Diamond growth from oxidized carbon sources beneath the Northern Slave Craton, Canada: A δC-N study of eclogite-hosted diamonds from the Jericho kimberlite

Diamonds from high- and low-MgO groups of eclogite xenoliths from the Jericho kimberlite, Slave Craton, Canada were analyzed for carbon isotope compositions and nitrogen contents. Diamonds extracted from the two groups show remarkably different nitrogen abundances and δ¹³C values. While diamonds from high-MgO eclogites have low nitrogen contents (5-82 ppm) and extremely low δ¹³C values clustering at ∼−40‰, diamonds from the low-MgO eclogites have high nitrogen contents (>1200 ppm) and δ¹³C values from −3.5‰ to −5.3‰.Coupled cathodoluminescence (CL) imaging and SIMS analysis of the Jericho diamonds provides insight into diamond growth processes. Diamonds from the high-MgO eclogites display little CL structure and generally have constant δ¹³C values and nitrogen contents. Some of these diamonds have secondary rims with increasing δ¹³C values from −40‰ to ∼−34‰, which suggests secondary diamond growth occurred from an oxidized growth medium. The extreme negative δ¹³C values of the high-MgO eclogite diamonds cannot be produced by Rayleigh isotopic fractionation of average mantle-derived carbon (−5‰) or carbon derived from typical organic matter (∼−25‰). However, excursions in δ¹³C values to −60‰ are known in the organic sedimentary record at ca. 2.7 and 2.0 Ga, such that diamonds from the high-MgO eclogites could have formed from similar organic matter brought into the Slave lithospheric mantle by subduction.SIMS analyses of a diamond from a low-MgO eclogite show an outer core with systematic rimwards increases in δ¹³C values coupled with decreases in nitrogen contents, and a rim with pronounced alternating growth zones. The coupled δ¹³C-nitrogen data suggest that the diamond precipitated during fractional crystallization from an oxidized fluid/melt from which nitrogen was progressively depleted during growth. Model calculations of the co-variation of δ¹³C-N yielded a partition coefficient (K_N) value of 5, indicating that nitrogen is strongly compatible in diamond relative to the growth medium. δ¹³C values of diamond cores (−4‰) dictate the growth medium had higher δ¹³C values than primary mantle-derived carbon. Therefore, possible carbon sources for the low-MgO eclogite diamonds include oxidized mantle-derived (e.g. protokimberlite or carbonatite) fluids/melts that underwent some fractionation during migration or, devolatilized subducted carbonates.     

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.     

