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The Sheahan Diamond Literature Reference Compilation - Technical Articles based on Major Region - Technology
The Sheahan Diamond Literature Reference Compilation is compiled by Patricia Sheahan who publishes on a monthly basis a list of new scientific articles related to diamonds as well as media coverage and corporate announcements called the Sheahan Diamond Literature Service that is distributed as a free pdf to a list of followers. Pat has kindly agreed to allow her work to be made available as an online digital resource at Kaiser Research Online so that a broader community interested in diamonds and related geology can benefit. The references are for personal use information purposes only; when available a link is provided to an online location where the full article can be accessed or purchased directly. Reproduction of this compilation in part or in whole without permission from the Sheahan Diamond Literature Service is strictly prohibited. Return to Diamond Region Index
Sheahan Diamond Literature Reference Compilation - Scientific Articles by Author for all years
Each article reference in the SDLRC is tagged with one or more key words assigned by Pat Sheahan to highlight the main topics of the article. In addition most references have been tagged with one or more region words. In an effort to make it easier for users to track down articles related to a specific region, KRO has extracted these region words and developed a list of major region words presented in the Major Region Index to which individual region words used in the article reference have been assigned. Each individual Region Report contains in chronological order all the references with a region word associated with the Major Region word. Depending on the total for each reference type - technical, media and corporate - the references will be either in their own technical, media or corporate Region Report, or combined in a single report. Where there is a significant number of technical references there will be a technical report dedicated to the technical articles while the media and corporate references are combined in a separate region report. References that were added in the most recent monthly update are highlighted in yellow within the Region Report. The Major Region words have been defined by a scale system of "general", "continent", "country", "state or province" and "regional". Major Region words at the smaller scales have been created only when there are enough references to make isolating them worthwhile. References not tagged with a Region are excluded, and articles with a region word not matched with a Major Region show up in the "Unknown" report.
Kimberlite - diamondiferous
Lamproite - diamondiferous
Lamprophyre - diamondiferous
Other - diamondiferous
Kimberlite - non diamondiferous
Lamproite - non diamondiferous
Lamprophyre - non diamondiferous
Other - non diamondiferous
Kimberlite - unknown
Lamproite - unknown
Lamprophyre - unknown
Other - unknown
Future Mine
Current Mine
Former Mine
Click on icon for details about each occurrence. Works best with Google Chrome.
CITATION: Faure, S, 2010, World Kimberlites CONSOREM Database (Version 3), Consortium de Recherche en Exploration Minérale CONSOREM, Université du Québec à Montréal, Numerical Database on consorem.ca. NOTE: This publicly available database results of a compilation of other public databases, scientific and governmental publications and maps, and various data from exploration companies reports or Web sites, If you notice errors, have additional kimberlite localizations that should be included in this database, or have any comments and suggestions, please contact the author specifying the ID of the kimberlite: [email protected]
Morphological, chemical and geochronological techniques for characterizing detrital zircon.
Geochemistry of sediments and sedimentary rocks: evolutionary considerations mineral deposits, D.R.Lenz, Geological Association of Canada GEOtext 4, pp. 105-119
Galimov, E., Kudin, A., Skorobogatskii, V., Plotnichenko, V., Bondarev, O., Zarubin, B., Strazdovskii, V., Aronin, A., Fisenko, A., Bykov, I., Barinov, A.
Experimental corrobation of the synthesis of diamond in the cavitation process.
Doklady Physical Chemistry, Vol. 49, 3, pp. 150-153.
Development of a Built in scanning near field microscope head for an atomic force microscope system and its application to natural polycrystalline diamonds
International Mineralogical Association 19th. General Meeting, held Kobe, Japan July 23-28 2006, Abstract p. 114.
Modified ion exchange separation for tungsten isotopic measurements from kimberlite samples using multi-collector inductivity coupled plama mass spectrometry.
Analyst, ( Royal Society of Chemistry), Vol. 131, 3, pp. 434-439.
Prediction of and searching for kimberlites by multispectral satellite images (MSI) on the basis of the stability theory of frames and encoding images.
Melting relations in the chloride carbonate silicate systems at high pressure and model for formation of alkalic diamond forming liquids in the upper mantle.
Earth and Planetary Science Letters, in press available
Lang, A.R., Bulanova, G.P., Fisher, D., Fukert, S., Saruna, A.
Defects in a mixed habit Yakutian diamond: studies by optical and cathodluminescence microscopy, infrared absorption, Raman Scattering and photoluminesence spect
Journal of Crystal Growth, Vol. 309, 2, pp. 170-180.
Kimberlites, orangeites, lamproites, meliltites and minettes: a petrographic atlas.
Almaz Press, info @almazpress.com 1427 Ridgeway St Thunder Bay Ontario P7E 5J7 Canada fax 807 623-7526, $US 85.00 plus ship & Hand 15.00 surface $ 28.00 air
Experimental studies of the system Na2Ca(COs)2 NaCl KCL at 0.1 GPa: implications for the differentiation and low temperature crystallization of natrocarbonatite.
Experimental evidence for liquid immiscibility in the model system CaCO3 pyrope pyrrhotite at 7.0 GPa: role of carbonatite and sulfide melts in diamond genesis
Thompson-Howarth error analysis: unbiased alternatives to the large sample method for assessing non-normally distributed measurement error in geochemical samples.
Geochemistry, Exploration, Environment Analysis, Vol. 8, pp. 173-182.
Yamaguchi, H.,Kudo, Y., Masuzawa, T., Kudo, M., Yamada, Takakuwa, Okano
Combine x-ray photoelectron spectroscopy/ultraviolet photoelectron spectroscopy/field emission spectroscopy for characterization of electron emmision of diamond.
Journal of Vacuum Science and Technology B Microelectronics and Nanometer Structures, Vol. 26, 2, pp. 730-734. American Vacuum Society
New gemstone treatments - a coming crisis. Overview of treatments - more specific to range of all gemstones (not diamonds in particular). Scientific explanations
The 'type' classification system of diamonds and its importance in gemology. A guide to determining diamond type, and its implications for identifying treated and
Gems & Gemology, Vol. 45, 2, Summer, pp. 96-111.
Technology
Diamond classification Type 1 and type 11; synthetics
Fullea, J.J.C., Afonso, L.A.D., Connolly, M., et al.
LitMod3D: an interactive 3-D software to model the thermal, compositional, density, seismological, and rheological structure of the lithosphere and sublithos
Majoritic garnet: a new approach to pressure estimation of shock events in meteorites and the encapsulation of sub-lithospheric inclusions in diamonds.
Geochimica et Cosmochimica Acta, Vol. 74, 20, pp. 5939-5937.
An AEM study of garnet clinopyroxenite from the Sulu ultrahigh pressure terrane: formation mechanisms of oriented ilmenite, spinel, magnetite, amphibole and
Contributions to Mineralogy and Petrology, in press available, 14p.
Silicate carbonate liquid immiscibility and phase relations in the system SiO2-Na2O-Al2O3-CaO-CO2 at 0.1-2.5 GPa with application to carbonatite genesis.
Journal of Petrology, Vol. 52, 7-8, pp. 1281-1305.
An improved and extended internally consistent thermodynamic data set for phases of petrological interest, involving a new equation of state for solids.
Experimental studies of the system Na2CO3-CaCO3-MgF2 at 0.1 GPa: Implications for the differentiation and low temperature crystallization of natrocarbonatite.
Journal of Petrology, Vol. 52, 7-8, pp. 1265-1280.
Experimental study of partition of rare elements between minerals and melts of diamond forming eclogite carbonatite and peridotite carbonatites systems.
Geochemistry International, Vol. 49, 6, pp. 555-567.
Technology
Nanodiamonds
Abstract: Anomalous Xe enriched in both heavy and light isotopes (Xe-HL) was identified in the high-temperature Xe fraction in relict nanodiamond grains from chondrites, whereas the low-temperature Xe fraction (Xe-P3) typically has the normal isotopic composition. The paper presents a concise review of current models put forth to account for the genesis of nanodiamond with anomalous noble gas components and specifies a real process and major regularities during the generation of the isotopic relations of the anomalous Xe-HL component in relict nanodiamond grains. This component is demonstrated to be formed and captured simultaneously with the synthesis of nanodiamond, when shock waves induced by supernova explosions propagated. It is important that diamond synthesis during the passage of shock waves and the enrichment of this diamond in Xe-HL are also possible in the wave forefront region under extremal P-T conditions, in the pressure drop region behind the wave front (by means of nucleation), and by means of irradiation of carbonic grains with high-energy particles. The isotopic composition of Xe-HL results from an increase in the hardness of the spectrum of nuclear-active particles and its enrichment in heavy ions at acceleration in shock waves. Arguments are presented in support of the hypothesis that the nanodiamond population found in chondrites was produced during the latest supernova explosion before the development of the Solar System, with the supernova likely being a SnIa carbon detonation supernova. This furnishes evidence in support of recently advanced hypotheses that the nanodiamond population of chondrites is not presolar.
Melilite-type and melilite related compounds: structural variations along the join Sr2a, Bax, MgS2iO7 and high pressure behaviour of the two end members.
Physics and Chemistry of Minerals, Vol. 39, 3, pp.199-211.
Howell, D., Piazolo, S., Dobson, D.P., Wood, I.G., Jones, A.P., Watte, N., Frost, D.J., Fisher, D., Griffin, W.L.
Quantitative characterization of plastic deformation of single diamond crystals: a high pressure high temperature (HPHT) experimental deformation study combines with electron backscatter diffraction.
Diamond and Related Materials, Vol. 30, pp. 20-30.
Martin, A.M., Laporte, D., Koga, K.T., Kawamoto, T., Hammouda, T.
Experimental study of the stability of a dolomite + coesite assemblage in contact with peridotite: implications for sediment-mantle interaction and diamond formation during subduction.
Experimental study in the Na2OCaOMgOAl203Si02CO2 system at 3 Gpa: the effect of sodium on mantle melting to carbonate -rich liquids and implications for the petrogenesis of silicocarbonatites.
Carbonatites out of a subducted altered oceanic crust? New experimental evidences for "low temperature" carbonatitic melts in COH bearing gabbros at 3.8-4.2 Gpa.
Quantification of vesicle characteristerics in some diatreme filling deposits, and the explosivity levels of magma water interactions within diatremes.
Journal of Geothermal Volcanology and Research, Vol. 245-246, pp. 55-67.
Combined U-Pb geochronology and Sr-Nd isotope analysis of the Ice River perovskite standard, with implications for kimberlite and alkaline rock petrogenesis.
An open source software environment for visualizing and refining plate tectonic reconstructions using high resolution geological and geophysical dat a sets.
Diamond rain falls on Saturn and Jupiter. Diamonds big enough to be worn by Hollywood film stars could be raining down on Saturn and Jupiter, US scientists have calculated.
Nitrogen and its (Biogeocosmo) chemical cycling: nitrogen isotopes and mantle geodynamics: the emergence of life and the atmosphere-crust-mantle connection.
Surface dissolution features on kimberlitic chromites as indicators of magmatic fluid and diamond quality.
Proceedings of the 10th. International Kimberlite Conference, Vol. 1, Special Issue of the Journal of the Geological Society of India,, Vol. 1, pp. 297-308.
Howell, D., Stern, R.A., Griffin, W.L., Southworth, R., Mikhail, S., Stachel, T., Verchovsky, A.B., O'Reilly, S.Y., Pearson, N.J.
New thermodynamic models and calculated phase equilibration temperatures in NCFMAS for basic and ultrabasic compositions through the transition zone into the uppermost lower mantle.
Resource estimation and valuation of alluvial diamond deposits.
Proceedings of the 10th. International Kimberlite Conference, Vol. 2, Special Issue of the Journal of the Geological Society of India,, Vol. 2, pp. 281-288.
Paragenesis and oxygen isotopic studies of serpentine in kimberlite.
Proceedings of the 10th. International Kimberlite Conference, Vol. 1, Special Issue of the Journal of the Geological Society of India,, Vol. 1, pp. 1-12.
Multiple growth episodes or prolonged formation of diamonds? Inferences from infrared absorption data.
Proceedings of the 10th. International Kimberlite Conference, Vol. 1, Special Issue of the Journal of the Geological Society of India,, Vol. 1, pp. 281-296.
An experimental study of Fe oxidation states in garnet and clinopyroxene as a function of temperature in the system CaO FeO Fe2O3 MgO Al2O3 SiO2: implications for garnet-clinopyroxene geothermometry.
Contributions to Mineralogy and Petrology, Vol. 164, 4, pp. 623-639.
Kimberlite: rapid ascent of lithospherically modified carbonatitic melts.
Proceedings of the 10th. International Kimberlite Conference, Vol. 1, Special Issue of the Journal of the Geological Society of India,, Vol.1, pp. 195-210.
Scott Smith, B.H., Nowicki, T.E., Russell, J.K., Webb, K.J., Mitchell, R.H., Hetman, C.M., Harder, M., Skinner, E.M.W., Robey, Jv.A.
Kimberlite terminology and classification.
Proceedings of the 10th. International Kimberlite Conference, Vol. 2, Special Issue of the Journal of the Geological Society of India,, Vol. 2, pp. 1-17.
The IR absorption spectrum of water in microinclusion-bearing diamonds.
Proceedings of the 10th. International Kimberlite Conference, Vol. 1, Special Issue of the Journal of the Geological Society of India,, Vol. 1, pp. 271-280.
Dymshits, A., Litasov, K., Sharygin, I., Shatskiy, A., Ohtani, E.
Mineral physics of high pressure garnets.
V.S. Sobolev Institute of Geology and Mineralogy Siberian Branch Russian Academy of Sciences International Symposium Advances in high pressure research: breaking scales and horizons ( Courtesy of N. Poikilenko), Held Sept. 22-26, 2p. Abstract
Eiler, J.M., Berquist, B., Bourg, I., Cartigny, P., Farquhar, J., Gagnon, A., Guo, W., Halevy, I., Hofman, A., larson, T.E., Levin, N., Schauble, E.A., Stolper, D.
Development of ultrasonic measurement technique under lower mantle conditions.
V.S. Sobolev Institute of Geology and Mineralogy Siberian Branch Russian Academy of Sciences International Symposium Advances in high pressure research: breaking scales and horizons ( Courtesy of N. Poikilenko), Held Sept. 22-26, 1p. Abstract
Prencipe, M., Bruno, M., Nestola, F., De La Pierre, M., Nimis, P.
Toward an accurate ab initio estimation of compressibility and thermal expansion of diamond in the (0, 3000K) temperature and (0,30 Gpa) pressure ranges, at the hybrid HF/DFT theoretical level.
Sharygin, I., Litasov, K., Shatskiy, A., Golovin, A., Ohtani, E., Pokhilenko, N.
Is kimberlite magma ascent fuelled by CO2 degassing via orthopyroxene assimilation?
V.S. Sobolev Institute of Geology and Mineralogy Siberian Branch Russian Academy of Sciences International Symposium Advances in high pressure research: breaking scales and horizons ( Courtesy of N. Poikilenko), Held Sept. 22-26, 2p. Abstract
Shatskiy, A., Litasov, K., Palyanov, Y.N., Ohtaini, E.
Phase relationships on the K2CO3 MgCOs join at 6 Gpa and 900-1400C: implications for incipient melting in carbonated mantle domains.
V.S. Sobolev Institute of Geology and Mineralogy Siberian Branch Russian Academy of Sciences International Symposium Advances in high pressure research: breaking scales and horizons ( Courtesy of N. Poikilenko), Held Sept. 22-26, 2p. Abstract
Russian Geology and Geophysics, Vol. 56, 1-2, pp. 211-220.
Technology
Diamond inclusions
Abstract: The formation conditions of diamond can be determined from the residual pressure of inclusions trapped within the diamond, as measured at ambient conditions, and the equations of state (EoS) of the mineral inclusion and the host diamond. The EoS parameters of the diamond and the inclusion phase are therefore critical for determining the precision and accuracy of the calculation of formation conditions of diamonds. The questions we address are (i) How precise are these calculations? and, in particular, (ii) Do we know the EoS parameters of diamond to a precision and accuracy which do not contribute significantly to uncertainties in the geological conclusions drawn from these calculations? We present a review of the most recent compressional data, simulations, and direct elastic measurements of diamond and show them to be consistent with a room-temperature bulk modulus of K0T = 444(2) GPa and a pressure derivative K = 4.0. In combination with a thermal-pressure model with parameters aV300,0 = 2.672(3) x 10- 6 K- 1 and a single Einstein temperature 0E = 1500 K, the volume variation of diamond from room conditions to pressures and temperatures exceeding those in the Earth’s transition zone is described to within the levels of uncertainty inherent in both experimental and computational determinations. For the example of olivine inclusions in diamond, these uncertainties in the diamond EoS parameters lead to uncertainties in the entrapment pressures of no more than 0.001 GPa at low temperatures and 0.008 GPa at higher temperatures.
