Structural defects in natural plastically deformed diamonds: Evidence from EPR spectroscopy

Structural defects formed as a result of plastic deformation in natural diamond crystals have been studied by EPR spectroscopy. The spectra of brown, pink-brown, black-brown, pink-purple, and gray plastically deformed diamonds of type Ia from deposits in Yakutia and the Urals were recorded. The results of EPR spectroscopy allowed us to identify various deformation centers in the structure of natural diamonds and to show that nitrogen centers were transformed under epigenetic mechanical loading. Abundant A centers, consisting of two isomorphic nitrogen atoms located in neighboring structural sites, were destroyed as a result of this process to form a series of N1, N4, W7, M2, and M3 nitrogen centers. Such centers are characterized by an anisotropic spatial distribution and a positive charge, related to the mechanism of their formation. In addition, N2 centers (probably, deformation-produced dislocations decorated by nitrogen) were formed in all plastically deformed diamonds and W10 and W35 centers (the models have not been finally ascertained) were formed in some of them. It has been established that diamonds with various types of deformation-induced color contain characteristic associations of these deformation centers. The diversity of associations of deformation centers indicates appreciable variations in conditions of disintegration of deep-seated rocks, transfer of diamonds to the Earth’s surface, and formation of kimberlitic deposits. Depending on the conditions of mechanical loading, the diamond crystals were plastically deformed by either dislocation gliding or mechanical twinning. Characteristic features of plastic deformation by dislocation gliding are the substantial prevalence of the N2 centers over other deformation centers and the occurrence of the high-spin W10 and W35 centers. The attributes of less frequent plastic deformation by mechanical twinning are unusual localization of the M2 centers and, in some cases, the N1 centers in microtwinned lamellae. Numerous data on models of deformation centers in natural diamonds, including the M2 and M3 centers, which were observed in the studied collection for the first time, are discussed.     

CVD合成钻石的层状生长结构和紫外荧光特征

最近NGTC实验室检测出多批次CVD合成钻石,这些CVD合成钻石均具有明显的鉴定特征,使用钻石观测仪（DiamondViewTM）观察可见蓝色、橙红色荧光和蓝色磷光以及细密层状生长纹理,光致发光光谱中可见737 nm处的特征发光线.这些特征均与其生长结构及生长过程中进入钻石晶体中的杂质有关.笔者以最近检测过程中发现的一颗CVD合成钻石为例,使用高倍率显微技术对其层状结构的微细特征及其在钻石观测仪下的荧光特征的关系进行了详细观察和对比.结果显示,此样品与之前检测到的CVD合成钻石略有差异.此次检测到的样品在钻石观测仪（DiamondViewTM）下观察具有较宽的层状生长分区,层与层之间的分界线十分明显且在高倍显微镜下也可见到细微的生长特征.通过对样品特征的分析,了解了晶体生长过程中多阶段生长条件的变化,更直观的展现了CVD合成钻石的生长过程.     

The Effect of Aggregation of Impurity Nitrogen on Diamond X-Ray Luminescence

Two samplings of 65 diamond crystals divided by the intensity of a slow X-ray luminescence component are studied from the Arkhangel’skaya and Karpinskogo-1 pipes. IR and EPR spectroscopies revealed a relationship between the nitrogen A and P2 centers of the diamonds and the presence of a slow X-ray luminescence component. Its absence in most diamonds with high content of P1 (C) centers is explained by the low number of A and P2 centers.     

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.     

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.     

以碳酸盐为碳源生成金刚石的实验研究

本世纪五十年代初,在金属触媒物质的参与下,由石墨得到金刚石的成功,标志着人工合成超硬材料及高温高压技术两方面的巨大突破。三十年来的科学研究和生产实践推动着这一领域不断地向纵深发展,并提出了建立在不同理论基础上的金刚石生成方法,如爆破法、晶种法、气相生长法、常压高温法、薄膜推移法等等。     

Comparison of enigmatic diamonds from the Tolbachik arc volcano (Kamchatka) and Tibetan ophiolites: Assessing the role of contamination by synthetic materials