Nitrogen components in ureilites

Abundances and isotopic compositions of nitrogen and argon have been investigated in bulk samples as well as in acid-resistant C-rich residues of a suite of ureilites consisting of six monomict (Haverö, Kenna, Lahrauli, ALH81101, ALH82130, LEW85328), three polymict (Nilpena, EET87720, EET83309), and the diamond-free ureilite ALH78019. Nitrogen in bulk ureilites varies from 6.3 ppm (in ALH 78019) to ∼55 ppm (in ALH82130), whereas C-rich acid residues have ∼65 to ∼530 ppm N, showing approximately an order of magnitude enrichment, compared with the bulk ureilites, somewhat less than trapped noble gases. Unlike trapped noble gases that show uniform isotopic composition, nitrogen shows a wide variation in δ¹⁵N values within a given ureilite as well as among different ureilites. The variations observed in δ¹⁵N among the ureilites studied here suggest the presence of at least five nitrogen components. The characteristics of these five N components and their carrier phases have been identified through their release temperature during pyrolysis and combustion, their association with trapped noble gases, and their carbon (monitored as CO + CO₂ generated during combustion). Carrier phases are as follows: 1) Amorphous C, as found in diamond-free ureilite ALH78019, combusting at ≤500°C, with δ¹⁵N = -21‰ and accompanied by trapped noble gases. Amorphous C in all diamond-bearing ureilites has evolved from this primary component through almost complete loss of noble gases, but only partial N loss, leading to variable enrichments in ¹⁵N. 2) Amorphous C as found in EET83309, with similar release characteristics as component 1, δ¹⁵N ≥ 50‰ and associated with trapped noble gases. 3) Graphite, as clearly seen in ALH78019, combusting at ≥700°C, δ¹⁵N ≥ 19‰ and devoid of noble gases. 4) Diamond, combusting at 600-800°C, δ¹⁵N ≤ -100‰ and accompanied by trapped noble gases. 5) Acid-soluble phases (silicates and metal) as inferred from mass balance are expected to contain a large proportion of nitrogen (18 to 75%) with δ¹⁵N in the range -25‰ to 600‰. Each of the ureilites contains at least three N components carried by acid-resistant C phases (amorphous C of type 1 or 2, graphite, and diamond) and one acid-soluble phase in different proportions, resulting in the observed heterogeneity in δ¹⁵N. In addition to these five widespread components, EET83309 needs an additional sixth N component carried by a C phase, combusting at <700°C, with δ¹⁵N ≥ 153‰ and accompanied by noble gases. It could be either noble gas-bearing graphite or more likely cohenite. Some excursions in the δ¹⁵N release patterns of polymict ureilites are suggestive of contributions from foreign clasts that might be present in them.Nitrogen isotopic systematics of EET83309 clearly confirm the absence of diamond in this polymict ureilite, whereas the presence of diamond is clearly indicated for ALH82130. Amorphous C in ALH78019 exhibits close similarities to phase Q of chondrites.The uniform δ¹⁵N value of −113 ± 13 ‰ for diamond from both monomict and polymict ureilites and its independence from bulk ureilite δ¹⁵N, Δ¹⁷O, and %Fo clearly suggest that the occurrence of diamond in ureilites is not a consequence of parent body-related process. The large differences between the δ¹⁵N of diamond and other C phases among ureilites do not favor in situ shock conversion of graphite or amorphous C into diamond. A nebular origin for diamond as well as the other C phases is most favored by these data. Also the preservation of the nitrogen isotopic heterogeneity among the carbon phases and the silicates will be more consistent with ureilite formation models akin to “nebular sedimentation” than to “magmatic” type.     

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.     

Nitrogen isotope fractionations during progressive metamorphism: A case study from the Paleozoic Cooma metasedimentary complex, southeastern Australia

The well-studied Paleozoic Cooma metamorphic complex in southeastern Australia is characterized by a uniform siliciclastic protolith, of uniform age, with a continuous range of metamorphic grade from subgreenschist- to upper amphibolite-facies, and migmatite-grade in an annular pattern around the Cooma granodiorite. Those conditions are optimal for investigating variations of N concentrations and δ¹⁵N values during progressive metamorphism. Nitrogen concentrations decrease and δ¹⁵N increases with increasing metamorphic grade (sub-chlorite zone: 120 ppm N, δ¹⁵N = 2.3‰; chlorite zone: 110 ppm N, δ¹⁵N = 3.0‰; biotite and andalusite zone: 85 ppm N, δ¹⁵N = 3.8 ‰; sillimanite and migmatite zones: 40 ppm N, δ¹⁵N = 10.7‰). Covariation of K and N contents is consistent with N substituting for K as NH₄⁺ in micas. Observed trends of increasing δ¹⁵N values with decreasing nitrogen concentrations can be explained by a continuous release of nitrogen depleted in ¹⁵N with progressive metamorphism, which causes an enrichment of ¹⁵N in the residual nitrogen of the rock. Equilibrium models for Rayleigh distillation and batch volatilisation for data of the greenschist and amphibolite facies metasedimentary rocks can be explained by N₂-NH₄⁺ exchange at temperatures of 300-600 °C, whereas observed large fractionations for the upper amphibolite-facies and melt products in the migmatite-grade samples may be interpreted as NH₃-NH₄⁺ exchanges at temperature of 650-730 °C. Lower values in the highest grade zones may also stem in part from input of ¹⁵N-depleted fluids from the granodiorite.The magnitude of isotope fractionation of nitrogen is about 1-2‰ during progressive metamorphism of metasedimentary rocks from sub-chlorite zone to biotite-andalusite zone, which is consistent with previous studies. Consequently, the large spread of δ¹⁵N values in Archean greenschist-facies metasedimentary rocks of −6‰ to 30‰ can be accounted for by variable mixtures of mantle plume-dominated volatiles with a δ¹⁵N of −5‰, and a ¹⁵N-enriched marine sedimentary kerogen component inherited from a CI chondrite veneer having δ¹⁵N of 30‰ to 42‰.     