Economic Geology Research Institute 2015, Vol. 17,, # 2121, 1p. Abstract
Technology
Barometer
Abstract: Original monomineral thermobarometers for mantle peridotites for clinopyroxene, garnet, chromite and ilmenites for the mantle peridotites were statistically calibrated on the PT estimates for mantle peridotites [Ashchepkov et al., 2010] were tested using the mineral phases obtained in high pressure experiments with the natural peridotites (380 runs) [Brey et al.,1990; 2008 etc] and eclogites (240 runs)[Dasgupta et al., 2006 etc]. In the original program of that written on FORTRAN are assembled the most reliable methods of mineral thermometers (45) and barometers (36) and oxybarometers (5), including original monomineral and methods [Ashchepkov, 2003 Ashchepkov et al., 2008; 2009; 2010; 2011] for the mantle peridotites bases on the compositions of on clinopyroxene, garnet, chromite and ilmenite. Program reads the text files, which converted from Excel. Original data include standard silicate compositions for 12 components in standard order. The text file includes 15 columns of 8 symbols. The first is file name which is the same for all the minerals in the association. The second is indicator symbol for phases. E- enstatite, D - diopside, O-olivine, S-spinel, G- garnet, I –ilmenite, A- amphibole, F – phlogopite, P-plagioclase, L- liquid, R- bulk rock. Then follow oxides: SiO2, TiO2, Al2O3, Cr2O3, FeO, MnO, MgO, CaO, Na2O, K2O, NiO, V2O3 written with 2–3 decimals. The last column may contain description of the mineral or association up to 64 symbols. Monomineral methods use calculated values for Fe#Ol or Fe#Cpx. The input from console includes file name (8 symbols) (A8), then amount of PT pairs of numbers thermometers and barometers (2I2) and one for FO2 method. Program allows input of the iteration numbers (to 25 by default). It allow to choose whether to use the calculated Fe3+ for the minerals and also. It is possible also to put fixed values of T and P (default 1000oC and 40 kbar ).
The equations of state of forsterite, wadsleyite, ringwoodite, akimotoite, Mg2SiO4 perovskite and post perovskite and phase diagram for the Mg2SiO4 system at pressures of up to 130 Gpa.
Russian Geology and Geophysics, Vol. 56, 1-2, pp. 172-189.
Interface partition coefficients of trace elements in carbonate-silicate parental media for diamonds and paragenetic inclusions ( experiments at 7.0-8.5 Gpa)
Russian Geology and Geophysics, Vol. 56, 1-2, pp. 221-231.
Valentine, G.A., Graettinger, A.H, Macorps, E., Ross, P-S., White, J.D.L., Dohring, E., Sonder, I.
Experiments with vertically and laterally migrating subsurface explosions with applications to the geology of phreatomagmatic and hydrothermal explosion craters and diatremes.
Abstract: To test if hydrogen incorporation by ionic diffusion can occur between a volatile-rich kimberlitic liquid and forsterite, results of high-pressure and high-temperature experiments using a piston-cylinder apparatus at 1200–1300 °C and 1 GPa for durations of 1 min, 5 h, and 23 h, are reported here. Kim-berlitic liquid in the system CaO-MgO-Al 2 O 3-SiO 2-CO 2-H 2 O and synthetic forsterite single crystals were chosen as a first simplification of the complex natural kimberlite composition. Unpolarized Fourier transform infrared spectroscopy was used to quantify the concentrations of OH in the crystallographically oriented forsterite. Scanning electron microscopy, electron backscattered diffraction, electron microprobe analyses, and transmission electron microscopy were performed to identify the run products. After 5 and 23 h, a forsterite overgrowth crystallized with the same orientation as the initial forsterite single crystal. The kimberlitic liquid has crystallized as micrometer-scale euhedral forsterite neocrystals with random crystallographic orientations, as well as a nanoscale aluminous phase and a calcic phase. Despite theoretical water-saturation of the system and long duration, none of the initial forsterite single crystals display signs of hydration such as hydrogen diffusion profile from the border toward the center of the crystal. Most likely, the presence of CO 2 in the system has lowered the H 2 O fugacity to such an extent that there is no significant hydration of the starting forsterite single crystal or its overgrowth. Also, the presence of CO 2 enhances rapid forsterite crystal growth. Forsterite growth rate is around 2 × 10 8 mm 3 /h at 1250 °C. These experimental results suggest a deep mantle origin of the high OH content found in natural mantle-derived xenoliths transported in kimberlites, as reported from the Kaapvaal craton. In agreement with previous studies, it also points out to the fact that significant hydration must take place in a CO 2-poor environment.
Contributions to Mineralogy and Petrology, Vol. 170, 25p.
Technology
Experimental petrology
Abstract: Melting of carbonated sediment in the presence of graphite or diamond was experimentally investigated at 7.5–12 GPa and 800–1600 °C in a multianvil apparatus. Two starting materials similar to GLOSS of Plank and Langmuir (Chem Geol 145:325–394, 1998) were prepared from oxides, carbonates, hydroxides and graphite. One mixture (Na-gloss) was identical in major element composition to GLOSS, and the other was poorer in Na and richer in K (K-gloss). Both starting mixtures contained ~6 wt% CO2 and 7 wt% H2O and were doped at a ~100 ppm level with a number of trace elements, including REE, LILE and HFSE. The near-solidus mineral assemblage contained a silica polymorph (coesite or stishovite), garnet, kyanite, clinopyroxene, carbonates (aragonite and magnesite-siderite solid solution), zircon, rutile, bearthite and hydrous phases (phengite and lawsonite at <9 GPa and the hydrous aluminosilicates topaz-OH and phase egg at >10 GPa). Hydrous phases disappear at ~900 °C, and carbonates persist up to 1000-1100 °C. At temperatures >1200 °C, the mineral assemblage consists of coesite or stishovite, kyanite and garnet. Clinopyroxene stability depends strongly on the Na content in the starting mixture; it remains in the Na-gloss composition up to 1600 °C at 12 GPa, but was not observed in K-gloss experiments above 1200 °C. The composition of melt or fluid changes gradually with increasing temperature from hydrous carbonate-rich (<10 wt% SiO2) at 800-1000 °C to volatile-rich silicate liquids (up to 40 wt% SiO2) at high temperatures. Trace elements were analyzed in melts and crystalline phases by LA ICP MS. The garnet-melt and clinopyroxene-melt partition coefficients are in general consistent with results from the literature for volatile-free systems and silicocarbonate melts derived by melting carbonated peridotites. Most trace elements are strongly incompatible in kyanite and silica polymorphs (D < 0.01), except for V, Cr and Ni, which are slightly compatible in kyanite (D > 1). Aragonite and Fe-Mg carbonate have very different REE partition coefficients (D Mst-Sd/L ~ 0.01 and D Arg/L ~ 1). Nb, Ta, Zr and Hf are strongly incompatible in both carbonates. The bearthite/melt partition coefficients are very high for LREE (>10) and decrease to ~1 for HREE. All HFSE are strongly incompatible in bearthite. In contrast, Ta, Nb, Zr and Hf are moderately to strongly compatible in ZrSiO4 and TiO2 phases. Based on the obtained partition coefficients, the composition of a mobile phase derived by sediment melting in deep subduction zones was calculated. This phase is strongly enriched in incompatible elements and displays a pronounced negative Ta-Nb anomaly but no Zr-Hf anomaly. Although all experiments were conducted in the diamond stability field, only graphite was observed in low-temperature experiments. Spontaneous diamond nucleation and the complete transformation of graphite to diamond were observed at temperatures above 1200-1300 °C. We speculate that the observed character of graphite-diamond transformation is controlled by relationships between the kinetics of metastable graphite dissolution and diamond nucleation in a hydrous silicocarbonate melt that is oversaturated in C.
The Journal of Gemmology, Vol. 334, 6, pp. 518-522.
Technology
Synthetics
Abstract: During the March 2015 Diamond Show in Basel, Switzerland, a parcel of 6,000 melee-sized colourless diamonds was analysed using the GGTL Diamond Fluorescence Imaging (DFI) Laser+ fluorescence imaging and spectroscopy system. From the entire parcel, one sample stood out clearly with unusual fluorescence colours and distribution, combined with a photoluminescence spectrum that clearly indicated it was a synthetic diamond grown by chemical vapour deposition (CVD).
International Geology Review, Vol. 57, 15, pp. 1940-1974.
Technology
Peridotite, experimental petrology
Abstract: Experimental synthesis of spinel peridotite phase assemblages for a range of compositions that mimic natural samples is used to derive a set of empirical geothermometers and geothermobarometers represented by multiple linear regression best-fit surfaces that link the variables of temperature, pressure, and composition. The calibrated geothermometers use reactions that govern the solubility of Al and Cr in both pyroxenes and the Mg–Fe exchange between silicates and spinel. Geothermobarometers map the Mg–Fe exchange between coexisting olivine and clinopyroxene and pyroxenes and Ca–Mg exchange between coexisting pyroxenes. Application of the geothermometers and geothermobarometers to suites of naturally occurring samples indicates that while reactions governing the Cr and Al solubility and solvus of orthopyroxene give useful estimates of ‘original’ mantle temperatures and pressures, respectively, comparable reactions for clinopyroxene yield estimates that are variably dependent on the transport phase of the sample suites. Temperature and pressure estimates from reactions governing Mg and Fe exchange between silicates and spinel and coexisting silicates are all sensitive to the later transport stage of the samples.
Diamond and Related Materials, Vol. 58, pp. 40-45.
Technology
Diamond synthetics
Abstract: Diamond crystallization from the tin–carbon system has been studied at 7 GPa and temperatures ranging from 1600 to 1900 °C with reaction times from 1 to 20 h. Both diamond growth on the seed crystals and diamond spontaneous nucleation were established, providing evidence for the catalytic ability of tin. A distinctive feature of the Sn–C system is the existence of a significant induction period preceding diamond spontaneous nucleation. Temperature and kinetics are found to be the main factors governing diamond crystallization process. The minimum parameters of diamond spontaneous nucleation are determined to be 7 GPa, 1700 °C and 20 h. The stable form of diamond growth is octahedron and it does not depend on temperature. Synthesized diamonds contain high concentrations of nitrogen impurities up to about 1600 ppm.
Abstract: Until recently, film was the preferred medium used for capturing images through the microscope, primarily due to resolution limitations of digital-format cameras. The image quality that can now be achieved by digital cameras is equal, and in many ways superior, to the quality offered by film. Digital photomicrography allows gemologists the opportunity to instantly see the resultant images, which can then be adjusted with image-refining software so that they represent their subject as realistically as possible. This article offers examples of some basic techniques and tips on the application of digital processing to get the most out of photomicrographs.
2015 IEEE 10th International Conference on Nan/Micro Engineered and Molecular Systems, NEMS 2015, pp. 372-374.
Technology
X-ray dectector
Abstract: Development synthesizing diamond film on silicon substrate was processed by Hot Filament Chemical Vapor Deposition (HFCVD). The gas processes using of H2 and CH4 to produce intrinsic diamond and MSM device constructed on the diaphragm of diamond film. Schottky junctions on the top and the lower diaphragm were produced by aluminum metal. After that, the result of detecting a direct and indirect X-ray of MSM diamond was satisfactory because it could respond along with increasing of X-ray intensity. The X-ray expose time of indirect expose by BaF2 scintillator faster more than direct expose.
Journal of Mining Science, Vol. 50, 4, pp. 788-799.
Technology
Diamond morphology
Abstract: The article describes modeling and analysis of formation, attachment and dissolving of mineral substances on surface of diamond crystals. Based on the thermodynamic analysis and experimental research, the author validates deposition of chemical compounds as the main factor to govern mineral formations on natural diamond surface under contact with mineralized water in the occurrence conditions of kimberlite ore and during mining and processing. The efficiency of electrochemically modified water in dissolving and removal of mineral formations from diamond surface is ascertained.
GSA Annual Meeting, Paper 300-12, 1p. Abstract only Booth
Technology
Synthetic diamonds
Abstract: Defect of [Si-V]- is common in CVD synthetic diamonds, and its occurrence was also reported in some rare natural diamonds (Breeding and Wang, 2008). It is an important feature employed for gem diamond identification, and also has great potential for applications in industry. However little is known about how the silicon impurity gets into diamond lattice either in synthetic or natural diamonds. In this study, we discovered the occurrence of [Si-V]- in HPHT synthetic diamonds and the correlation between its precipitation and diamond growth sectors was successfully determined.
Total 20 samples, HPHT grown diamond wafers from NDT (New Diamond Technology) were studied in addition to one type IIb HPHT synthetic diamond submitted to GIA Laboratory for grading. Distributions of defects in these samples were carefully mapped using infrared microscopy at room temperature and an imaging Raman microscope at liquid nitrogen temperature.
Defect of [Si-V]- has doublet emissions at 736.6/736.9 nm (Clark et al., 1995), and can be effectively excited using 633 nm laser. Analyses were conducted at Liquid Nitrogen temperature as the detection of the Si related emissions peak is temperature dependent (Feng and Schwartz 1993). Additionally, the solvent catalysts used in the HPHT methods to grow synthetic diamond either intentionally or unintentionally contain nickel in varying quantities. Nickel impurity creates optical centers which emit a doublet peak at 882.6/884.3nm, and can be easily excited using 780 nm laser.
The [SiV]- is clearly observed in only certain growth sectors of the synthetic crystal and the distribution is not homogeneous. By comparing the two acquired maps one acquired at 633nm excitation showing the [Si-V]- distribution and one acquired with 780nm excitation showing the nickel defect distribution, it was found that the [Si-V]- is confined to the same growth sector as Ni related defect with higher concentrations/intensity at the edges of these sectors. Since it is well known that the Ni defect is confined exclusively to the octahedral growth sectors {111} of diamond (Lawson et al., 1993), this study for the first time confirmed that [Si-V]- is confined to the {111} octahedral growth sectors.
This new discovery leads to discussion as to the incorporation of silicon in diamond and the relationship to other impurities.
Abstract: The prosperity of our societies and our standards of living are directly related to our ability to find, exploit, and manage our metal and mineral resources. Metal and mineral deposits are, in fact, geochemical anomalies and, as such, applied geochemistry plays a critical role throughout the mineral resources value chain, from early stage exploration to mine closure. The fundamentals of element mobility (i.e. transport and fixation) in the near-surface environment are used by geochemists to detect mineral deposits at depth, reveal element distributions in and around deposits, assess the total geochemical environment, and refine effective and benign extraction and waste disposal techniques. Both pure- and applied-research ventures play fundamental roles in providing the techniques to manage metal resources and thereby benefit society.
Russian Geology and Geophysics, Vol. 56, pp. 1154-1161.
Technology
Spectrometry
Abstract: The results of electron probe microanalysis of several rock-forming minerals by wavelength-dispersive spectrometry (WDS) and energy-dispersive spectrometry (EDS) are compared, and the metrological characteristics of both methods are studied. The measurements were made with the use of a JXA-8100 (JEOL) microanalyzer with five wavelength-dispersive spectrometers and a MIRA 3 LMU (Tescan) scanning electron microscope equipped with an INCA Energy 450 XMax 80 (Oxford Instruments) microanalysis system. Specimens with olivine, garnet, pyroxene, ilmenite, and Cr-spinel grains were analyzed.
The variation coefficients that characterize the repeatability of a single determination are found to be ~ 0.5% for WDS and ~ 0.9% for EDS in the compositional range of the main components (C > 10%). For minor components (1% < C < 10%), the variation coefficients are 1.4% and 3.0%, respectively, and for impurities (0.3% < C < 1%), 2.7% and 13%, respectively. For lower contents EDS is almost inapplicable. The ratio of the results obtained by the two methods is reproduced with high precision: For major components, the variation coefficient is 0.56%; for minor components, 1.7%; and even for impurities, it is ~ 8%. The magnitude of the bias is between 0.2 and 3.2 rel.%, which is acceptable.
The results show that the accuracies of WDS and EDS are similar for measuring major and minor components of rock-forming minerals. Energy-dispersive spectrometry is inferior to wavelength-dispersive spectrometry for impurities and is completely inapplicable for still lower contents. This method is easier to implement, and the results are available soon after switching on the instrument. Wavelength-dispersive spectrometry needs more time for preparation, but it ensures a precise high-efficiency large-scale analysis of samples of similar compositions, even when the element contents are lower than 1%.
