAB diamonds indicate formation and storage under lower temperature in normal lithospheric conditions.     

Carbon and nitrogen isotope,and mineral inclusion studies on the diamonds from the Pozanti–Karsanti chromitite,Turkey

The Pozanti–Karsanti ophiolite (PKO) is one of the largest oceanic remnants in the Tauride belt, Turkey. Micro-diamonds were recovered from the podiform chromitites, and these diamonds were investigated based on morphology, color, cathodoluminescence, nitrogen content, carbon and nitrogen isotopes, internal structure and inclusions. The diamonds recovered from the PKO are mainly mixed-habit diamonds with sectors of different brightness under the cathodoluminescence images. The total δ¹³C range of the PKO diamonds varies between ??18.8 and ??28.4‰, with a principle δ¹³C mode at ??25‰. Nitrogen contents of the diamonds range from 7 to 541 ppm with a mean value of 171 ppm, and the δ¹⁵N values range from ??19.1 to 16.6‰, with a δ¹⁵N mode of ??9‰. Stacking faults and partial dislocations are commonly observed in the Transmission Electron Microscopy foils whereas inclusions are rather rare. Combinations of (Ca_0.81Mn_0.19)SiO₃, NiMnCo-alloy and nano-sized, quenched fluid phases were observed as inclusions in the PKO diamonds. We believe that the ¹³C-depleted carbon signature of the PKO diamonds derived from previously subducted crustal matter. These diamonds may have crystallized from C-saturated fluids in the asthenospheric mantle at depth below 250 km which were subsequently carried rapidly upward by asthenospheric melts.     

Evidence for large scale fractionation of carbon isotopes and of nitrogen impurity during crystallization of gem quality cubic diamonds from placers of North Yakutia

The spatial distribution of carbon and nitrogen isotopes and of nitrogen concentrations is studied in detail in three gem quality cubic diamonds of variety II according to Orlov’s classification. Combined with the data on composition of fluid inclusions our results point to the crystallization of the diamonds from a presumably oxidized carbonate fluid. It is shown that in the growth direction δ¹³C of the diamond becomes systematically lighter by 2–3‰ (from –13.7 to –15.6‰ for one profile and from –11.7 to –14.1‰ for a second profile). Simultaneously, we observe substantial decrease in the nitrogen concentration (from 400–1000 to 10–30 at ppm) and a previously unrecognized enrichment of nitrogen in light isotope, exceeding 30‰. The systematic and substantial changes of the chemical and isotopic composition can be explained using the Burton-Prim-Slichter model, which relates partition coefficients of an impurity with the crystal growth rate. It is shown that changes in effective partition coefficients due to a gradual decrease in crystal growth rate describes fairly well the observed scale of the chemical and isotopic variations if the diamond-fluid partition coefficient for nitrogen is significantly smaller than unity. This model shows that nitrogen isotopic composition in diamond may result from isotopic fractionation during growth and not reflect isotopic composition of the mantle fluid. Furthermore, it is shown that the infra-red absorption at 1332 сm^-1 is an integral part of the Y-defect spectrum. In the studied natural diamonds the 1290 сm^-1 IR absorption band does not correlate with boron concentration.     

Morphological Features of Diamond Crystals Dissolved in Fe<Subscript>0.7</Subscript>S<Subscript>0.3</Subscript> Melt at 4 GPa and 1400°C

An experimental study of the dissolution of natural and synthetic diamonds in a sulfur-bearing iron melt (Fe_0.7S_0.3) with high P–T parameters (4 GPa, 1400°С) was performed. The results demonstrated that under these conditions, octahedral crystals with flat faces and rounded tetrahexahedral diamond crystals are transformed into rounded octahedroids, which have morphological characteristics similar to those of natural diamonds from kimberlite. It was suggested that, taking into account the complex history of individual natural diamond crystals, including the dissolution stages, sulfur-bearing metal melts up to sulfide melts were not only diamond-forming media during the early evolution of the Earth, but also natural solvents of diamond in the mantle environment before the formation of kimberlitic melts.     