Platelet development in cuboid diamonds: insights from micro-FTIR mapping

Fourier transform infrared mapping of diamonds can reveal detailed information on impurities, with a spatial context. We apply this technique, combined with in situ isotopic analysis of carbon, to the study of cuboid diamond growth in a sample that exhibits some mixed-habit growth. While there has been some uncertainty in the literature regarding sectoral differences in nitrogen aggregation and subsequent platelet development, the data from this study appear far more conclusive. We show that despite nitrogen being concentrated in octahedral sectors, there is no detectable difference in the concentration-adjusted rate of nitrogen aggregation within octahedral and cuboid sectors. However, the resultant platelet development is significantly reduced in cuboid sectors compared to contemporaneously formed octahedral sectors. This finding has significant implications for the classification of diamonds using the relationship between their platelet intensity and the absorption caused by B centres. It means that cuboid diamonds naturally fall below the linear relationship that has been termed regular, which would lead to them being incorrectly interpreted as having experienced heating or deformation. The data also support earlier suggestions that large hydrogen concentrations in the diamond-forming fluid may be required for cuboid growth. We further suggest that high nitrogen and hydrogen concentrations are required for mixed-habit diamond growth, which might be the product of specific fluid chemistries that occur in reducing mantle environments.     

Enigmatic diamonds in Archean calc-alkaline lamprophyres of Wawa, southern Ontario, Canada

A suite of 80 macrodiamonds recovered from volcaniclastic breccia of Wawa (southern Ontario) was characterized on the basis of morphology, nitrogen content and aggregation, cathodoluminescence (CL), and mineral inclusions. The host calc-alkaline lamprophyric breccias were emplaced at 2.68–2.74 Ga, contemporaneously with voluminous bimodal volcanism of the Michipicoten greenstone belt. The studied suite of diamonds differs from the vast majority of diamond suites found worldwide. First, the suite is hosted by calc-alkaline lamprophyric volcanics rather than by kimberlite or lamproite. Second, the host volcanic rock is amongst the oldest known diamondiferous rocks on Earth, and has experienced regional metamorphism and deformation. Finally, most diamonds show yellow-orange-red CL and contain mineral inclusions not in equilibrium with each other or their host diamond. The majority of the diamonds in the Wawa suite are colorless, weakly resorbed, octahedral single crystals and aggregates. The diamonds contain 0–740 ppm N and show two modes of N aggregation at 0–30 and 60–95% B-centers suggesting mantle storage at 1,100–1,170°C. Cathodoluminescence and FTIR spectroscopy shows that emission peaks present in orange CL stones do not likely result from irradiation or single substitutional N, in contrast to other diamonds with red CL. The diamonds contain primary inclusions of olivine (Fo₉₂ and Fo₈₉), omphacite, orthopyroxene (En₉₃), pentlandite, albite, and An-rich plagioclase. These peridotitic and eclogitic minerals are commonly found within single diamonds in a mixed paragenesis which also combines shallow and deep phases. This apparent disequilibrium can be explained by effective small-scale mixing of subducted oceanic crust and mantle rocks in fast “cold” plumes ascending from the top of the slabs in convergent margins. Alternatively, the diamonds could have formed in the pre-2.7–2.9 Ga cratonic mantle and experienced subsequent alteration of syngenetic inclusions related to host magmatism and ensuing metamorphism. Neither orogenic nor cratonic model of the diamond origin fully explains all of the observed characteristics of the diamonds and their host rocks. Electronic Supplementary Material Supplementary material is available for this article at and is accessible for authorized users.     