Abstract: Carbon dioxide and water, being present in the Earth's mantle at concentration levels of tens to hundreds of ppm, greatly lower the peridotite solidus temperature and drastically modify the composition of produced melts. The presence of CO2 produces silica-poor, carbonate-rich liquids at the onset of melting, and these liquids shift toward silica rich compositions as the degree of melting increases. Numerous geochemical observations and experimental studies have revealed the complexity of the transition between carbonate-rich and silicate-rich melts. It is characterized by a strongly non-linear evolution and, under specific conditions, by immiscibility. To better constrain this transition, we have used the thermodynamic activity of silica as a probe of the mixing properties between molten carbonate and molten silicate. The activity of silica (aSiO2(l))aSiO2l was calculated for a large number of experimental liquids from two equilibria: olivine-orthopyroxene-melt and immiscible silicate-rich melt-carbonate-rich melt (491 data points ranging from 1 to 14 GPa and 1090 to 1800 °C). We modelled aSiO2(l)aSiO2l during incipient melting of the peridotite in presence of CO2 with a generalized Margules function. Our model reproduces well the silica activity-composition relationships of the experimental database, and can be used to predict the silica content of the melts coexisting with olivine and orthopyroxene. We show that water content and Ca/Mg ratio in the melts have an important influence on the aSiO2(l)aSiO2l. In contrast to a recent empirical model (Dasgupta et al., 2013), the analysis of the experimental database reveals that the transition from carbonate to silicate melt with decreasing depth should occur abruptly in oceanic mantle. Our model predicts that carbonatitic melts with ~ 5 wt.% SiO2 can be stabilized from ~ 150 km depth, at the onset of incipient melting by "redox melting", up to ~ 75 km, above which the liquid evolves abruptly to a carbonated silicate composition (> ~ 25 wt.% SiO2). In the cratonic mantle lithosphere, our model predicts that carbonatitic melts are prevailing up to shallow depth, and conflicts the recent model (Russell et al., 2012) of CO2-saturation triggered by orthopyroxene assimilation during kimberlite ascent.
GSA Annual Meeting, Paper 300-4, 1p. Abstract only Booth
Technology
Spectroscopy
Abstract: The ability to accurately determine the provenance of gem diamonds impacts economic, political, and national security arenas. Currently, provenance determinations rely on: 1) gemological and mineralogical features of stones, such as spectroscopic measurements, geochemistry, and inclusions, and 2) certification and tracking of individual stones through the Kimberly Process Certificate Scheme. Unfortunately, during cutting and polishing, many gemological features are obliterated and tracking individual stones through the chain of custody can be difficult. This study resulted in a highly successful method for determining provenance of cut diamonds from information in the stone itself.
A set of 30 cut diamonds from each of ten controlled localities and one set of 30 synthetic diamonds were analyzed by Laser-Induced Breakdown Spectroscopy (LIBS). The sample set (330 total diamonds) includes both kimberlite and placer diamonds from five countries and five different cratons. LIBS acquires the atomic emission spectra released from a material during laser ablation. The spectra contain information from nearly every element in the periodic table, and thus are unique chemical, or quantagenetic, signatures of the material. Spectra were analyzed using a Bayesian statistical method that compares groups of samples defined by the reported locations of the stones to clusters of samples defined by spectral similarity. Ideally, each spectral cluster coincides with a group of stones. The spectrum of each sample is compared to a set of reference spectra from each group to determine the probable provenance of the sample. The correlation between groups and clusters was excellent, with average accuracy of 98%, suggesting that diamonds from each location are spectrally similar to each other and distinct from those from other locations. This is true even for diamonds from kimberlites in close proximity to each other. Synthetic diamonds are easily distinguished from natural diamonds (100% success). Some groups of diamonds in the study are more heterogeneous than others. For instance, a placer group has five recognizable spectrally-defined sub-clusters. This work demonstrates that diamond provenance can be determined at a high level of confidence on individual cut gemstones.
GSA Annual Meeting, Paper 300-2, 1p. Abstract only Booth
Technology
GIA library
Abstract: Through its digitization project, the Gemological Institute of America’s (GIA) Richard T. Liddicoat Library is making available digital copies of historic and unique books to geoscientists worldwide. By the end of 2015, more than 100 volumes from the library’s rare book collection, including the gemology and mineralogy library collected by John and Marjorie Sinkankas, will be posted online in a readily accessible, searchable format.
In December 2014, the library purchased the BC100 Book Capture system by Digital Transitions. This equipment includes two Phase One digital camera backs with Schneider Kreuznach lenses, which photograph the two pages of an open book simultaneously. Images are captured at a minimum resolution of 300 pixels per inch, with higher resolutions used for books that are small, have highly detailed color images, or have small or faded text.
Capture One imaging software is used to generate a TIFF image for each page. These TIFF files will be saved indefinitely as preservation masters, from which derivative files can be created and modified for future use. Then docWorks post-processing software by Content Conversion Specialists is used to perform optical character recognition (OCR) and generate a searchable PDF and ePub output for each book. The OCR supports a variety of languages including those using European and Cyrillic alphabets, as well as Chinese, Japanese, and Korean characters.
A number of GIA’s digital books are now available online to view and download for free through Internet Archive (https://archive.org/details/@gia_library) with new books being uploaded every few days. Available books include out-of-copyright titles dating from 1496 to the 1920s. One of the oldest digitized books, Libellus de Lapidibus Preciosis (Book of Precious Stones) by Marbode, Bishop of Rennes, printed in 1511, was originally written in the 11th century and discusses properties of 60 gems. Another title, René Just Haüy’s influential Traité de Minéralogie (Treatise of Mineralogy) published in 1801, describes the laws governing crystal structure and was the first rational system for identifying and classifying minerals. The digitization project is ongoing with plans to ultimately post hundreds of volumes related to gems and minerals.
GSA Annual Meeting, Paper 300-7, 1p. Abstract only Booth
Technology
HPHT
Abstract: Defects H3 and H4 are common in natural, HPHT treated, and artificially irradiated fancy colored diamonds. Understanding of their formation is important for color origin determination in gem labs. However, there are still substantial challenges. Davies (1972) studied the effect of different forms of nitrogen on the annealing of radiation damage, and found A/B = H3/H4. However, Collins (1982, 2001) pointed out that some natural type Ia diamonds could have H3 absorption but even when they contain substantial amounts of nitrogen in the B-form, the H4 absorption is negligible. In this study, based on investigation of a group of 39 (0.12 - 7.03 ct) natural green - yellow diamonds, vacancy source for formation H3 and H4 is identified and preference formation of H3 over H4 is discussed. Nitrogen concentrations of these diamonds fell in a range of 32- 496 ppm, with average 0.67 for B/(B+A). So, significant amount of B-form nitrogen exist. No irradiation feature of H1a, H1b, H1c, or 595 nm absorption was detected. Absorption spectra in the UV-Vis region were dominated by defects N3 and H3. Strong emission bands from H3 were observed, and its fluorescence substantially contributed to the body colors of green - yellow. As an outstanding feature, absorption or emission of defect H4 is entirely absent, despite significant concentrations of B-form nitrogen. Strong plastic deformation is a common feature in all samples. Green fluorescence from defect H3 clearly followed dislocation by showing up to 3 sets of parallel lines, instead of following growth zonation. These sharp lines are continuous throughout the whole stones. Strong dislocations indicated that these diamonds were originlly in brown color after the plastic deformation and thus with significant concentrations of vacancy clusters. Annealed in the earth’s mantle over a long geological history, single vacancies released from vacancy clusters could combine with the A-form nitrogen to form H3. Strong preference in forming H3 over H4 could be related to the unknown disaggregation process of vacancy clusters and the annealing in the earth’s mantle over long geological time. Absence of H4 in this type of diamonds could be considered as a useful indication of natural color origin.
GSA Annual Meeting, Paper 300-6, 1p. Abstract only Booth
Technology
Tanzanite
Abstract: Colored stones are increasingly accepted in China gem market in recent years. Tanzanite owing to its unique violetish blue color is readily recognized and attracts broad attention. Natural, unheated blue tanzanite is known for its trichroic colors in bluish violet, violetish blue, yellow-green. Much lesser known, tanzanite also exhibits metachromatism, a color shift, when illuminated by cold and warm light sources. However, limited existing reports and studies have been mostly descriptive on general gem deposit and basic gemological characteristics. Very little data exit on color shift and pleochroism distinctive to tanzanite. Quantitative analysis on these color characteristics under heating virtually is lacking, even though over 95% tanzanite materials on gem market are reported to have been heated to improve its appearance. This study presents direct observational results on color shift with controlled warm (`3200K) and cold (`6500K) light sources under polarization and known crystallographic orientations. Further quantitative analysis have been performed by polarized spectroscopic measurement on trichroic to dichroic color conversion in tanzanite samples from a set of heating experiments between 650 and 900 °C. Optimal heating temperature for these experiments was determined by thermal analysis (TG-DTA), which showed that tanzanite became unstable above 960 °C. Our optical observation and quantitative results revealed that a yellow-green coloration along the c-crystallographic direction converted and virtually merged into existing blue coloration after heating. Consequently, tanzanite converted from natural, unheated trichroic to heated dichroic.
Abstract: Analysing the size frequency distributions (SFDs) of both micro diamonds and macro diamonds from primary deposits shows that the distributions are continuous across all sizes and that there are two regions of different character with a transition about 1-2 mm. Using log axes, the frequency curve is linear for the smaller sizes allowing slope and intercept parameters to be determined which are less ambiguous than stone counts and ratios of macro to micro populations that are generally reported. Modelling a diamond population that has undergone removal of a uniform thickness of the outer layer transforms a linear frequency curve into a quadratic form, which is also the form of the frequency curve for macro diamonds. Diamonds grown synthetically also display a linear distribution across a smaller fraction of their size distribution curve.
Abstract: The first small manufactured industrial diamonds were produced in 1953 by the Swedish company ASEA but their accomplishment went unannounced. In 1970, General Electric (GE) produced synthetic diamond crystals using the HPHT method with a belt type of press and created a 0.78ct polished RBC colorless diamond. In the 1980’s and 1990’s Russians used their own technology (“BARS” and “TOROID” high pressure apparatus (HPA) with high pressure presses of up to 25 MN load) to grow industrial and crystals up to 2.00ct in polished size, mostly orange to yellow in colour. In the last 15 years, companies including Lucent, Chatham, AOTC, Gemesis (now IIa Technologies) and many other producers in China, Germany, India, Russia, Ukraine, USA and Taiwan have improved the technology yet again and used their expertise to successfully grow diamond crystals that cut to 1.00ct up to 2.00ct in size. This “next generation” of diamonds exhibited high clarities (VS and VVS) and colours (D-H), as well as new blue and pink colours (after irradiation). Other companies (ref. 2-3) including Scio Diamonds, Washington Diamonds, Taidiam, PDC diamonds and Pure Grown Diamonds (selling arm of IIa technologies) are also using a very different technology/process of Chemical Vapour Deposition (CVD) to produce laboratory-grown diamonds up to 3.00 ct in size (table 1).
Diamond and Related Materials, in press available, 16p.
Technology
Synthetics
Abstract: Diamond synthesis and its morphology by in-liquid plasma chemical vapor deposition (CVD) method are investigated in this study. Diamond films were grown on Si substrates from mixed alcohol solution. Very high growth rate of 170 ?m/h was achieved by this method. Microcrystalline and nanocrystalline diamond films were formed in different conditions. In the case of microcrystalline film, the shapes of diamond grains depend on the location in the film. All morphological differences in this study can be explained by the same mechanism of conventional gas phase CVD method. It means diamond morphology by in-liquid plasma CVD method can be controlled by process parameters as well as gas phase CVD method.
Abstract: Recent studies of mineral diversity and distribution lead to the prediction of >1563 mineral species on Earth today that have yet to be described-approximately one fourth of the 6394 estimated total mineralogical diversity. The distribution of these "missing" minerals is not uniform with respect to their essential chemical elements. Of 15 geochemically diverse elements (Al, B, C, Cr, Cu, Mg, Na, Ni, P, S, Si, Ta, Te, U, and V), we predict that approximately 25% of the minerals of Al, B, C, Cr, P, Si, and Ta remain to be described - a percentage similar to that predicted for all minerals. Almost 35% of the minerals of Na are predicted to be undiscovered, a situation resulting from more than 50% of Na minerals being white, poorly crystallized, and/or water soluble, and thus easily overlooked. In contrast, we predict that fewer than 20% of the minerals of Cu, Mg, Ni, S, Te, U, and V remain to be discovered. In addition to the economic value of most of these elements, their minerals tend to be brightly colored and/or well crystallized, and thus likely to draw attention and interest. These disparities in percentages of undiscovered minerals reflect not only natural processes, but also sociological factors in the search, discovery, and description of mineral species.
Abstract: In mid-2012, one of the international diamond grading laboratories in Antwerp reported undisclosed CVD synthetic diamonds, causing a stir in the diamond industry (Even-Zohar, 2012). Since then, reports of undisclosed CVD synthetics have also emerged from gem testing laboratories in India and China (D’ Haenens-Johanson et al., 2013; Song et al., 2014). Central Gem Laboratory (CGL) also reported on undisclosed over 1 ct size CVD synthetic diamonds (Kitawaki et al., 2013). Gem quality CVD products have been improved in their size and quality year after year, and a variety of colours have appeared. Most of the CVD synthetic diamonds reported previously are type II, however, recently some yellow CVD synthetic diamonds containing isolated substitutional nitrogen have been supplied to the gem market (Moe et al., 2014; Hainschwang, 2014). This report describes the gemmological features of fifteen yellow to brownish yellow type Ib CVD synthetic diamonds submitted to CGL without disclosure.
Kryvoshlyk, 38ppt. Available ppt. Email ikryvoa481 @hotmail.com
Technology
Microdiamonds - responses
Abstract: Diamond grade is the most important parameter of a kimberlite rock. A few hundreds of microprobe analyses of garnets picked randomly from a kimberlite concentrate might be enough to calculate mathematically accurate diamond grade.
Diamond and Related Materials, Vol. 39, pp. 89-97.
Technology
Microdiamonds - responses
Abstract: Geometrical crystallographic features of rare diamond micro-crystals (0.3-0.5 mm in diameter) from kimberlites having different complex flat and smooth faces are described. Such polyhedrons of microdiamonds are typically composed of two or more combinations of seven different crystal forms belonging to hexoctahedral symmetry class: octahedron, cube, rhombic dodecahedron, trisoctahedron, trapezohedron, tetrahexahedron and hexoctahedron. Many of them are not yet known for macro-crystals of this mineral. All these forms are found as small faces on the octahedral crystals. Both flat and smooth faces of octahedron and cube on such crystals have their own growth sectors. Flat faces of rhombic dodecahedron, different trisoctahedrons, trapezohedrons and hexoctahedrons occur as so-called faces of degeneration of octahedral growth planes. Nature of tetrahexahedron flat faces is not clear. An investigation of the complex diamond polyhedrons should give a new idea on crystal morphology of diamond, make more precise its symmetry and be important for the explanation of the nature of diamond on the whole.
Diamond and Related Materials, Vol. 40, pp. 24-31.
Technology
Microdiamonds - responses
Abstract: A transmission electron microscopy study of garnet from diamond-grade gneisses of the Betic Cordillera (Spain) has revealed the presence of abundant, previously unrecognized, nanosized carbonaceous grains, coexisting with micrometer-sized graphite and diamond. The nanosized particles occur as multiwall nanotubes, and as polyhedral and quasi-spherical graphite + diamond nanoparticles, whereas larger graphite particles appear as rods and as tabular crystals. The topotactic relationships between graphite in nanoparticles and in micrometer-sized particles and the host garnet suggest that carbon nano- and microparticles precipitated from an originally homogeneous solid solution of carbon in the garnet. Based on orientation relationships and on experimental data it is suggested that the three main types of nanosized particles (nanospheres, polyhedral particles and nanotubes) were the precursor of the three main types of larger carbon phases (diamond, tabular and rod-shaped graphite particles, respectively). It is interpreted, as in the case of diamond-graphite nanocomposites, that diamond formation in the core of the nanoparticles is due to an increase of the cross-links between the layers, and then, to the collapse, at a certain point, of the whole graphite structure into diamond. This finding opens a new door for explaining the origin of some metamorphic diamonds and of coexisting graphite and diamond in ultrahigh pressure rocks.
Diamond and Related Materials, Vol. 59, pp. 69-72.