The enigmatic appearance of cuboctahedral diamonds in ophiolitic and arc volcanic rocks with morphology and infrared characteristics similar to synthetic diamonds that were grown from metal solvent requires a critical reappraisal. We have studied 15 diamond crystals and fragments from Tolbachik volcano lava flows, using Fourier transform infrared spectrometry (FTIR), transmission electron microscopy (TEM), synchrotron X-ray fluorescence (SRXRF) and laser ablation inductively coupled plasma mass-spectrometry (LA-ICP-MS). FTIR spectra of Tolbachik diamonds correspond to typical type Ib patterns of synthetic diamonds. In TEM films prepared using focused ion beam technique, we find Mn-Ni and Mn-Si inclusions in Tolbachik diamonds. SRXRF spectra indicate the presence of Fe-Ni and Fe-Ni-Mn inclusions with Cr, Ti, Cu, and Zn impurities. LA-ICP-MS data show variable but significantly elevated concentrations of Mn, Fe, Ni, and Cu reaching up to 70 ppm. These transition metal concentration levels are comparable with those determined by LA-ICP-MS for similar diamonds from Tibetan ophiolites. Mn-Ni (+Fe) solvent was widely used to produce industrial synthetic diamonds in the former USSR and Russia with very similar proportions of these metals. Hence, it appears highly probable that the cuboctahedral diamonds recovered from Kamchatka arc volcanic rocks represent contamination and are likely derived from drilling tools or other hard instruments. Kinetic data on diamond dissolution in basaltic magma or in fluid phase demonstrate that diamond does not form under the pressures and temperature conditions prevalent within the magmatic system beneath the modern-day Klyuchevskoy group of arc volcanoes. We also considered reference data for inclusions in ophiolitic diamonds and compared them with the composition of solvent used in industrial diamond synthesis in China. The similar inclusion chemistry close to Ni₇₀Mn₂₅Co₅ for ophiolitic and synthetic Chinese diamonds scrutinized here suggests that most diamonds recovered from Tibetan and other ophiolites are not natural but instead have a synthetic origin. In order to mitigate further dubious reports of diamonds from unconventional tectonic settings and source rocks, we propose a set of discrimination criteria to better distinguish natural cuboctahedral diamonds from those produced synthetically in industrial environments and found as contaminants in mantle- and crust-derived rocks.     

Experimental Test of Possible Formation of Diamond under the Differentiation of the Earth

The first results are presented for the synthesis of diamond at 6.5 GPa and 1600°C during migration of molten iron through a silicate matrix, which is composed of olivine crystals with interstitial graphite. The experiment shows that diamonds in the Earth’s mantle and the terrestrial planets could have formed during differentiation. Diamond crystals, which were formed during iron segregation of the Earth’s differentiation, could be centers for further crystallization of mantle diamonds.

     

New data of typomorphic features of diamonds from placers in North Timan

The morphological and spectral-optical properties of diamond crystals from placers in North Timan rivers have been studied with IR-spectroscopy and cathode luminescence methods. As a result, correlation between external characteristics of diamonds (size and degree of mechanical damage) and number of optically active centers has been revealed. The habit and the type of distribution of structural defects in diamond crystals studied are comparable with those in diamonds from the Archangelsk Region and North Timan’s placers. Based on the obtained data, origin issues and possible primary sources of diamonds from North Timan’s placers are discussed.     

Zoning of diamonds from the Mir kimberlite pipe: Results of Fourier-transformed infrared spectroscopy

Plates prepared of diamonds from the Mir kimberlite pipe were examined with FTIR spectroscopy. It is shown that B1 defects were formed by annealing during crystal growth, whereas B2 centers arose after growth cessation. The development of B2 centers in a natural diamond is the secondary process with respect to the aggregation of the nitrogen admixture. The kinetics of this process is related to the breakdown of an oversaturated solid solution. The results obtained make it possible to estimate the temperature and duration of natural diamond growth.     