Gold and platinum group minerals in placers of the South Urals: Composition,microinclusions of ore minerals and primary sources

Gold and platinum group minerals from the gold placers of the South Urals are studied in order to identify the metal sources. In placers from the Main Uralian fault zone (MUF), the primary gold contains Ag (up to 29 wt.%), Cu (up to 2 wt.%) and Hg (up to 4 wt.%) and its fineness ranges from 538 to 997‰. Tetra-auricupride and cupriferous gold (up to 20 wt.% Cu) are common for the Nizhny Karabash placer of the MUF zone. In the eastern part of the South Urals, the placer gold is mainly characterized by high fineness of 900–1000‰ and low Cu contents (max 1.38 wt.%). Most of the placer gold grains consist of the primary domains, which are rimmed by secondary high-fineness gold with diffuse and clear boundaries. The secondary gold also develops along the shear dislocations of primary gold. Gold contains microinclusions of geerite, balkanite, chalcopyrite, Se-bearing galena, sphalerite, pyrite, pyrrhotite, arsenopyrite and hematite.Twenty four (including five unnamed) platinum group minerals (PGMs) were found in 28 placers; those from the Kialim and Maly Iremel placers of the Miass placer zone were studied in details. In the Kialim placer, ruthenium is most abundant PGM, which hosts microinclusions of isoferroplatinum, ferroan platinum, laurite, cupriferous gold, a mineral similar in composition to tolovkite, heazlewoodite and unnamed RhSbS phase. The osmium contains microinclusions of erlichmanite and laurite. The iridium grains hosts various sulfides and arsenides of platinum group elements (PGEs). The inclusion-free PGMs form Ru compositional trend in contrast to Os–Ru trend of the Ir-depleted inclusion-hosted PGMs. The isoferroplatinum from the Maly Iremel placer hosts laurite, rhodarsenite, bowieite, a mineral similar in composition to miassite and unnamed sulfide of Pt (Pt_1.11S_2.00) and antimonide of Pd ((Pd_2.41Rh_0.43Fe_0.17)_3.01(Sb_0.91Te_0.09)_1.00). Ruthenium is a host to isoferroplatinum, PGE sulfides and arsenides, and heazlewoodite. Osmium contains microinclusions of ferroan platinum; iridium is a host to a mineral similar in composition to hongshiite. Three types of PGM intergrowths were identified in the Maly Iremel samples: (1) the intergrowths of platy grains of ruthenium with isoferroplatinum and a mineral similar in composition to tulameenite; (2) the open-latticework intergrowths of platy crystals of ruthenium with interstitial aggregates made up of gold, isoferroplatinum and a mineral similar in composition to xingzhongite and (3) the intergrowths of osmium and irarsite and iridarsenite, which are developed along cleavage of the osmium grains. Nickel sulfides associated with some PGMs contain Ru (11.32 wt.%) and Rh (2.21 wt.%) in millerite and Ir (31.00 wt.%), Ru (5.81 wt.%) and Rh (2.87 wt.%) in vaesite.The primary metal sources were determined on the basis of the mineral assemblages and composition of minerals, taking into account the nearby mineral deposits and directions of rivers. The rodingite-associated gold, gold-bearing massive sulfide and chromite deposits are major sources of gold and PGMs in placers of the Miass placer zone confined to the MUF structure of the South Urals. In the southern part of this structure, gold was mainly originated from orogenic gold–sulfide deposits associated with volcanic/volcaniclastic rocks and listvenite-associated gold deposits. The placer PGMs were derived from the adjacent ultramafic massifs of ophiolitic origin. The distance between the placers and primary deposits varies from 2 to 5 km (up to 20 km in the extended valley of the Miass River). Usage of ore microinclusions and associated PGMs in study of placer gold is far more advanced than an ordinary consideration of gold composition alone. This approach allowed us to identify the concrete sources for individual placers and to predict some mineralogical findings in already known primary occurrences.