Technology
Lonsdaleite
Abstract: Hexagonal diamond has been predicted computationally to display extraordinary physical properties including a hardness that exceeds cubic diamond. However, a recent electron microscopy study has shown that so-called hexagonal diamond samples are in fact not discrete materials but faulted and twinned cubic diamond. We now provide a quantitative analysis of cubic and hexagonal stacking in diamond samples by analysing X-ray diffraction data with the DIFFaX software package. The highest fractions of hexagonal stacking we find in materials which were previously referred to as hexagonal diamond are below 60%. The remainder of the stacking sequences are cubic. We show that the cubic and hexagonal sequences are interlaced in a complex way and that naturally occurring Lonsdaleite is not a simple phase mixture of cubic and hexagonal diamond. Instead, it is structurally best described as stacking disordered diamond. The future experimental challenge will be to prepare diamond samples beyond 60% hexagonality and towards the so far elusive 'perfect' hexagonal diamond.
International Journal of Luminescence and Applications, Vol. 5, 3, pp. 293-297.
Technology
Luminescence
Abstract: Some of the minerals like Corundum, chryso beryl, beryllium alumino silicate (emerald) and also Diamond exhibit exceptional optical properties[1] and in some cases attractive colours; in India these were recognized quite early since the days of Indus valley civilization. In more recent times there has been a lot of scientific interest in colours and colour modifications in Gem minerals and in Diamonds. Science of gem stones deals with their identification by non destructive means and understanding of origin of colour and excellent optical properties[1]. Optical methods have long been used to obtain properties like ‘Refractive Index’ which still remains an important parameter as a preliminary test to identify the gemstone/mineral. The spectroscopic studies of gem grade minerals are essentially directed towards some of these features in identifying and understanding the spectral properties of chromophores, either chemical impurities and/or radiation induced point defects, in solids. In this context a variety of spectroscopic methods are used to address the problems of the Gem stone identification and identification of origin of colours and colour modification treatments. The methods frequently used in Gem testing labs are the following: (i)Electronic absorption in UV-Visible-NIR range.(ii)UV-Vis excited luminescence, (iii) Vibrational spectra – Absorption in the Infra red range (iv) Vibrational spectra using Light Scattering (Raman spectroscopy) (v)Surface Fluorescence mapping Under deep UV excitation. The present paper deals with the luminescence studies in rubies, sapphires, emeralds and diamonds. Special mention may be made of fluorescence mapping using deep UV excitation (around 205 nm) corresponding to the band gap of diamond. Under such an excitation inter band excitation takes place creating a e-h pair and most of the absorption and subsequent emission being restricted to the surface. This makes surface mapping possible and thereby elucidating the growth patterns. This is invaluable in the diagnostics for the detection of synthetic diamonds. In this introductory presentation on the Luminescence methods in Gemmology, we give a brief account of optical spectroscopic methods which mainly deal with identification of corundum based gem stones (rubies, sapphire) and diamonds including the electronic absorption and luminescence of chromophore centres. In gem testing infrared absorption and Raman scattering methods are main work horses and they will be brought in as and when necessary to give a complete picture.
Australian Gemmologist, Vol. 25, 3, July-Sept. pp.
Technology
Diamond features
Abstract: This study describes how visual properties determine the perception of a diamond’s appearance and its performance attributes of brilliance, scintillation and fire, and how these influence beauty. Further articles will describe other parts of our cut study project. This research enables the development of methods and instruments for diamond performance analyses, shifting from current diamond cut rejection based tools, to diamond performance scoring systems, and the introduction of a new consumer language for communication between diamond buyers and sellers. The proposed Performance Scoring System is consumer friendly and can be used to design and manufacture new diamond cuts with improved optical appearance.
Diamond and Related Materials, in press available, 6p.
Technology
Synthetics - Radiation detectors
Abstract: Radiation detectors based on diamond are highly favored for particle physics research due to the superior radiation hardness. In this work, we investigate the influence of impurities and crystalline imperfections on the charge collection efficiency (CCE) of single crystal diamond. Seventeen (17) ultra-low fluorescent diamond samples grown by microwave plasma chemical vapor deposition method from IIa Technologies PTE LTD are pre-selected for this study. The measured CCE of all samples using 241Am (?-particles) as ionizing source are analyzed together with the concentration of trace impurities and crystalline imperfection in the crystal. The amounts of impurities are quantified from integrated fluorescence intensity arising from the nitrogen vacancies (NV) created during different CVD growth process conditions. The crystal imperfections are assessed by X-ray rocking curves from X-ray topography images obtained at the Cornell High Energy Synchrotron Source. The CCE decays rapidly as the intensity of NV (INV), phonon sideband approaches that of diamond 2nd order Raman peak which follows the relation: View the MathML sourceCCEINV=100/1+INV1.052. The energy resolution, ?E/E (ratio of the energy spectrum width to the most probable peak) highly correlates with broader rocking curve width distribution. Prime novelty statement: This work provides an understanding on the most important factors that contribute to degradation of charge collection efficiency (CCE) in diamond based detectors and sensors. The CCE decays rapidly as the intensity of nitrogen vacancy phonon sideband approaches that of diamond 2nd order Raman peak which follows the relation: View the MathML sourceCCEINV=100/1+INV1.052. The energy resolution, that is the ratio of the energy spectrum width to the most probable peak, highly correlates with broader X-ray rocking curve width distribution.
Diamond and Related Materials, in press available, 29p.
Technology
Synthetics - nitrogen
Abstract: This study describes the growth of 13C-enriched (100)-oriented diamond single crystals by the MPCVD (microwave plasma chemical vapour deposition) process. All crystals are at least 6 × 6 mm2 in area and 0.5-1.0 mm in thickness. The samples with nominal 13C percentages (R = [13C] / [13C + 12C]) of 0.011 (natural abundance), 0.10, 0.21, 0.24 and 0.34 were obtained by controlling the flow of the carbon-13 and carbon-12 methane feed gases. To obtain thicker and near-colourless quality 13C-enriched diamond, 190 ppm of nitrogen was added into the gas mixture. The shift towards lower frequency in the Raman peak positions and decrease in the thermal conductivities of the near-colourless crystals with increasing 13C percentages are similar to previous studies of isotopically-controlled diamond grown with no nitrogen additive. The images of the structural defects associated with 13C-enrichment obtained by spatially-resolved X-ray rocking curve measurement show distinct patterned structures that runs parallel to the < 100 > direction. Moreover, the broadening in the line width of the nuclear magnetic resonance (NMR) peak from sp313C correlates with increasing R. We also expand the study by injecting 500 ppm of nitrogen. Higher nitrogen concentration leads to the formation of brown crystals. The brown crystals show far greater 13C NMR peak intensity than the near-colourless. This suggests that paramagnetic nitrogen impurities in the brown crystals hasten the spin-lattice relaxation time of the 13C nuclear spin that resulted in higher intensity. The isotopic splitting observed for the localized vibrational mode of the NVH0 defect in brown crystals is attributed to the co-existence of both the 13C (3114.2 cm? 1) and 12C (3123.5 cm? 1). Unlike the isotopic splitting observed for NVH0 defect, the peak position of the Ns+ defect shifts towards lower frequency as R increases. Not only have we demonstrate the growth of bigger isotopically-controlled diamond single crystals, the results shown here have provided a framework to further investigate the interplay between 13C atoms and nitrogen impurity.
Symposium on critical and strategic materials, British Columbia Geological Survey Paper 2015-3, held Nov. 13-14, pp. 231-240.
Technology
Rare earths
Abstract: Biogeochemical exploration is an effective but underutilized method for delineating covered mineralization. Plants are capable of accumulating rare earth elements (REEs) in their tissue, and ferns (pteridophytes) are especially adept because they are one of the most primitive land plants, therefore lack the barrier mechanisms developed by more evolved plants. The Norra Kärr Alkaline Complex, located in southern Sweden approximately 300km southwest of Stockholm, is a peralkaline nepheline syenite enriched in heavy rare earth elements (HREEs). The deposit, roughly 300m wide, 1300m long, and overlain by up to 4 m of Quaternary sediments, has been well-defined by diamond drilling. The inferred REE mineral resource, over 60 million tonnes averaging 0.54% Total Rare Earth Oxide (TREO), is dominantly hosted within the pegmatitic “grennaite” unit, a eudialyte-catapleiite-aegerine nepheline syenite. Vegetation and soil samples were collected from the surficial environment above Norra Kärr to address four key questions: which plant species is the most effective biogeochemical exploration medium; what are the annual and seasonal REE variations in that plant; how do the REEs move through the soil profile; and into which part of the plant are they concentrated. Athyrium filix-femina (lady fern) has the highest concentration of LREEs and HREEs (up to 125.17ppm Ce and 1.03ppm Dy) in its dry leaves; however, there is better contrast between background and anomalous areas in Dryopteris filix-mas (wood fern), which makes it the preferred biogeochemical sampling medium. The REE content in all fern species was shown to decrease from root > frond > stem, and chondrite normalized REE patterns within the plant displayed preferential fractionation of the LREEs in the fronds relative to the roots. Samples collected from an area directly overlying the deposit had up to five times greater HREE content (0.74ppm Dy) in August than the same plants did in June (0.14ppm Dy). The elevated REE content and distinct contrast to background demonstrate that biogeochemical sampling is an effective method for REE exploration in this environment.
Abstract: Most kimberlites contain abundant dunitic nodules. These are centimetre-sized, rounded and multi-grained assemblages of xenocrystic olivine with a wide range of compositions (Fo83 to Fo94). The absence of orthopyroxene and other mantle minerals and the range of olivine compositions have been attributed to reaction between mantle peridotite and (proto)kimberlitic fluid or melt, but the timing of the reaction is a subject of debate. In a kimberlite from the Kangamiut region of Greenland, nodule cores are surrounded by fine-grained outer margins with near-constant Fo contents (~Fo88) but highly variable minor element contents (e.g. 500-2500 ppm Ni). These margins crystallized from the kimberlite melt and we show that their compositions can be explained by crystallization of olivine alone, if a high partition coefficient for Ni between melt and olivine (DNi > 20) is assumed. Orthopyroxene assimilation is not required, removing the constraint that its dissolution occurred during ascent of the kimberlite magma. Within some nodules, in addition to the usual core-to-margin gradients, we observe asymmetric compositional changes (variable Fo but near-constant minor element contents) across mobile grain boundaries. These changes document fluid percolation at the grain scale that occurred during dynamic recrystallization in the deforming lithospheric mantle. We note that chemical gradients associated with mobile grain boundaries are observed in olivines that cover the entire compositional range of the nodules, and propose that fluid-assisted dynamic recrystallization took place in dunite that was already compositionally heterogeneous. Reaction between peridotite and protokimberlitic melt or fluid and dissolution of orthopyroxene thus occurred within the lithospheric mantle, immediately (a few days) prior to the ascent of the kimberlite melt and the entrainment of the dunite nodules. We propose that the grain boundary zones probably mimic, at a fine scale, the fluid-peridotite interaction that caused, at a larger scale, orthopyroxene dissolution and formation of compositionally diverse olivine in kimberlites.
Abstract: The Russian company New Diamond Technology is producing colorless and near-colorless HPHT-grown synthetic diamonds for the gem trade. Forty-four faceted samples synthesized using modified cubic presses were analyzed using a combination of spectroscopic and gemological techniques to characterize the quality of the material and determine the means of distinguishing them from natural, treated, and alternative laboratory-grown diamonds. These samples, with weights ranging from 0.20 to 5.11 ct, had color grades from D to K and clarity grades from IF to I2. Importantly, 89% were classified as colorless (D-F), demonstrating that HPHT growth methods can be used to routinely achieve these color grades. Infrared absorption analysis showed that all were either type IIa or weak type IIb, and photoluminescence spectroscopy revealed that they contained Ni-, Si-, or N-related defects. Their fluorescence and phosphorescence behavior was investigated using ultraviolet excitation from a long-wave/short-wave UV lamp, a DiamondView instrument, and a phosphorescence spectrometer. Key features that reveal the samples’ HPHT synthetic origin are described.
Mini-Reviews in Organic Chemistry, Vol. 12, 4, pp. 355-366.
Technology
Fullerenes
Abstract: Fullerenes being allotropes of carbon, have been considered as new class of molecules. Unlike diamond and graphite, this is made up of hollow carbon cage structure. The idea of spheroidal cage structures of C60 arose from construction of geodesic domes made by renowned architect Buckminster Fuller. Although fullerenes have low solubility in physiological media they finds promising biological applications. The photo, electrochemical and physical properties of C60 and other fullerene derivatives finds applications in medical fields. The ability of fullerenes to fit inside the hydrophobic cavity of HIV proteases makes them potential inhibitor for substrates to catalytic active site of enzyme. It possesses radical scavenging and antioxidant property. At the same time, when it exposed to light it can form singlet oxygen in high quantum yields which with direct electron transfer from excited state of fullerenes and DNA bases finally results in cleavage of DNA. The fullerenes are also used as a carrier for gene and drug delivery system. The associated low toxicity of fullerenes is sufficient to attract the researchers for investigation of these interesting molecules.
Abstract: Under high pressures, water can react with surrounding rock to make diamonds and oil. These are just two consequences of a new picture of water's versatile chemistry in the mantle. The Deep Earth Water model is showing that, under extreme pressures down to 200 kilometers, water can dissolve many ions and host unexpected new reactions. It is replacing a geochemical framework, published in 1981, which made predictions for water-rock interactions, but only down to 15 kilometers. The idea that oil can be made from water and rock in the mantle is controversial, because it has long been assumed that oil arises through the compaction and burial of organic matter.
Symposium on critical and strategic materials, British Columbia Geological Survey Paper 2015-3, held Nov. 13-14, pp. 245-250.
Technology
Carbonatite
Abstract: We measured 10 major (SiO2, TiO2, Al2O3, total Fe2O3, MnO, MgO, CaO, Na2O, K2O, and P2O5) and 32 trace (Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb, Cs, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Pb, Th, and U) elements in 16 geochemical reference samples (AGV-1, AGV-2, BCR-1, BCR- 2, BHVO-2, BIR-1a, DNC-1a, G-2, GSP-1, GSP-2, MAG-1, QLO-1, RGM-1, RGM-2, SGR-1b, and STM-1) distributed by United States Geological Survey (USGS) and three reference rock samples (SY-2, SY-3, and MRG-1) provided by Canadian Certifi ed Reference Materials Project (CCRMP) using inductively coupled plasma -mass spectrometry coupled with the femtosecond laser ablation sample introduction technique (fsLA-ICP-MS). Before the elemental analysis, fused glassbeads were prepared from the mixture of sample powder and high-purity alkali fl ux with a mixing ratio of 1:10. The abundances of the major and trace elements were externally calibrated by using glass beads containing the major and trace elements prepared from 17 Geological Survey of Japan (GSJ) geochemical reference samples (JB-1, JB-1a, JB-2, JB-3, JA-1, JA-2, JA-3, JR-1, JR-2, JR-3, JP-1, JGb-1, JGb-2, JG-1a, JG- 2, JG-3, and JSy-1). Typical analysis repeatabilities for these geochemical reference samples were better than 3% for Al2O3 and Na2O; <5% for SiO2, TiO2, total Fe2O3, MnO, MgO, CaO, K2O, P2O5, Zn, Rb, Sr, Zr, Nb, Ba, Nd, and U; <8% for Sc, V, Cr, Co, Y, Cs, La, Ce, Pr, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Pb, and Th; <11% for Ni and Cu. These data clearly demonstrate that high analytical repeatability can be achieved by the fsLA-ICP-MS technique with glass beads made from 0.5 g larger samples.
Symposium on critical and strategic materials, British Columbia Geological Survey Paper 2015-3, held Nov. 13-14, pp. 211-218.
Technology
Rare earths
Abstract: Quantitative Evaluation of Materials by Scanning electron microscopy (QEMSCAN®) was used to assess carbonatite indicator minerals in fl uvial sediments from the drainage area of the Aley carbonatite, in north-central British Columbia. QEMSCAN® is a viable method for rapid detection and characterization of carbonatite indicator minerals with minimal processing other than dry sieving. Stream sediments from directly above, and up to 11 km downstream, of the carbonatite deposit were selected for this indicator mineral study. The geology of the Aley carbonatite is described by Mäder (1986), Kressal et al. (2010), McLeish (2013), Mackay and Simandl (2014), and Chakhmouradian et al. (2015). Traditional indicator mineral exploration methods use the 0.25-2.0 mm size fraction of unconsolidated sediments (Averill, 2001, 2014; McCurdy, 2006, 2009; McClenaghan, 2011, 2014). Indicator minerals are detectable by QEMSCAN® at particle sizes smaller than those used for hand picking (<0.25 mm). Pre-concentration (typically by shaker table) is used before heavy liquid separation, isodynamic magnetic separation, optical identifi cation using a binocular microscope, and hand picking (McClenaghan, 2011). Following additional sieving, the 0.5-1 and 1-2 mm fractions are hand picked for indicator minerals while the 0.25-0.5 mm fraction is subjected to paramagnetic separation before hand picking (Averill, 2001; McClenaghan, 2011). Hand picking indicator minerals focuses on monomineralic grains, and composite grains may be lost during processing. Composite grains are diffi cult and time consuming to hand pick and characterize using optical and Scanning Electron Microscopy (SEM) methods. A single grain mount can take 6-12 hours to chemically analyse (Layton- Matthews et al., 2014). Detailed sample analysis using the QEMSCAN® Particle Mineral Analysis routine allows for 5-6 samples to be analyzed per day. When only mineral identifi cation and mineral concentrations and counts are required, the use of a Bulk Mineral Analysis routine reduces the analysis time from ~4 hours to ~30 minutes per sample.