Volatile composition of microinclusions in diamonds from the Panda kimberlite, Canada: Implications for chemical and isotopic heterogeneity in the mantle

In order to better investigate the compositions and the origins of fluids associated with diamond growth, we have carried-out combined noble gas (He and Ar), C and N isotope, K, Ca and halogen (Cl, Br, I) determinations on fragments of individual microinclusion-bearing diamonds from the Panda kimberlite, North West Territories, Canada. The fluid concentrations of halogens and noble gases in Panda diamonds are enriched by several orders of magnitude over typical upper mantle abundances. However, noble gas, C and N isotopic ratios (³He/⁴He = 4-6 Ra, ⁴⁰Ar/³⁶Ar = 20,000-30,000, δ¹³C = −4.5‰ to −6.9‰ and δ¹⁵N = −1.2‰ to −8.8‰) are within the worldwide range determined for fibrous diamonds and similar to the mid ocean ridge basalt (MORB) source value. The high ³⁶Ar content of the diamonds (>1 × 10⁻⁹ cm³/g) is at least an order of magnitude higher than any previously reported mantle sample and enables the ³⁶Ar content of the subcontinental lithospheric mantle to be estimated at ∼0.6 × 10⁻¹² cm³/g, again similar to estimates for the MORB source. Three fluid types distinguished on the basis of Ca-K-Cl compositions are consistent with carbonatitic, silicic and saline end-members identified in previous studies of diamonds from worldwide sources. These fluid end-members also have distinct halogen ratios (Br/Cl and I/Cl). The role of subducted seawater-derived halogens, originally invoked to explain some of the halogen ratio variations in diamonds, is not considered an essential component in the formation of the fluids. In contrast, it is considered that large halogen fractionation of a primitive mantle ratio occurs during fluid-melt partitioning in forming silicic fluids, and during separation of an immiscible saline fluid.     

津巴布韦金刚石中石墨包裹体及金刚石异常双折射特征分析

津巴布韦马朗(Marange)金刚石矿以产出混合习性(八面体与近立方体)金刚石为特征,其石墨包裹体仅存在于近立方体区.石墨包裹体的形态、分布及金刚石的异常双折射与应变特征,能反映其从开始结晶到被搬运至地表过程中经历的地质作用.因此,对津巴布韦混合习性金刚石及石墨包裹体的研究不仅能提供与其他产地金刚石有对比意义的数据,且...     

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.     

Causes of variations in morphology and impurities of diamonds from the Udachnaya Pipe eclogite

A unique xenolith of eclogite, 23×17×11 cm in size and 8 kg in weight, was found in the Udachnaya kimberlite pipe. One hundred twenty-four diamond crystals recovered from it were analyzed by a number of methods. The diamonds differ in morphology, internal structure, color, size, and composition of defects and impurities. The xenolith contains diamonds of octahedral and cubooctahedral habits. In cathodoluminescence, the octahedral crystals have a brightly glowing core with octahedral zones of growth and a weakly glowing rim. In the cores of these crystals the N impurity is mostly present in the B1 form (30 to 60%). At the same time, N in the rim is chiefly in the A form. The cubooctahedral crystals show a weak luminescence. The content of nitrogen and degree of its aggregation are close to those in the rim of octahedral crystals. The diversity of morphology and impurity composition of diamonds from the xenolith can be explained by their formation in two stages. At the first stage, the diamonds formed which became the cores of octahedra. After a long-time interruption, at the second stage of diamond formation crystals of cubooctahedral habit appeared and the octahedral crystals were overgrown. Wide variations in nitrogen contents in the xenolith crystals allowed their use to estimate the kinetics of aggregated nitrogen. The data obtained show that the aggregation of A centers into B1 centers in the diamonds is described by a kinetic reaction of an order of 1.5.     

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.     

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.     