中国3个商业性钻石产地天然钻石的Diamond ViewTM图像及其意义

对采自我国3个商业性产地山东蒙阴、辽宁瓦房店、湖南常德地区的236片/颗天然钻石样品进行了系统的DiamondViewTM(DV)荧光图像分析,结合CL照相和FTIR的定量计算,探讨了钻石样品DV图像发光结构模式和荧光颜色方面的差异性及其原因。结果表明,3个产地钻石的DV图像和CL图像显示的钻石生长结构基本一致;钻石的发光结构模式与钻石内部氮、氢元素的种类和浓度分布趋势没有明显的一致性,DV图像模式并不完全受钻石类型控制,但DV图像的色调与钻石存在的杂质元素及晶体缺陷有关。钻石的DV图像特征受钻石的生长环境、结晶条件、后期熔蚀、辐照损伤等因素综合制约。从统计学的角度看,3个产地钻石的DV发光模式和荧光颜色有一定的差异,这种差异可以作为区分不同产地来源的钻石的宏观的统计学特征。DiamondViewTM技术在揭示天然钻石生长结构方面和CL发光照相技术效果近似,但更加便利。     

Fe–S melt as a likely solvent of diamond under mantle conditions

The first results of experimental study of diamond dissolution in a S-bearing Fe melt at high P–T parameters are reported and the morphology of partially dissolved crystals is compared with that of natural diamonds. Our results show that under the experimental conditions (4 GPa, 1400°C), flat-faced octahedral diamond crystals are transformed into curve-faced octahedroids with morphological features similar to those of natural diamonds.     

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.     

Zonal distribution of impurities in diamond

The zonal distribution of impurities in six diamonds (2 clear. 1 green-skinned, 2 green-bodied and 1 coated) was studied by neutron activation followed by dissolution of the diamond into a number of fractions. High surface concentrations of impurities found here and by other workers were attributed to both laboratory and natural contaminants. No unusual element distributions were found in the outer layer of the green-skinned diamond, the green skin probably being caused by natural radiation damage. The green-bodied diamonds had very different compositions from each other and from the other diamonds and it is suggested that such stones owe their colour to a high general level of impurities. All the diamonds, including the clear core of the coated diamond, contained impurities thought to be submicroscopic inclusions, either silicates, carbonates or immiscible sulphides derived from the parental magma. Variations in the composition of these inclusions in one diamond suggest changes in the host magma composition during growth. Sulphides apparently occurred in very small amounts throughout all the diamonds. Variations in the concentration of impurities are probably related to changes in growth rate or environment during diamond formation, and could explain some of the zonal variations in the physical properties of diamonds.     

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.     

Metal films on the surfaces and within diamond crystals from Arkhangelskaya and Yakutian diamond provinces

Representative samples of diamonds from five kimberlite pipes (Lomonosovskaya, Archangel’sk, Snegurochka, XXIII Congress of the Communist Party of the Soviet Union (CPSU), and Internationalnaya) of the Arkhangelskaya and Yakutian diamond provinces in Russia have been studied. Thirty-three varieties of metal films have been identified as syngenetic associated minerals. The films consist of 15 chemical elements that occur in the form of native metals and their natural alloys. Remnants of metal films were detected within diamond crystals. The metal films coating diamonds are a worldwide phenomenon. To date, these films have been described from Europe, Asia, South America, and Africa. Native metals, their alloys, and intermetallides are actual companion minerals of diamond.     

Carbon isotopic composition of diamonds in Ukraine and their probable polygenetic nature

The paper presents newly obtained data on the mineralogical and geochemical characteristics of Ukrainian endogenic and supergenic diamonds, including pioneering data on the carbon isotopic composition of individual diamond crystals. The endogenic diamonds occur as euhedral microcrystals (their morphology varies from octahedral to rhombododecahedral and cubic) with broadly varying concentrations of the structural nitrogen admixture and with mostly low aggregation of nitrogen centers. According to their carbon isotopic composition, Ukrainian diamonds range from kimberlitic–lamproitic to metamorphic and even carbonado-like, i.e., are polygenetic. Our data confirm the earlier conclusion that the supergenic diamonds are of impact genesis.     