Symposium on critical and strategic materials, British Columbia Geological Survey Paper 2015-3, held Nov. 13-14, pp. 251-264.
Technology
Rare earths
Abstract: Fluorite (CaF2) belongs to the isometric system, with a cubic, face-centred lattice. Fluorite commonly forms cubes or octahedrons, less commonly dodecahedrons and, rarely, tetrahexahedrons, trapezohedrons, trisoctahedrons, hexoctahedrons, and botyroidal forms. Fluorite is transparent to translucent, and has vitreous luster. It occurs in a variety of colours including purple, green, blue, or yellow, however it can also be colourless, and can exhibit colour zoning, (Staebler et al., 2006). Fluorite from many localities is fl uorescent (Verbeek, 2006). Fluorite density varies from 3.0-3.6 g/cm3, depending to a large extent on inclusions and impurities in the crystal lattice (Staebler et al., 2006), and its hardness is 4 on Mohs scale (Berry et al., 1983). Many single fl uorite crystals display sector zoning, refl ecting preferential substitution and incorporation of trace elements along successive crystal surfaces (Bosce and Rakovan, 2001). The Ca2+ ion in the fl uorite crystal structure can be substituted by Li+, Na+, K+, Mg2+, Mn2+, Fe2+,3+, Zn2+, Sr2+, Y3+, Zr4+, Ba2+, lanthanides ions, Pb2+, Th4+, and U4+ ions (Bailey et al., 1974; Bill and Calas, 1978, Gagnon et al., 2003; Schwinn and Markl, 2005; Xu et al., 2012; Deng et al., 2014). Concentrations of these impurities do not exceed 1% (Deer, 1965) except in yttrofl uorite (Ca,Y)F2-2.33 and cerfl uorite (Ca,Ce)F2-2.33 (Sverdrup, 1968). Fluorite occurs in a variety of rocks, as an accessory and as a gangue mineral in many metalliferous deposits and, in exceptional cases, as the main ore constituent of economic deposits (Simandl, 2009). Good examples of fl uorite mines are Las Cuevas, Encantada-Buenavista (Mexico); St. Lawrence pluton-related veins and the Rock Candy Mine (Canada); El Hamman veins (Morocco) and LeBurc Montroc -Le Moulinal and Trebas deposits (France) as documented by Ruiz et al. (1980), Grogan and Montgomery (1975), González-Partida et al. (2003), Munoz et al. (2005), and Fulton III and Miller (2006). Fluorite also commonly occurs adjacent to or within carbonatites and alkaline complexes (Kogut et al., 1998; Hagni,1999; Alvin et al., 2004; Xu et al., 2004; Salvi and Williams-Jones, 2006); Mississippi Valley-type (MVT) Pb- Zn-F-Ba deposits; F-Ba-(Pb-Zn) veins (Grogan and Bradbury, 1967 and 1968; Baxter et al., 1973; Kesler et al., 1989; Cardellach et al., 2002; Levresse et al., 2006); hydrothermal Fe (±Au, ±Cu) and rare earth element (REE) deposits (Borrok et al., 1998; Andrade et al., 1999; Fourie, 2000); precious metal concentrations (Hill et al., 2000); fl uorite/metal-bearing skarns (Lu et al., 2003); Sn-polymetallic greissen-type deposits (Bettencourt et al., 2005); and zeolitic rocks and uranium deposits (Sheppard and Mumpton, 1984; Cunningham et al., 1998; Min et al., 2005). Ore deposit studies that document the trace element distribution in fl uorite are provided by Möller et al. (1976), Bau et al. (2003), Gagnon et al. (2003), Schwinn and Markl (2005), and Deng et al. (2014). The benchmark paper by Möller et al. (1976) identifi ed variations in the chemical composition of fl uorites according their origin (sedimentary, hydrothermal, or pegmatitic). Recently, Makin et al. (2014) compiled trace-element compositions of fl uorite from MVT, fl uorite-barite veins, peralkaline-related, and carbonatite-related deposits. They showed that fl uorite from MVT and carbonatite deposits can be distinguished through trace element concentrations, and that the REE concentration of fl uorite from veins is largely independent of the composition of the host rock. Based on the physical and chemical properties of fl uorite, its association with a variety of deposit types, and previous studies, it is possible that fl uorite can be used as a proximal indicator mineral to explore for a variety of deposit types. Unfortunately, the compilation by Makin et al. (2014) contained chemical analyses performed at different laboratories using different analytical techniques (including laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS), electron microprobe, neutron activation, and ICP-MS), and precision and accuracy varied accordingly. As an orientation survey, herein we present data from fi ve deposits, with two samples from the Rock Candy deposit (British Columbia), and one sample from each of Kootenay Florence (British Columbia), Eaglet (British Columbia), Eldor (Quebec), and Hastie quarry (Illinois) deposits (Table 1). The main objectives of this study are to: 1) assess variations in chemical composition of fl uorite in the samples and deposit types; 2) evaluate relations between analyses made using laser ablation-inductively coupled plasma mass spectrometry on individual grains [LA-ICP-MS(IG)], and those made using laser ablation-inductively coupled plasma mass spectrometry on fused beads [LA-ICP-MS(FB)] and X-ray fl uorescence (XRF); 3) test the use of stoichiometric Ca content as an internal fl uorite standard, such has been done by Gagnon et al. (2003) and Schwinn and Markl, (2005); 4) select the elements that are commonly present in concentrations above the lower limit of detection of LA-ICP-MS and available for constructing discrimination diagrams; 5) consider if our results agree with the preliminary discrimination diagrams of Makin et al. (2014).
Abstract: Google Earth has been part of most geoscientists' computer (and mobile) desktops for a decade, and this year Google Earth Professional has become freely available to all with a universal license key. Many users are still, however, not aware of the full potential that it can offer across a range of teaching and research areas in the geosciences. Here a pragmatic look is taken at some of the current key uses in terms of resources and applications and how they can help in research and training educational roles in the geosciences.
Abstract: Current desktop technology is largely mouse-driven, but many analysts predict that in less than five years we will have a professional workforce that have only experienced learning in a touchscreen environment. Midland Valley have developed a digital mapping tool for smartphones called FieldMove Clino, which has been downloaded more than 20 000 times over the past year. The free version offers an effective way of introducing students to digital field mapping. However, many geoscience departments and teachers of field mapping have yet to make the switch from traditional paper-based methods to digital technology. This article aims to answer some of the frequently asked questions about digital field mapping and outlines some of the advantages for improving field skills and geological thinking in students.
Symposium on critical and strategic materials, British Columbia Geological Survey Paper 2015-3, held Nov. 13-14, pp. 199-210.
Technology
Rare earths
Abstract: For decades, gamma ray spectrometry has been used worldwide to map rocks and locate mineralization in diverse geological settings (Shives et al., 1997). The method is particularly well suited to rare metal and REE (rare earth element) exploration because primary host rocks are enriched in incompatible elements known as LILE (large-ion lithophile elements K, Rb, Cs, Sr, Ba) and HSFE (high fi eld strength elements Zr, Nb, Hf, REEs, Th, U and Ta). As a result, the ores of REEs are commonly radioactive because host rocks, orebearing minerals, or associated accessory minerals may contain trace to anomalous concentrations of radioactive elements K, U and Th. These radioactive elements provide a useful and direct exploration vectors. Gamma ray data are often collected simultaneously with magnetic, electromagnetic, and gravity data in multisensor surveys. The objective of this extended abstract is to emphasize the importance of gamma ray spectrometry as a primary exploration tool for rare metal deposits. Case histories presented herein illustrate radioactive element and magnetic signatures associated with diverse rare metal deposit types in different geological settings. Canadian examples include: Cantley, Quebec (Quinnville and Templeton carbonatites); Oka, Quebec (carbonatite); Bancroft, Ontario (pegmatites); Allan Lake, Ontario (a blind carbonatite discovery); Nechalacho, Northwest Territories (previously called Thor Lake; altered ultra-alkaline layered complex); Strange Lake, Quebec (peralkaline granite, pegmatite); and one each from British Columbia and Labrador. Also presented are examples from Greenland, Norway, and Mozambique.
Abstract: Diamond formation has typically been attributed to redox reactions during precipitation from fluids or magmas. Either the oxidation of methane or the reduction of carbon dioxide has been suggested, based on simplistic models of deep fluids consisting of mixtures of dissolved neutral gas molecules without consideration of aqueous ions. The role of pH changes associated with water–silicate rock interactions during diamond formation is unknown. Here we show that diamonds could form due to a drop in pH during water–rock interactions. We use a recent theoretical model of deep fluids that includes ions, to show that fluid can react irreversibly with eclogite at 900?°C and 5.0?GPa, generating diamond and secondary minerals due to a decrease in pH at almost constant oxygen fugacity. Overall, our results constitute a new quantitative theory of diamond formation as a consequence of the reaction of deep fluids with the rock types that they encounter during migration. Diamond can form in the deep Earth during water–rock interactions without changes in oxidation state.
Journal of Physics Condensed Matter, Vol. 541, 1, pp. 12090-12094.
Technology
Diamond crystallography
Abstract: The optical and ODMR spectra of nitrogen vacancy (NV) centers in diamond were investigated as applied to the development of micro-scale diamond magnetometer sensor. It is shown that the NV0 center (unlike the NV? center) has an absorption line in the UV range. The inversion of the zero phonon line of the NV? center was observed and explained. ODMR signals in high magnetic fields (as compared with inner fields in the crystal) as well as in weak fields also were investigated. We propose the solution to the problem of the magnetometer sensitivity reduction at low magnetic field, that is of interest for quantum magnetometry applications. Peculiarities of optical and ODMR Spectra of Nitrogen-Vacancy Color Centers in Diamond Crystals.
Symposium on critical and strategic materials, British Columbia Geological Survey Paper 2015-3, held Nov. 13-14, pp. 193-198.
Technology
Rare earths
Abstract: Geochemical exploration for Nb, Ta, Zr and rare earth element (REE) mineralization associated with carbonatite, pegmatite, and peralkaline intrusions presents unique challenges and opportunities. The challenges are mainly due to the tendency of these elements, as High Field Strength Elements (HFSE), to be relatively immobile in surface environments in addition to commonly forming minerals that are resistant to weathering. In addition, many of the host minerals are resistant to routine exploration geochemistry digestions, which are typically aimed at dissolving soluble oxides or extracting more labile ionic forms (Reimann et al., 2014). Opportunities arise because host rocks typically represent relatively rare end products of the magmatic processes that generate peralkaline magmas including, at the far end of the spectrum, carbonatites. Hence host rocks are relatively easy to identify geochemically and commonly defi ne classic lithological zoning (e.g., Modreski et al., 1995). In addition, many of the minerals that contain these elements are resistant to weathering, mechanically durable, have relatively high densities, and have the have the potential to form heavy mineral concentrates when released by weathering. This is particularly so for Zr, Nb, and Ta, which form primary minerals such as tantalite (Ta Nb), pyrochlore (Nb), coltan (Ta Nb), columbianite (Ta Nb), dysanalite-perovskite (Nb) and zircon (Zr). In contrast, the REE are mobile in the weathering environment and commonly re-locate from primary carbonate and phosphate minerals (e.g., synchysite, monazite, xenotime, bastnäsite, allanite) to secondary phosphate minerals such as churchite (Lottermoser, 1990) and gorceixite (Mariano, 1989).
Weidenfeld & Nicholson London Book Publisher, Amazon.com approx. 12.00 paperback
Technology
Book
Abstract: Humans have put the Earth’s resources to extraordinary use. Carbon provides us with heat, light and mobility at the flick of a switch. From silver came photography, the preservation of memories, and a task which for centuries was confined to painters, sketchers and our imaginations. Silver in turn was eventually replaced by silicon, an element which enables us to communicate and transmit information across the globe in an instant. But our use of the Earth’s resources is not always for the benefit of humankind. Our relationship with the elements is one of great ambivalence. Uranium produces both productive nuclear power and destructive atomic bombs; iron is the bloody weapon of war, but also the economic tool of peace; our desire for alluring gold is the foundation of global trade, but has also led to the death of millions. This book vividly describes how seven key elements have shaped the world around us - for good and for bad. Seven Elements takes you on an adventure of human passion, ingenuity and discovery. This journey is far from over: we continue to find surprising new uses for these seven elements. Discover how titanium pervades modern consumer society; how natural gas is transforming the global energy sector; and how an innovative new form of carbon could be starting a technological revolution. Seven Elements is a unique mix of science, history and politics, interwoven with the author’s extensive personal and professional experience.
Abstract: Spinel is ubiquitous as a rock-forming mineral in terrestrial, lunar, and planetary basalts and closely associated meteoritic equivalents. A major unknown is whether these rocks formed under similar conditions of partial melting of primary or modified mantle, whether redox environments played a role in evolutionary trends, and did mineral crystal chemistry have any influence on elemental partition between solids and liquids? In a novel approach by Papike et al. (2015), spinel is used as an informative, albeit complex indicator of oxygen fugacity, site occupancy of multiple valence elements, and spinel structural types. Planetary basalts may be reduced (IW-3), oxidized (Earth at FMQ), or of intermediate redox state (Mars). Taking an expansive view, the spinel approach holds enormous promise in understanding the magmatic differentiation of asteroids.
Abstract: It is known that carbon melts at temperatures around 4000 K or higher, and, therefore, this will be for the first time, when liquid carbon state formation preserved within diamond is documented in a carbon-carbonate system at the PT-conditions around 8.0 GPa and 2000 K, that is essentially far from the carbon diagram liquid field, so the newly reported liquid carbon was formed by neither fusion nor condensation. Based on a preponderance of such a strong circumstantial evidence, as morphological features of globular glass-like carbon inclusions within the globular-textured host diamond crystals resulting from liquid segregation process under synthesis conditions, it is suggested, that the produced carbon state has general properties of liquid and is formed through agglomeration alongside with diffusion process of carbon within carbonate melt solvent, and, thus, can potentially open a novel route for liquid carbon production and manufacturing of advanced high-refractory alloys and high-temperature compounds at lower than commonly accepted standard temperatures. A new model of diamond formation via metastable liquid carbon is presented.
Diamond and Related Materials, in press available 29p.
Technology
Green diamonds
Abstract: The green coloration of natural diamonds typically results from exposure to natural irradiation. This creates the GR1 optical center and in many diamonds, surficial damage, principally due to alpha radiation, which helps verify natural origin. In this study, 13 naturally irradiated diamonds with pronounced radiation stains were stepwise annealed from 200 °C to 1400 °C and the changes in color and defects were documented by photomicrography and spectroscopy. Additionally 3 diamonds were subjected to isothermal annealing at 550 °C. The radiation stains correlated with radiation-damage Raman peaks — a broad and shifted diamond Raman peak and radiation-related peaks at 1500 and 1640 cm? 1. The color transitioned from green to brown after heating to 550-600 °C and the stains were essentially decolorized at 1400 °C. Confocal Raman depth profiling showed that the depth penetration of the radiation stain was about 10-15 ?m into the diamond and this depth profile was distinctly different from depth profiles of ion-irradiation stains generated in a laboratory.
Abstract: Images of diamonds appear everywhere in American culture. And everyone who has a diamond has a story to tell about it. Our stories about diamonds not only reveal what we do with these tiny stones, but also suggest how we create value, meaning, and identity through our interactions with material culture in general. Things become meaningful through our interactions with them, but how do people go about making meaning? What can we learn from an ethnography about the production of identity, creation of kinship, and use of diamonds in understanding selves and social relationships? By what means do people positioned within a globalized political-economy and a compelling universe of advertising interact locally with these tiny polished rocks? This book draws on 12 months of fieldwork with diamond consumers in New York City as well as an analysis of the iconic De Beers campaign that promised romance, status, and glamour to anyone who bought a diamond to show that this thematic pool is just one resource among many that diamond owners draw upon to engage with their own stones. The volume highlights the important roles that memory, context, and circumstance also play in shaping how people interpret and then use objects in making personal worlds. It shows that besides operating as subjects in an ad-burdened universe, consumers are highly creative, idiosyncratic, and theatrical agents.