Isotopic composition of carbon in diamonds of diamondites: record of mass fractionation in the upper mantle

Carbon isotope data have been obtained for diamonds in diamondites (framesites, polycrystalline diamond) of unknown origin (presumably from southern Africa), which contain minor amounts of garnet (plus rare clinopyroxene). The carbon isotope abundance ratios show wide inter- and intra-sample ranges. The δ¹³C variations of diamonds from diamondites with “peridotitic” or “eclogitic” garnets are indistinguishable from each other, with a range from −3.2 to −27.9‰, and a peak around −18‰, indicating a depletion in ¹³C relative to most silicate-bearing single crystal diamonds. This ¹³C depletion could have been produced by mass fractionation of C from an isotopically homogeneous mantle source in a C-O-H fluid system. Fluids traveling between regions of varying redox conditions in the mantle could have provided the necessary vehicle. The variations of δ¹³C can be explained by different degrees of oxidation during the fluid/melt ascent.     

Directional chemical variations in diamonds showing octahedral following cuboid growth

A progression from cuboid to octahedral growth has been observed in 16 natural diamonds from Yakutian kimberlites. X-ray and cathodoluminescence topography have revealed that the change in morphology of diamonds with cloudy cuboid cores may occur without mixed-habit growth but via generation of numerous octahedral apices on cuboid surfaces and subsequent gradual transformation into regular octahedral morphology. Nitrogen aggregation in both cuboid and octahedral domains of such diamonds suggests that they have had a long residence time under mantle conditions. Micro-inclusions in the cuboid domains of the diamonds testify to the nucleation and growth of cuboid cores from a hydrous-carbonatitic (oxidized) fluid. The transition from cuboid hummocky growth rich in inclusions to octahedral growth without inclusions may be linked to decreasing supersaturation in the parent fluid. Measurements of δ¹³C and N_ppm by ion microprobe show that the chemical variations observed between inner cuboid domains and outer octahedral zones commonly have a systematic character and as such they are probably not due to purely kinetic effects. The peripheral octahedral zones are always enriched in ¹³C in comparison with inner cuboid ones, and the total nitrogen content decreases with the change from cuboid to octahedral growth. The octahedral outer zones show a gradual progressive increase in δ¹³C, with an overall change of up to 5‰ from the cuboid core (δ¹³C usually between −8 and −6‰) to the diamond margin (δ¹³C usually between −4 and −2‰). Decreases in δ¹³C of this magnitude with a gradual increase in ¹³C may be attributed to the Rayleigh fractionation operating on a single parent fluid of close to normal mantle δ¹³C composition with diamond precipitating by the reduction of carbonatitic fluid in a closed system. However, one sample shows a variation of δ¹³C of approximately −17 to −6‰ and therefore suggests a possible change of fluid source composition from one containing subducted crustal organic carbon to one with common mantle carbon. An erratum to this article can be found at     

Origin of sub-lithospheric diamonds from the Juina-5 kimberlite (Brazil): constraints from carbon isotopes and inclusion compositions

Forty-one diamonds sourced from the Juina-5 kimberlite pipe in Southern Brazil, which contain optically identifiable inclusions, have been studied using an integrated approach. The diamonds contain <20 ppm nitrogen (N) that is fully aggregated as B centres. Internal structures in several diamonds revealed using cathodoluminescence (CL) are unlike those normally observed in lithospheric samples. The majority of the diamonds are composed of isotopically light carbon, and the collection has a unimodal distribution heavily skewed towards δ¹³C ~ ?25 ‰. Individual diamonds can display large carbon isotope heterogeneity of up to ~15 ‰ and predominantly have isotopically lighter cores displaying blue CL, and heavier rims with green CL. The light carbon isotopic compositions are interpreted as evidence of diamond growth from abiotic organic carbon added to the oceanic crust during hydrothermal alteration. The bulk isotopic composition of the oceanic crust, carbonates plus organics, is equal to the composition of mantle carbon (?5 ‰), and we suggest that recycling/mixing of subducted material will replenish this reservoir over geological time. Several exposed, syngenetic inclusions have bulk compositions consistent with former eclogitic magnesium silicate perovskite, calcium silicate perovskite and NAL or CF phases that have re-equilibrated during their exhumation to the surface. There are multiple occurrences of majoritic garnet with pyroxene exsolution, coesite with and without kyanite exsolution, clinopyroxene, Fe or Fe-carbide and sulphide minerals alongside single occurrences of olivine and ferropericlase. As a group, the inclusions have eclogitic affinity and provide evidence for diamond formation at pressures extending to Earth’s deep transition zone and possibly the lower mantle. It is observed that the major element composition of inclusions and isotopic compositions of host Juina-5 diamonds are not correlated. The diamond and inclusion compositions are intimately related to subducted material and record a polybaric growth history across a depth interval stretching from the lower mantle to the base of the lithosphere. It is suggested that the interaction of slab-derived melts and mantle material combined with subsequent upward transport in channelised networks or a buoyant diapir explains the formation of Juina-5 diamonds. We conclude that these samples, despite originating at great mantle depths, do not provide direct information about the ambient mantle, instead, providing a snapshot of the Earth’s deep carbon cycle.     