First diamonds from placers in Primorie

The paper reports the results obtained by the detailed studying of carbonado (the first find in a gold placer in Primorie) and a collection of diamonds that was confiscated in 1937 from a poaching small digger and was kept safe at the Nezametnyi mine (near the village of Vostretsovo), which had developed this placer deposit. In the concentrate from the placer, carbonado is associated with green corundum, various ilmenite, zircon titanian amphiboles and pyroxenes, rutile, anatase, and fragments of subvolcanic biotite picrites. All of these minerals, native aluminum, and tin occur as inclusions in the diamonds. The carbonado from Primorie was determined to be practically identical to this mineral from Brazil, has a porous structure, is characterized by orange luminescence, contains inclusions of Y, Ce, La, Ba, and Sr phosphates, and has an isotopically light composition of its carbon (¹³C from ?25 to ?32‰). Pores of the carbonado aggregates contain clusters of diamond crystals. The collection of diamonds from an unknown source included six gem-quality transparent crystals, one rounded ballas, two cuboctahedral crystals (one of greenish and the other of silver-gray color, both with outer coats), and one black carbonado grain. The data obtained on the mineralogy of the diamonds have demonstrated that they are completely identical to this mineral from kimberlites and lamproites but bear traces of intense dissolution, fragmentation, multiple recrystallization, and graphitization at defects, which are the most widespread in the ballas. One of the crystals was determined to contain inclusions: aggregates of potassic omphacite (0.50 wt % K₂O) and corundum. Ilmenite (containing up to 8 wt % MgO), titanaugite, kaersutite (4 wt % TiO₂, 0.8 wt % K₂O), and churchite (aqueous phosphate) were obtained from the core of the ballas. The titanaugite, kaersutite, and ilmenite were proven to be compositionally analogous to these minerals from picrites occurring near the placer. The carbon isotopic composition δ¹³C of the cores of the single diamond crystals varies from ?6 to ?11‰. The margins of the grains were proved to be enriched in the light carbon isotope (δ¹³C from ?19 to ?21‰). The gem-quality transparent diamond crystals are characterized by blue luminescence, and the color of luminescence in the carbonado varies from orange red in the bulk of the aggregate to yellowish green in its core. The aforementioned transformations of diamonds were likely caused by their transportation in pipes of micaceous picrites of the Jurassic meymechite complex. The carbonado are thought to correspond to the final stage of the metastable recrystallization (in pores, within the temperature range of the rutile-anatase transition) of the original isotopically heavy diamonds under the effect of various oxidizers (H₂O, CO₂, F, and others) and in the presence of catalytically acting REE, Ti, and P. The primary diamond source (kimberlite or lamproite) can be older and more distant from the study area. The complete geological analogy between the study area in Primorie, Kalimantan Island in Indonesia, and West Australia (where no sources of the placers are known) led us to consider the territory of Primorie as promising for exploration for diamondiferous placers.     

Diamond crystallization in the Fe-Co-S-C and Fe-Ni-S-C systems and the role of sulfide-metal melts in the genesis of diamond

Diamond crystals 0.1–0.8 carats were synthesized in experiments conducted in a BARS split-sphere multianvil high-pressure apparatus in the systems Fe-Co-S-C and Fe-Ni-S-C at a pressure of 5.5 GPa and temperature of 1300°C. The microtextures of the samples and the phases accompanying diamond (carbides, graphite, monoslufide solid solution, pentlandite, and taenite) are examined in much detail, the properties of metal-sulfide-carbon alloys are discussed, and issues related to the genesis of sulfide inclusions in diamonds and graphite crystallization in the diamond stability field are considered. The experiments demonstrate that diamonds can be synthesized and grow in pre-eutectic metal-sulfide melts with up to 14 wt % sulfur at relatively low P-T parameters, which correspond to the probable temperatures and pressures of natural diamond-forming processes at depths of approximately 150 km in the Earth’s upper mantle.     

金刚石中微量元素的同步辐射X射线荧光分析

利用同步辐射X射线荧光技术,对人工合成金刚石以及产自山东、辽宁、湖南的天然金刚石进行了微量元素的测试分析。结果表明,在合成金刚石中,检测到了第四周期的元素(除As、Ge、Kr和Br外)和Pb;其中Fe、Co、Ni相对含量高,可能是合成时触媒的混入引起的。天然金刚石中检测到的微量元素有Ca、Ti、Cr、Mn、Fe、Co、Ni、Cu、Zn、W、Au和Pb,但相对含量比合成金刚石中相应的微量元素相对含量低。不同产地的天然金刚石中的微量元素种类及含量存在差异,反映了金刚石地幔生长环境的不同及岩浆对金刚石生长过程的影响。