Earth and Planetary Science Letters, Vol. 434, pp. 129-140.
Technology
Petrology - experimental
Abstract: Transitional melts, intermediate in composition between silicate and carbonate melts, form by low degree partial melting of mantle peridotite and might be the most abundant type of melt in the asthenosphere. Their role in the transport of volatile elements and in metasomatic processes at the planetary scale might be significant yet they have remained largely unstudied. Their molecular structure has remained elusive in part because these melts are difficult to quench to glass. Here we use FTIR, Raman, 13C and 29Si NMR spectroscopy together with First Principle Molecular Dynamic (FPMD) simulations to investigate the molecular structure of transitional melts and in particular to assess the effect of CO2 on their structure. We found that carbon in these glasses forms free ionic carbonate groups attracting cations away from their usual ‘depolymerising’ role in breaking up the covalent silicate network. Solution of CO2 in these melts strongly modifies their structure resulting in a significant polymerisation of the aluminosilicate network with a decrease in NBO/Si of about 0.2 for every 5 mol% CO2 dissolved. This polymerisation effect is expected to influence the physical and transport properties of transitional melts. An increase in viscosity is expected with increasing CO2 content, potentially leading to melt ponding at certain levels in the mantle such as at the lithosphere-asthenosphere boundary. Conversely an ascending and degassing transitional melt such as a kimberlite would become increasingly fluid during ascent hence potentially accelerate. Carbon-rich transitional melts are effectively composed of two sub-networks: a carbonate and a silicate one leading to peculiar physical and transport properties.
Abstract: The compound [CH3 CH2 NH3 ][Cu(HCOO)3 ] undergoes a phase transition at 357 K, from a perovskite to a diamond structure, by heating. The backward transition can be driven by pressure at room temperature but not cooling under ambient or lower pressure. The rearrangement of one long copper-formate bond, the switch of bridging-chelating mode of the formate, the alternation of N-H???O H-bonds, and the flipping of ethylammonium are involved in the transition. The strong N-H???O H-bonding probably locks the metastable diamond phase. The two phases display magnetic and electric orderings of different characters.
Diamond and Related Materials, Vol. 62, pp. 42-48.
Technology
Carbon
Abstract: It is known that carbon melts at temperatures around 4000 K or higher, and, therefore, this will be for the first time, when liquid carbon state formation preserved within diamond is documented in a carbon-carbonate system at the PT-conditions around 8.0 GPa and 2000 K, that is essentially far from the carbon diagram liquid field, so the newly reported liquid carbon was formed by neither fusion nor condensation. Based on a preponderance of such a strong circumstantial evidence, as morphological features of globular glass-like carbon inclusions within the globular-textured host diamond crystals resulting from liquid segregation process under synthesis conditions, it is suggested, that the produced carbon state has general properties of liquid and is formed through agglomeration alongside with diffusion process of carbon within carbonate melt solvent, and, thus, can potentially open a novel route for liquid carbon production and manufacturing of advanced high-refractory alloys and high-temperature compounds at lower than commonly accepted standard temperatures. A new model of diamond formation via metastable liquid carbon is presented.
Nuclear Instruments and Methods in Physics Research Section A., A785, pp. 9-13.
Technology
Methodology
Abstract: A new technology for diamond detection in kimberlite based on the tagged neutron method is proposed. The results of experimental researches on irradiation of kimberlite samples with 14.1-MeV tagged neutrons are discussed. The source of the tagged neutron flux is a portable neutron generator with a built-in 64-pixel silicon alpha-detector with double-sided stripped readout. Characteristic gamma rays resulting from inelastic neutron scattering on nuclei of elements included in the composition of kimberlite are registered by six gamma-detectors based on BGO crystals. The criterion for diamond presence in kimberlite is an increased carbon concentration within a certain volume of the kimberlite sample.
Science Advance AEON and Earth Stewardship Science Research Institute, Nelson Mandela Metropolitan Univerisity, 13p.
Technology
Glacial remnants, exosphere, silica pipes
Abstract: Estimates of ocean temperatures on Earth 3.5 billion years ago (Ga) range between 26° and 85°C. We present new data from 3.47- to 3.43-Ga volcanic rocks and cherts in South Africa suggesting that these temperatures reflect mixing of hot hydrothermal fluids with cold marine and terrestrial waters. We describe fossil hydrothermal pipes that formed at ~200°C on the sea floor >2 km below sea level. This ocean floor was uplifted tectonically to sea level where a subaerial hydrothermal system was active at 30° to 270°C. We also describe shallow-water glacial diamictites and diagenetic sulfate mineral growth in abyssal muds. These new observations reveal that both hydrothermal systems operated in relatively cold environments and that Earth’s surface temperatures in the early Archean were similar to those in more recent times.
GAC MAC Meeting Special Session SS11: Cratons, kimberlites and diamonds., Keynote abstract
Technology
Emplacement
Abstract: The study develops a new approach utilizing parameters of trigonal etch pits on diamond crystals to infer the conditions of diamond residence in kimberlite magma. Diamond crystals from dissolution experiments conducted at 1 GPa and 1150-1350 °C in the presence of H2O-rich or CO2-rich fluid were studied with atomic force microscopy (AFM). The AFM data of resorbed diamond surfaces show that much deeper surface relief was produced in CO2 fluid. It also clearly distinguishes the profiles of the trigonal etch pits forming regular flat-bottomed trigons in H2O fluid, and round- or pointed-bottomed trigons in CO2 fluid. The relationship between the diameter and the depth of the trigonal pits is found to be another important indicator of the fluid composition. Dissolution in H2O fluid develops trigons with constant diameter and variable depth where the diameter increases with temperature. Trigons developed in CO2 fluid have a large range of diameters showing a strong positive correlation with the depth. The developed criteria applied to the natural diamond crystals from three Ekati Mine kimberlites indicate significant variation in CO2-H2O ratio and temperature of their magmatic fluid. This conclusion based on diamond resorption agrees with the mineralogy of microphenocrysts and groundmass of the studied kimberlites offering new method to study crystallization conditions of kimberlite magma.
Abstract: Kevin Heather’s (SEG 1998 F) presentation at the September 2015 Chile- Explore Congress, entitled “The Lost Art of Geological Mapping: Should We Care?,” regrettably came as no surprise to me, although I have to admit to being more than a little disappointed. Most senior explorationists, I suspect, would probably share these sentiments. Geological mapping is, after all, the very embodiment of all the basic field skills we learn as geologists, and the simple fact is that the alarm bells have been sounding loudly for some time now in our industry: basic field geological skills have been lost in the emerging generation of exploration geologists. As a geologist with some 30 years of experience in the exploration and mining industry, almost entirely in a fieldbased technical capacity, I have always maintained that careful geological mapping, based on sound observation, is one of the cornerstones of successful exploration. Indeed, given that our industry is founded on combinations of fortuitous geological phenomena in a complex framework, why would geological mapping and field geology not be positioned at the very forefront the discovery process? A large part of the debate as to the underlying causes for the general demise of geological field skills has focused on issues at the university level (e.g., fieldwork reduction due to funding cuts and increased liability, changes in undergraduate curricula to more closely reflect the broadening range of geological disciplines to serve wider needs of society, an emphasis on rapidly publishable experimental and modeling research at the expense of more costly field-based studies, etc.). The mining industry has responded by promoting its specific technical and skill set requirements at university level via collaborative research, student training initiatives, and funding programs. The focus of this Views contribution is to examine several internal industry issues which I believe have contributed to falling standards of geological fieldwork, and which have become apparent to me during extensive time spent in the field in a consulting capacity for numerous major, mid-tier, and junior companies.
Developments in FTIR spectroscopy of diamond ( part 1): nitrogen aggregation in zoned diamonds, the timing of diamond growth and the thermal history of the lithosphere.
Enigmatic relationship between silicic and volcanic and plutonic rocks: geophysical evidence for silicic crustal melt in the continents: where. What kind, and how much?
Abstract: The last of a group of dense minerals that make up much of Earth’s crust and upper mantle has been found tucked inside a meteorite that slammed into Australia 135 years ago. The newly discovered mineral, a variety of majorite, is potentially abundant in sinking tectonic plates and could help illuminate the behavior of the deep Earth, its discoverers say. ach identical component of this mineral contains 32 magnesium atoms, 32 silicon atoms and 96 oxygen atoms arranged in a distorted cube. Natural samples of MgSiO3 tetragonal garnet, the mineral’s scientific moniker, had eluded scientists since the mineral was first artificially produced in 1985. aotaka Tomioka, a mineralogist at the Kochi Institute for Core Sample Research in Japan, and colleagues discovered 0.5-micrometer-wide grains of the mineral in a slice of the 19th century meteorite. While many minerals found in meteorites form when slamming into Earth, the new mineral formed in space when two asteroids collided at a relative speed of about 2 kilometers per second, the researchers report online March 25 in Science Advances. ne challenge remains for the researchers: As discoverers of the mineral, they now get to name it.
Abstract: MgSiO3 tetragonal garnet, which is the last of the missing phases of experimentally predicted high-pressure polymorphs of pyroxene, has been discovered in a shocked meteorite. The garnet is formed from low-Ca pyroxene in the host rock through a solid-state transformation at 17 to 20 GPa and 1900° to 2000°C. On the basis of the degree of cation ordering in its crystal structure, which can be deduced from electron diffraction intensities, the cooling rate of the shock-induced melt veins from ~2000°C was estimated to be higher than 103°C/s. This cooling rate sets the upper bound for the shock-temperature increase in the bulk meteorite at ~900°C.
Abstract: Photoluminescence (PL) spectroscopy is frequently mentioned in the gemological literature, but its relevance to the wider trade audience is rarely discussed. Due to the possibility of an undisclosed treatment or a synthetic origin, all type II diamonds (both colorless and fancy-color) and colorless type IaB diamonds submitted to gemological laboratories should ideally be tested using PL spectroscopy. Although the proportion of samples that require this testing is small, the failure to properly identify treated and synthetic diamonds could destabilize the diamond industry. This article seeks to clarify the underlying physics and methodology of this important tool for gemologists.
Geochimica et Cosmochimica Acta, Vol. 157, pp. 1-12.
Technology
Diamond morphology
Abstract: Nitrogen isotope values from mantle diamonds are a commonly used tracer in the quest to track volatiles within the Earth’s mantle through deep time. Interpretations of this isotope data are valid so long as stable isotope fractionation processes in the mantle are understood. The fractionation of nitrogen isotopes between {1 1 1} and {1 0 0} growth sectors is well documented for high-pressure high-temperature (HPHT) synthetic diamonds, but there is little data on whether it also occurs in natural mixed-habit diamonds. We present 91 in-situ nitrogen isotope (?15N) measurements, along with carbon isotope (?13C) values and nitrogen abundances [N], obtained from three mixed-habit diamonds by secondary ion mass spectrometry (SIMS). While the well-documented enrichment of nitrogen concentrations in octahedral sectors compared to contemporaneous cuboid sectors is observed, a similarly clear disparity is not obvious in the ?15N data. Whereas HPHT synthetic diamonds exhibit 15N enrichment in the {1 0 0} sectors by ?+30‰, the mixed-habit diamonds studied here show enrichment of the octahedral sectors in 15N by only 0.4-1‰. This major difference between HPHT synthetic and natural mixed-habit diamonds is proposed to be the result of different physical properties of the growth interfaces. The smooth interfaces of the octahedral sectors are the same in both types of crystal, but the outermost atoms on the smooth cube interfaces of an HPHT synthetic diamond behave differently to those on the rough cuboid interfaces of the natural mixed-habit diamonds, resulting in different ?15N values. Both the ?13C (average of ??8.7‰) and ?15N (average of ?0‰) data show only minor offsets from the typical mantle values (?13C = ?5 ± 3‰, ?15N = ?5 ± 4‰). This may indicate diamond formation from a mantle derived fluid/melt containing a minor subducted component (lowering ?13C values and elevating ?15N) or relate to moderate degrees of isotopic fractionation of a pure mantle fluid/melt by prior diamond precipitation. The homogeneous nature of both the carbon and nitrogen isotopic compositions of all three diamonds, however, documents continuous and unlimited supply of diamond forming fluid/melt, with a constant composition. Such homogenous isotopic compositions exclude fluid mixing or isotopic fractionation close to the site of diamond formation and preclude distinguishing between these two processes based on diamond analyses alone.
Sverkhtverdie Materiali ( Ukraine) in RUSSIAN, No. 2, pp. 3-17.
Technology
Morphology of lonsdaleite, diamond
Abstract: External and internal morphologies of natural impact apographitic diamonds (paramorphoses) have been studied. The (0001) surface morphology of the paramorphoses reflects their phase composition and the structural relationship of its constituting phases. Growth and etch figures together with the elements of crystal symmetry of lonsdaleite and diamond are developed on these surfaces. The crystal size of lonsdaleite is up to 100 nm, and that of diamond is up to 300 nm. Two types of structural relations between graphite, lonsdaleite, and diamond in the paramorphoses are observed: the first type (black, black-gray, colorless and yellowish paramorphoses): the (0001) graphite face is parallel to the (100) lonsdaleite face and parallel to (111) diamond; the second type (milky-white paramorphoses): the (0001) graphite is parallel to the (100) lonsdaleite and parallel to the (112) diamond. The first type of the paramorphoses contains lonsdaleite, diamond, graphite or diamond, lonsdaleite, the second type of the paramorphoses contains predominantly diamond. The direct phase transition of graphite ? lonsdaleite and/or graphite ?diamond occurred in the paramorphoses of the first type. A successive phase transition graphite ? lonsdaleite ? diamond was observed in the paramorphoses of the second type. The structure of the paramorphoses of this type shows characteristic features of recrystallization.
American Mineralogist, Vol. 101, 5, pp. 1129-1134.
Technology
Bastanesite
Abstract: Bastnaesite, [RE-CO3-OH/F] (RE = rare earth) is one of the major sources of rare earth elements found in commercial deposits at Mountain Pass, California, Bayan Obo, China, and elsewhere. Synthetic forms of bastnaesite have been explored for applications including optical devices and phosphors. Determination of thermodynamic properties of these phases is critical for understanding their origin, mining, and processing. We report the first experimental determination of formation enthalpies of several OH and F bastnaesites based on high-temperature oxide melt solution calorimetry of well-characterized synthetic samples. The formation enthalpies from binary oxides and fluorides for all the bastnaesite samples are highly exothermic, consistent with their stability in the garnet zone of the Earth’s crust. Fluoride bastnaesite, which is more abundant in nature than its hydroxide counterpart, is thermodynamically more stable. For both OH and F bastnaesite, the enthalpy of formation becomes more negative with increasing ionic radius of the RE3+ cation. This periodic trend is also observed among rare earth phosphates and several other rare earth ternary oxides. For a given RE, the formation enthalpies from binary oxides are more negative for orthophosphates than for bastnaesites, supporting the argument that monazite could have formed by reaction of bastnaesite and apatite at high temperature. The difference in formation enthalpy of monazite and bastnaesite provides insight into energetics of such reactions along the rare earth series.
Technical Physics ** in ENG, Vol. 50, 6, pp. 711-714.
Technology
Nitrogen
Abstract: Natural diamonds are studied by Fourier-transform IR (FTIR) spectroscopy, and it is shown that B2 centers in them form through intermediate stages, which are accompanied by the appearance of absorption bands with maxima near 1550 and 1526 cm?1. The concentration of interstitial carbon atoms in the centers responsible for these bands may be several times higher than the concentration of the interstitials in B 2 defects.
Abstract: The metallurgical recovery processes in diamond mining may, under certain circumstances, cause an under-recovery of large diamonds. In order to predict high quantiles or tail probabilities we use a Bayesian approach to fit a truncated Generalized Pareto Type distribution to the tail of the data consisting of the weights of individual diamonds. Based on the estimated tail probability, the expected number of diamonds larger than a specified weight can be estimated. The difference between the expected and observed frequencies of diamond weights above an upper threshold provides an estimate of the number of diamonds lost during the recovery process.