An infrared investigation of inclusion-bearing diamonds from the Venetia kimberlite,Northern Province,South Africa : implications for diamonds from craton-margin settings

The Venetia kimberlites in the Northern Province of South Africa sampled diamonds from the lithosphere underlying the Central Zone of the Limpopo Belt. Given the general correlation of diamond-bearing kimberlites with old stable cratons, this tectonic setting is somewhat anomalous and, therefore, it is desirable to characterise the diamonds in terms of their infrared characteristics. A suite of diamonds of known paragenesis from the Venetia mine spans a large range of nitrogen concentrations from less than the detection limit to 1,355 ppm. Diamond nitrogen contents are, on average, higher in the eclogitic diamond population relative to the websteritic and peridotitic diamonds. Nitrogen aggregation states are variable, ranging from almost pure type IaA diamond (poorly aggregated nitrogen) to pure type IaB diamond (highly aggregated nitrogen). On a nitrogen aggregation diagram two distinct groups can be identified based on nitrogen content and nitrogen aggregation state. These are a minor population of diamonds with nitrogen contents generally higher than 500 ppm and nitrogen aggregation states of less than 40% IaB, and another, dominant population that is characterised by higher and more variable nitrogen aggregation. The unusually aggregated nature of the majority of the diamonds analysed is unique to Venetia relative to other intrusives on the Kaapvaal-Kalahari craton, but is similar to aggregation states observed for diamonds from other craton margin or adjacent mobile belt settings such as the Argyle lamproite and the George Creek kimberlite. This could be a consequence of diamond mantle residence at mantle temperatures higher than the norm for other kimberlites from the interior of cratons. Deformation of the mantle, associated with dynamic processes such as orogenesis or subduction, might also be responsible for accelerating the rate of nitrogen aggregation in these diamonds. Low numbers of diamonds with degradation of platelets at the Venetia kimberlite, relative to diamonds from the Argyle lamproite, indicate that deformation was at a significantly lower level. The comparatively low value of diamonds from Argyle (at approximately US8/carat) as opposed to Venetia (US8/carat) as opposed to Venetia (US90/carat) is in large part because of the very high abundance of brown diamonds at Argyle. Therefore, it is apparent that deformational history of the mantle in which the diamonds were resident prior to or during sampling by the host may have an important role to play in the profitability of a primary diamond deposit. The apparently consistent association of diamonds with unusually aggregated nitrogen with kimberlites, or lamproites intruded into craton margin or mobile belt settings suggests that it may be possible to recognise such contributory sources in alluvial diamond deposits, through the study of the infrared characteristics of the diamonds. Electronic supplementary material to this paper can be obtained by using the Springer Link server located at http://dx.doi.org/10.1007/s00410-002-0385-2     

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.     

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.     

湖南金刚石内部不均一性特征研究

将湖南金刚石加工成片，利用宝石显微镜，偏光镜，阴极发光（CL）仪和傅里叶红外光谱（FTIR）仪对其内部显微特征进行了研究，发现金刚石的颜色深浅不一，内外颜色差异明显，呈带状，斑状分布；金刚石由生长中心至边缘，氮含量也有较大变化，中心与边缘最大相差约50倍，氮的富集类型由中心向边缘表现出B中心所占的比例越来越小，金刚石的类型也相应从I型→II型或I－aAB型→-I-aA型等，这些不均一性特征，反映金刚石在生长过程中环境条件发生了变化，以及生长期后可能受到了改造。