Abstract: High-pressure, high-temperature (HPHT) technology for gem diamond synthesis has made rapid progress in the last few years. It is now being used to produce many melee-size diamonds around 2-3 mm in diameter and large colorless single crystals, all with significantly improved quality and growth rate. One Russian company is reportedly growing multiple large, gem-quality colorless diamond crystals in a single run (U.F.S. D’Haenens-Johansson et al., “Large colorless HPHT-grown synthetic gem diamonds from New Diamond Technology,” Fall 2015 G&G, pp. 260-279). Here we report on large diamond crystals manufactured using a similar technology by Jinan Zhongwu New Materials Co. Ltd in Shandong, China. We visited the Chinese factory in early March 2016 and obtained 50 crystals (figure 1). The crystals were examined using the instrumentation and techniques applied to all diamonds submitted to GIA for grading; all exhibited the typical characteristics of HPHT growth and were identified as synthetic. These were basically colorless, with only a few metallic inclusions observed. These crystals showed typical cuboctahedral morphology, with well-developed {100}, {110}, and {111} growth sectors and a weakly developed {113} sector. The crystals we obtained ranged from about 0.5 to 1.2 ct each. Absorption spectra in the infrared region showed they were type IIa diamond, but trace absorption from boron was detected (2800 cm-1). Detailed gemological and spectroscopic analyses are ongoing and will be reported separately. According to the manufacturer, large quantities of gem-quality colorless and blue diamonds are produced in this factory, in sizes up to 3.5 ct each. While the total production volume remains unclear, it is undoubtedly significant, and capacity is likely to expand in the near future. This strongly suggests that even more large HPHT synthetic diamonds will be introduced into the jewelry industry.
Abstract: This study gives an analysis of the effect of high temperature annealing on the infrared and photoluminescence (PL) features as well as the inclusions of two hydrogen-rich diamond plates from Zimbabwe that were cut from the same rough. The samples showed strong inclusion-related zoning known as hydrogen clouds which consist of micron-sized particles of as yet undetermined structure. This allowed hydrogen-rich and hydrogen-poor areas to be compared throughout the annealing study. The diamond plates were annealed to temperatures of 300oC, 600oC, 800oC, 1000oC, 1400oC, and 1700oC. The infrared and PL, and Raman maps were collected after every temperature step to study the effects of heat on the defects, and photomicrographs were collected to study the inclusions. Several photoluminescence features were seen to decrease in size including the 637 nm peak, which is the negatively charged nitrogen-vacancy center [NV-] and the 503.2 nm peak, known as the H3 and consists of two nitrogen atoms and vacancy in the neutral charge state and normally has a high thermal stability. The H2 defect at 986.2 nm, which is the negative form of the H3, was shown to increase after annealing. The hydrogen clouds underwent dramatic changes in apparent color and particle size, going from a light translucent gray appearance to an opaque black. The particle size grew from less than one micron to an average of fourteen microns, and the hexagonal outline of the particles became noticeable. Spatial raman spectroscopy was used to show that the color change and size change were due to graphitization of the included particles.
Journal of Physical Chemistry, 10.1002/ chemv.201600068
Technology
Rare earths
Abstract: Scientists in the U.S. have provided a new understanding of the structure and crystal properties of the main mineral source of rare earth metals, bastnäsites. They are fluoro-carbonate minerals which contain ytterbium, lanthanum, and cerium, among other elements. The researchers used powder X-ray diffraction (XRD) and density functional theory (DFT) to reveal details of the minerals' structure and interfacial energy. The work could help in the design of new reagents for selective binding to mineral interfaces and could improve the recovery of rare metals by froth flotation, which is the major stage of ore beneficiation. Increasing flotation concentrate grades makes the subsequent leaching and rare earth separations more efficient and economic. Rare earth elements are increasingly important in modern technology - for electronics, catalysis, possible future quantum devices, and especially for clean energy applications like wind and solar energy, energy-efficient lighting, and electric vehicles. For example, neodymium and praseodymium are used in strong permanent magnets, lanthanum and cerium are used in batteries, metal alloys, petroleum refining, and catalysis, and ytterbium is a common material in phosphors for displays and in high-tech ceramics. These elements, which are defined as the fifteen lanthanides, as well as scandium and yttrium, are commonly found in the same ores. Despite what their name suggests, they are not actually rare, but they are difficult and costly to refine. As such, it is crucial that scientists and technologists optimize ore beneficiation to provide an enriched feedstock for the subsequent efficient extraction of these elements from the mined mineral ores in which they are found.
Abstract: Gem diamonds are highly valued for their color, or the absence of it. However, the myriad of colors and patterns that are revealed when a diamond is exposed to ultraviolet light are often more impressive than the stones themselves. High energy (i.e., ultra-shortwave <230 nm) UV light from the DiamondView instrument excites fluorescence from natural and synthetic diamonds that not only provides a tremendous amount of information about defect incorporation during growth, but also stunningly artistic designs. Fluorescence patterns reveal details about the original morphology of a diamond even after all of the natural surfaces are removed. In addition, concentrations of luminescent centers along structurally controlled planes in a natural diamond lattice provide information about the original distribution of impurities and other defects and the thermal and deformational history of diamonds as they spend millions (or billions) of years in the Earth’s mantle and then are rapidly erupted in a kimberlite magma. Likewise, the distribution of nitrogen, boron, and nickel-related luminescence in synthetic diamonds give clues to the temperature, pressure, and catalytic conditions under which they were grown in a laboratory. Evaluation of the fluorescence patterns from diamonds helps the scientist better understand the incorporation and migration of atomic level defects in the diamond structure while allowing the artist to appreciate some of the most unusual and amazing patterns that nature produces.
Abstract: There is a rising number of near-colorless synthetics diamonds detected in the market, which create concerns for the trade. The recent advent of near-colorless melee size synthetic diamonds has raised the question of how to test large numbers of small stones. Many have turned to specialized sorting machines, which are expensive and difficult to evaluate. The problem arises only within near-colorless type IIa diamond gems. This type is commonly identified by infrared spectroscopy, which is man- or instrument-intensive. For the jeweler-gemologist, this can be identified by UV transparency, which isolates type IIa and also the even rarer type IaB from other types. Then amongst type IIas, one has to determine which are synthetic. One of the most effective sorting methods is anomalous double refringence (ADR) observing between crossed polarizers in a high-index immersion liquid. However, this method finds its limit with very small diameter stones, as then the optical pathlength is so small that no birefringence is perceived. Another approach is luminescence, based on observation of the whole stone; typically synthetics luminesce stronger in shortwave than longwave ultraviolet: this is effective to pinpoint HPHT-grown colorless and yellows, but useless for generally inert CVD-grown ones. Then the observation of luminescence zoning is usually conclusive. It necessitates expensive specialized instruments and also, a good knowledge of the very varied forms of natural diamond growth to avoid mistaking a natural for a synthetic. Finally, the last resort is luminescence spectroscopy. this typically involves laser excitation with several lasers, at low temperature. Further, this implies a very thorough knowledge of natural and synthetic diamond emissions, which limits this approach to a small number of laboratories. In practice, for a small number of stones, the definitive interpretation of spectra may remain a matter of discussion. Thus, the separation of natural from synthetic diamond mélé may appear very difficult. Yet, there are a limited number of simple devices which can help the jeweler-gemologist, even more the diamond professional. The last resort appears to be luminescence spectroscopy, but it is expensive and a great deal of interpretation is required. Automated instruments offer only limited help.
Abstract: This article reviews the development of mineralogy as a science by focusing largely on the common silicate garnets of general formula {X3}[Y2](Si3)O12. It tells of important discoveries, analyses, and proposals by various scientists relating to crystallography, crystal structures, isomorphism, and solid solution starting in Europe in the late 1700s. The critical recognition of the importance of ionic size of atoms in determining crystal-chemical properties and solid-solution behavior is emphasized. The two garnet species “pyralspite” and “(u)grandite,” which were considered to represent two independent solid-solution series, were introduced by N.H. Winchell and A.N. Winchell (1927) in their well-known book Elements of Optical Mineralogy. Critical comments on the assumptions behind the classification scheme have been pointed out for at least 50 yr, but it remains in use. There is more, though, behind this garnet classification scheme than just simple terminology. There are a long series of scientific discoveries and advances that are largely forgotten by the broader mineralogical community. They begin, here, with the work of the “father of crystallography,” René-Just Haüy, concerning the microscopic nature of crystals around 1780 and include later discoveries and proposals by Mitscherlich, Beudant, Wollaston, and Kopp relating to isomorphism and solid-solution behavior all before 1850. A second key era started with the discovery of X-ray diffraction in 1912 that allowed the atomic structures of crystals and, furthermore, atomic and ion radii to be determined. In terms of isomorphism and solid solution, the proposals and studies of Vegard, Zambonini, Wherry, A.N. Winchell, and the “father of crystal chemistry” Goldschmidt are briefly discussed. The recognition of the sizes of atoms and ions, along with an understanding of chemical bonding behavior in crystals, was critical in the establishment of what can be termed “modern mineralogy,” a quantitative science as it is largely understood today that emerged by the mid-1930s. The silicate garnet system pyrope-almandine-spessartine-grossular-andradite-uvarovite shows extensive homovalent substitutional solid solution over two structural sites and complete compositional variation between “pyralspite species” and “ugrandite species” has been documented. Thus, the prerequisites behind the terms “pyralspite” and “(u)grandite,” as originally formulated and often accepted even today, are incorrect and use of this classification is not recommended. Diffraction determinations of the volumes of garnet end-members and volumes of mixing of garnet solid solutions give physical insight into solid-solution behavior. Today, investigations of local structural and crystal-chemical properties, together with determinations of lattice strain and thermodynamic mixing properties, of silicate solid solutions are leading to an ever more quantitative understanding of mineral behavior from the microscopic to macroscopic level.
Abstract: Establishing the history of HP and UHP metamorphic rocks is important for quantifying Earth dynamics. The history of these rocks defines, among other things, paleo-subduction rates, P-T paths, and the kinematics of continent-continent collision. Although the appearance of certain minerals, such as coesite, stishovite, or diamond, provides unequivocal evidence of an HP or UHP component to the history of a rock, they cannot provide details of the P-T-t path a rock has experienced. However, complex solid solutions can. This reflects the fact that solid solutions have the potential to provide a continuous thermodynamically controlled response to evolving P-T conditions. To the extent that such solid-solution characteristics are preserved unmodified in a mineral throughout its history, a detailed description of the trajectory of the rock during burial …
Abstract: Black diamonds with poor transparency due to an intensity of mineral inclusions and fractures are routinely traded in the gem market today. Although the inclusions and fractures are of natural origin this type of diamond is often heated to create a more uniform black color by further graphitizing these inclusions and fractures. Graphitization is often prominent at these fractures resulting in poor quality heavily fractured material. After nitrogen hydrogen is the most common impurity in natural diamond and is often responsible for a gem quality diamonds color. Color in diamond related or attributed to the hydrogen impurity can range from brown to green and gray. These colors are often undesirable to the gem trade and consumers. Recently GIA laboratories have seen a lot of faceted “Black” diamonds (graded as Fancy Black on GIA’s color scale) for identification. These diamonds are hydrogen rich and it is suspected that this material is treated (heated). Probably unattractive grayish green brown material that is virtually worthless in the gem trade before treatment. With such large quantities of this treated material available a serious threat and identification problem is posed to the Gem Diamond industry. Three faceted round cut hydrogen rich diamonds (0.30, 0.52 and 0.58 carats) colored by dense hydrogen clouds giving them a murky grayish appearance have been documented and systematically heated. A black color identical to that of the suspected treated black diamonds has been achieved, thus confirming this coloration treatment and new identification techniques to detect it. These treated black diamonds have a uniform color and lack the heavy fracturing and surface graphitization of typical treated black diamonds. Heating conditions and techniques will be discussed and we report on this new type of material and gem stone treatment.
Physics and Chemistry of Minerals, in press available 10p.
Technology
Impact diamond
Abstract: High-resolution transmission electron microscopy was applied for the detailed nanostructural investigation of Popigai impact diamonds with the aim of revealing the nature of the amorphous carbon of the matrix. The successful application of two complementary specimen preparation methods, focused ion beam (FIB) milling and mechanical cleavage, allowed direct imaging of nanotwinned nanodiamond crystals embedded in a native amorphous carbon matrix for the first time. Based on its stability under the electron beam, native amorphous carbon can be easily distinguished from the amorphous carbon layer produced by FIB milling during specimen preparation. Electron energy loss spectroscopy of the native amorphous carbon revealed the dominance of sp2-bonded carbon and the presence of a small amount of oxygen. The heterogeneous size distribution and twin density of the nanodiamond crystals and the structural properties of the native amorphous carbon are presumably related to non-graphitic (organic) carbon precursor material.
Abstract: An experimental study on diamond crystallization in CO2-rich sodium-carbonate melts has been undertaken at a pressure of 6.3 GPa in the temperature range of 1250-1570 °C and at 7.5 GPa in the temperature range of 1300-1700 °C. Sodium oxalate (Na2C2O4) was used as the starting material, which over the course of the experiment decomposed to form sodium carbonate, carbon dioxide and elemental carbon. The effects of pressure, temperature and dissolved CO2 in the ultra-alkaline carbonate melt on diamond crystallization, morphology, internal structure and defect-and-impurity content of diamond crystals are established. Diamond growth is found to proceed with formation of vicinal structures on the {100} and {111} faces, resulting eventually in the formation of rounded polyhedrons, whose shape is determined by the combination tetragon-trioctahedron, trigon-trioctahedron and cube faces. Spectroscopic studies reveal that the crystallized diamonds are characterized by specific infrared absorption and photoluminescence spectra. The defects responsible for the 1065 cm? 1 band dominating in the IR spectra and the 566 nm optical system dominating in the PL spectra are tentatively assigned to oxygen impurities in diamond.
Abstract: The Smithsonian’s National Gem Collection includes the Hope Diamond and an assortment of other significant fancy-colored diamonds, providing a unique opportunity to conduct detailed and sustained studies on an unprecedented selection of these rare and valuable stones. We present an overview and recent results from our work on pink, blue and chameleon diamonds. Boron causes the blue color of the Hope Diamond and other type IIb diamonds, but scarcity, high value, and the low concentration of B has inhibited B analyses of natural IIb diamonds. We used FTIR and ToF-SIMS to measure concentrations and distributions of B in the Hope and other blue diamonds. ToF-SIMS analyses gave spot B concentrations as high as 8.4 ± 1.1 ppm for the Hope Diamond to less than 0.08 ppm in other blue diamonds and revealed strong zoning of B in some diamonds, which was confirmed by mapping using synchrotron FTIR. Boron is also responsible for the phosphorescence emissions of IIb diamonds, at 660 nm and 500 nm; the emissions are likely caused by donor-acceptor pair recombination processes involving B and other defects. Approximately 50 type I natural pink diamonds were compared using UV-Vis, FTIR, and CL spectroscopies. All stones exhibit pink color zoning, ~1µm thick [111] lamellae, in otherwise colorless diamond. The pink diamonds fall into two groups: 1) those from Argyle in Australia and Santa Elena in Venezuela, and 2) those from other localities. TEM imaging from FIB sections revealed that twinning is the likely mechanism by which plastic deformation is accommodated for the pink diamonds. The deformation creates new centers, including the one responsible for the pink color, which remains unidentified. The differences in the plastic deformation features for the two groups might correlate to the particular geologic conditions under which the diamonds formed. Fluorescence and thermoluminescence experiments on natural chameleon diamonds reveal that an emission band, peaking near 556nm, may be stimulated via a number of different mechanisms. We discuss the implications of our observations for the electronic structure of the 556nm-fluorescing defect center, and the connections to the unidentified color center responsible for chameleon color changes.
Abstract: Type Ib diamonds contain abundant isolated nitrogen and account for less than 0.1% of natural diamonds. This rarity is because over geological time and at temperatures typical of the cratonic lithosphere, isolated nitrogen aggregates to A centres (N pairs) and B centres (4N around a vacancy). Preservation of isolated nitrogen in natural diamonds requires either short mantle residency times or storage at temperatures <700 °C, whereas most cratonic diamonds are billions of years old and resided >1000 °C. Eclogitic sulphides in Zimmi Ib diamonds (Sierra Leone) have 650 Ma Re-Os ages, whose origin is best explained by rapid tectonic exhumation after continental collision to shallower depths in the keel prior to kimberlite eruption (Smit et al., 2016). Here we present SIMS and spectroscopic data for a new suite of Zimmi sulphide-bearing diamonds. These new data allow us to evaluate the speciation of diamond source fluids, and the defects in these diamonds that are responsible for their distinctive canary yellow colours. The combined dataset establishes the link between the spectroscopic features in Zimmi Ib diamonds and their unusual history. Low ?13C values below -15 ‰ in 3 diamonds result from source fluids that originated as organic carbon in the oceanic crust, and were recycled into the lithosphere during subduction. In particular, a trend of decreasing ?13C and N content from core to rim in a single diamond indicates closed-system growth from CH4-rich subducted fluids. Recycled origins for organic carbon supports the temporal link of Zimmi diamond formation with deep underthrusting during Neoproterozoic continental assembly, recorded in the Rokelide orogen. CL imaging of Zimmi diamonds reveals irregular growth patterns with abundant deformation lines, associated with tectonic exhumation of the diamonds. Vacancies formed by deformation were subsequently annealed to form NV centres, where the negative charge state (637 nm) is more abundant due to isolated nitrogen donating an electron. Fancy brownish-yellow to greenish-yellow colours observed in Zimmi Ib diamonds result from a combination of isolated nitrogen, deformation-related amber centres and NV centres. These colour-forming defects can all be attributed to the unique geological history of Zimmi Ib diamonds and their rapid exhumation after formation.
A sublithospheric mantle, metallic liquid origin for the world's largest gem-quality diamonds.
GSA Annual Meeting, Abstract, 1p.
Technology
Type II diamonds
Abstract: Many of the world’s largest and most valuable diamonds (e.g. Cullinan, Lesedi La Rona, Star of Sierra Leone, Lesotho Promise, Koh-i-Noor) have an unusual set of physical characteristics, suggesting they may form by a unique and common mechanism. The most often noted characteristic is their nitrogen-deficient character, classifying them as Type II. In addition, these large diamonds are generally inclusion poor, irregularly shaped, and highly resorbed. The famous 3106 carat Cullinan diamond, discovered in 1905, is a prime example. These Cullinan-like Type II diamonds are especially valuable as gemstones and difficult to access for research. Furthermore, they very rarely contain any inclusions that might shed light on their geological origin. For these reasons the paragenesis of such diamonds has long remained so enigmatic that they have not been connected to the processes that form more common Type I diamonds or even any other Type II diamonds. Here we report the findings of a systematic search for inclusions among thousands of high-quality Type II diamonds, both polished gemstones and offcuts. Not only was the search successful in finding inclusions in 70 diamonds, it also revealed a recurring set of inclusions that are distinct from those of more familiar lithospheric/sublithospheric diamonds. The most abundant inclusion encountered was a metallic, Fe-Ni-C-S multi-phase assemblage, which was observed in 35 diamonds. The second most abundant inclusion type is former CaSiO3 perovskite, now retrogressed to lower-pressure minerals. The CaSiO3 phases constrain the depth of formation to deeper than 300 km. Two additional Cullinan-like Type IIa diamonds were found to have inclusions of low-Cr majoritic garnet, also indicative of a sublithospheric origin. Overall, the inclusions suggest that Cullinan-like, large, high-quality diamonds belong to a unique paragenesis with an intimate link to Fe-Ni metal in the deep mantle.
Contributions to Mineralogy and Petrology, in press available 9p.
Technology
Petrology
Abstract: Kimberlites are rare diamond-bearing volcanic rocks that originate as melts in the Earth’s mantle. The original composition of kimberlitic melt is poorly constrained because of mantle and crustal contamination, exsolution of volatiles during ascent, and pervasive alteration during and after emplacement. One recent model (Russell et al. in Nature 481(7381):352-356, 2012. doi:10.1038/nature10740) proposes that kimberlite melts are initially carbonatitic and evolve to kimberlite during ascent through continuous assimilation of orthopyroxene and exsolution of CO2. In high-temperature, high-pressure experiments designed to test this model, assimilation of orthopyroxene commences between 2.5 and 3.5 GPa by a reaction in which orthopyroxene reacts with the melt to form olivine, clinopyroxene, and CO2. No assimilation occurs at 3.5 GPa and above. We propose that the clinopyroxene produced in this reaction can react with the melt at lower pressure in a second reaction that produces olivine, calcite, and CO2, which would explain the absence of clinopyroxene phenocrysts in kimberlites. These experiments do not confirm that assimilation of orthopyroxene for the entirety of kimberlite ascent takes place, but rather two reactions at lower pressures (<3.5 GPa) cause assimilation of orthopyroxene and then clinopyroxene, evolving carbonatitic melts to kimberlite and causing CO2 exsolution that drives rapid ascent.
The 4th Colloquium on Diamonds - source to use held Gabarone March 1-3, 2010, 14p.
Technology
Crushing
Abstract: The diamond industry is no newcomer to High Pressure Grinding Rolls (HPGR) as it has used the technology for more than 20 years, predominantly in secondary crushing and recrushing roles. In fact it could be argued that the diamond industry has led the way for the wider minerals industry to consider its application. In existing conventional secondary cone crushing applications, large valuable diamonds are "won" through meticulously managing the recovery process within defined particle size ranges. COllventional crushers operate with relatively large closed side sehings, hut have the potential to damage diamonds by making direct contact with the sides of the crusher. Cone crushers also result in steep product size distributions that run a high risk of losing many of the smaller, un-liberated but more abundant diamonds from the rock. This current comminution paradigm of particle size reduction management results in recrushing processing applications or plants where HPGRs are often used. HPGRs operate under the seemingly odd condition where the gap between the rolls is largely a function of the roll diameter irrespective of the feed size. This otTern an opportun'ity for the diamond industry to consider using multiple HPGRs or units with high circulating loads to effectively generate a product with a very high proportion of fine material that can be rejected ahead of the beneficiation step. This in effect results in a new paradigm, a single comminution step, where all diamonds of all sizes are liberated and preserved. The circuit product size distribution will consist mainly of barren kimberlitic fines along with some grits, pebbJes, indicator minerals, as well as the prized lUldamaged diamonds. The HPGR product stream needs to be scrubbed, slurried and screened at t mm resulting in a greatly reduced volume of -diamond-rich particles that progress to the dense medium concentration and/or direct x-ray separation steps_ In this application, the HPGR is viewed "outside the box", but within the context of diamond winning processes. Examples of how "HPGR can go all the way" are presented in the paper. Page
The 4th Colloquium on Diamonds - source to use held Gabarone March 1-3, 2010, 8p.
Technology
Sorting - X-ray DE-XRT
Abstract: In May 2009 a test work programme was carried out at the sorting laboratory of CommodasUltrasort in Germany which was aimed at establishing the efficiency of Xray transmission sorting for the recovery of unliberated diamonds in a size range of +8mm. A PRO Tertiary XRT belt sorter with a working width of 600mm and a belt speed of - 3mJs was used for the test work. Dual energy X-ray transmission sorting is a type of sensor-based sorting which uses an X-ray scanning system, The attenuation of the transmitting X-rays is measured at two different energy levels, Thereby it is possible to eliminate the effect of the particle thickness on the measurement result. The effective measurement results in a classification by elemental order based on the periodic table. Diamonds are mostly composed of Carbon, which has an atomic number of 6. Compared to Silicon with an atomic number of 14, Diamonds show up much lighter on an XRT image than Silica-based gravels (typical DMS sinks material usually has more dense minerals such as Fe, and Mn which shows an even, darker X-ray image than Si). Tests were run with ele.ven Boarl Diamonds in a size range of -15+8mm mixed into 13kg alluvial DMS sinks gravel in a size range of -25+8mm. All liberated Boart Diamonds were recovered at feed rates of 15t/h at average yields of 7.6g per ejected Diamond. In a second test series the Boarl Diamonds were covered in 20% Gypsum by weight and run again at 15t/h. All unliberated Diamonds were recovered at an average yield of 12.2g per ejected Diamond. The paper outlines the test work results in detail.
The 4th Colloquium on Diamonds - source to use held Gabarone March 1-3, 2010, 10p.
Technology
Sorting
Abstract: The introduction of new diamond sorting technologies as well as additional manufacturers I vendors, has increased the equipment selection and combinations available for recovery flowsheet design. This paper describes the methodology used and the benefits realized in the design of recovery plants by ensuring a fundamental understanding of the advantages and limitations of the technology embodied in the equipment, a comprehensive knowledge of the ore body characteristics, and the effective matching of this information in combination with operational commercial requirements.
Aravanis, T., Chen, J., Fuechsle, M., Grujic, M., Johnston, P., Kok, Y., Magaraggia, R., Mann, A., Mann, L., McIntoshm S., Rheinberger, G., Saxey, D., Smalley, M., van Kann, F., Walker, G., Winterflood, J.
Abstract: The minerals exploration industry’s demand for a highly precise airborne gravity gradiometer has driven development of the VK1TM Airborne Gravity Gradiometer, a collaborative effort by Rio Tinto and the University of Western Australia. VK1TM aims to provide gravity gradient data with lower uncertainty and higher spatial resolution than current commercial systems. In the recent years of VK1TM development, there have been significant improvements in hardware, signal processing and data processing which have combined to result in a complete AGG system that is approaching competitive survey-ready status. This paper focuses on recent improvements. Milestone-achieving data from recent lab-based and moving-platform trials will be presented and discussed, along with details of some advanced data processing techniques that are required to make the most use of the data.
Abstract: Experiments on the synthesis of inclusions-bearing diamond were performed in the SiO2-((Mg,Ca)CO3-(Fe,Ni)S system at 6.3 GPa and 1650-1750 °C, using a multi-anvil high pressure apparatus of the "split-sphere" type. Diamond synthesis was realized in the "sandwich-type" experiments, where the carbonate-oxide mixture acted as a source of both CO2-dominated fluid and carbonate-silicate melt, and Fe,Ni-sulfide played a role of reducing agent. As a result of redox reactions in the carbonate-oxide-sulfide system, diamond was formed in association with graphite and Mg,Fe-silicates, coexisting with CO2-rich fluid, carbonate-silicate and sulfide melts. The synthesized diamonds are predominantly colorless or light-yellow monocrystals with octahedral habit (20-200 ?m), and polycrystalline aggregates (300-400 ?m). Photoluminescence spectroscopy revealed defects related to nickel impurity (S3 optical centers), which are characteristic of many diamonds in nature. The density of diamond crystallization centers over the entire reaction volume was ~3 × 102-103 cm? 3. The overwhelming majority of diamonds synthesized were inclusions-bearing. According to Raman spectroscopy data, diamond trapped a wide variety of inclusions (both mono- and polyphase), including orthopyroxene, olivine, carbonate-silicate melt, sulfide melt, CO2-fluid, graphite, and diamond. The Raman spectral pattern of carbonate-silicate melt inclusions have bands characteristic of magnesite and orthopyroxene (± SiO2). The spectra of sulfide melt displayed marcasite and pyrrhotite peaks. We found that compositions of sulfide, silicate and carbonate phases are in good agreement not only with diamond crystallization media in experiments, but with data on natural diamond inclusions of peridotitic and eclogitic parageneses. The proposed methodological approach of diamond synthesis can be used for experimental simulation of the formation of several types of mineral, fluid and melt inclusions, observed in natural diamonds.
Abstract: There is a rising number of near-colorless synthetics diamonds detected in the market, which create concerns for the trade. The recent advent of near-colorless melee size synthetic diamonds has raised the question of how to test large numbers of small stones. Many have turned to specialized sorting machines, which are expensive and difficult to evaluate. The problem arises only within near-colorless type IIa diamond gems. This type is commonly identified by infrared spectroscopy, which is man- or instrument-intensive. For the jeweler-gemologist, this can be identified by UV transparency, which isolates type IIa and also the even rarer type IaB from other types. Then amongst type IIas, one has to determine which are synthetic. One of the most effective sorting methods is anomalous double refringence (ADR) observing between crossed polarizers in a high-index immersion liquid. However, this method finds its limit with very small diameter stones, as then the optical pathlength is so small that no birefringence is perceived. Another approach is luminescence, based on observation of the whole stone; typically synthetics luminesce stronger in shortwave than longwave ultraviolet: this is effective to pinpoint HPHT-grown colorless and yellows, but useless for generally inert CVD-grown ones. Then the observation of luminescence zoning is usually conclusive. It necessitates expensive specialized instruments and also, a good knowledge of the very varied forms of natural diamond growth to avoid mistaking a natural for a synthetic. Finally, the last resort is luminescence spectroscopy. this typically involves laser excitation with several lasers, at low temperature. Further, this implies a very thorough knowledge of natural and synthetic diamond emissions, which limits this approach to a small number of laboratories. In practice, for a small number of stones, the definitive interpretation of spectra may remain a matter of discussion. Thus, the separation of natural from synthetic diamond mélé may appear very difficult. Yet, there are a limited number of simple devices which can help the jeweler-gemologist, even more the diamond professional. The last resort appears to be luminescence spectroscopy, but it is expensive and a great deal of interpretation is required. Automated instruments offer only limited help.
Abstract: Trapped-charge dating methods including luminescence and electron spin resonance dating have high potential as low temperature (< 100 °C) thermochronometers. Despite an early proof of concept almost 60 years ago, it is only in the past two decades that thermoluminescence (TL), electron-spin-resonance (ESR), and optically stimulated luminescence (OSL), have begun to gain momentum in geological thermochronometry and thermometry applications. Here we review the physics of trapped-charge dating, the studies that led to its development and its first applications for deriving palaeo-temperatures and/or continuous cooling histories. Analytical protocols, which enable the derivation of sample specific kinetic parameters over laboratory timescales, are also described. The key limitation of trapped-charge thermochronometry is signal saturation, which sets an upper limit of its application to < 1 Ma, thus restricting it to rapidly exhuming terrains (> 200 °C Ma? 1), or elevated-temperature underground settings (> 30 °C). Despite this limitation, trapped-charge thermochronometry comprises a diverse suite of versatile methods, and we explore potential future applications and research directions.
Abstract: The aim of this paper is to add confidence to existing methods using decay shape analysis to detect superparamagnetic responses in airborne electromagnetic data. While expensive to acquire, vertical spatial gradient measurements of the electromagnetic signals can discriminate near-surface superparamagnetic sources. This research investigated the use of horizontal spatial gradients and amplitude information as further indicators of superparamagnetic. High horizontal gradients were shown both theoretically and in field data to help discriminate superparamagnetic from deep mineral targets. Further, superparamagnetic responses have characteristically small amplitudes inconsistent with realistic mineral exploration targets at shallow depths.
Abstract: To study the kinetics of the spinel-to-garnet transformation in peridotite, we conducted reaction experiments in the garnet peridotite stability field (3.2 GPa, 1020-1220 °C, for 0.6-30 h) using a single spinel crystal embedded in monomineralic orthopyroxene powder or in a mixture of powdered orthopyroxene and clinopyroxene. The growth textures observed in the reaction rim between the spinel crystal and the polycrystalline pyroxenes show that the reaction rim grew in both the spinel and pyroxenes directions, suggesting mobility of both SiO2 and R2O3 components (where R is a trivalent cation). Olivine grains formed only in the presence of monomineralic orthopyroxene and were present in some domains without forming reaction rims. Based on a diffusion-controlled growth model, the growth kinetics of the garnet reaction rim can be described by [x(t)]2 = k0 exp(?H*/RT)t, where x(t) is the rim width at time t, R is the gas constant, T is the absolute temperature, and H* is the activation enthalpy of reaction; k0 and H* are, respectively, k0 = 10?19.8 ± 4.9 m2/s and H* = 171 ± 58 kJ/mol. The development of a garnet reaction rim around a spinel core has been observed in alpine-type peridotitic rocks and mantle xenoliths. The reaction rims experimentally produced in this study are characteristic of corona textures observed in natural rocks, and the experimentally measured growth rate of the rims places important constraints on dynamic transformation processes involving spinel and garnet in peridotite. However, to reconstruct the P-T-t history of the corona texture based on these elementary processes, additional detailed studies on the textural evolution and quantitative kinetics of the garnet-rim growth stage are required.
Abstract: One of the most controversial diamond types is carbonado, as its origin and geological history are still under debate. Here, we investigate selected carbonado samples using neutron diffraction and high resolution orientation mapping in combination with numerical simulations. Neutron diffraction analyses show that fine grained carbonado samples exhibit a distinct lack of crystallographic preferred orientation. Quantitative crystallographic orientation analyses performed on transmission electron microscope (TEM) sections reveal that the 2-10 ?m grains exhibit locally significant internal deformation. Such features are consistent with crystal plastic deformation of a grain aggregate that initially formed by rapid nucleation, characterized by a high number of nucleation sites and no crystallographic preferred orientation. Crystal plastic deformation resulted in high stress heterogeneities close to grain boundaries, even at low bulk strains, inducing a high degree of lattice distortion without significant grain size reduction and the development of a crystallographic preferred orientation. Observed differences in the character of the grain boundary network and internal deformation structures can be explained by significant post-deformation annealing occurring to variable degrees in the carbonado samples. Differences in intensity of crystal bending and subgrain boundary sharpness can be explained by dislocation annihilation and rearrangement, respectively. During annealing grain energy is reduced resulting in distinct changes to the grain boundary geometry. Grain scale numerical modelling shows that anisotropic grain growth, where grain boundary energy is determined by the orientation of a boundary segment relative to the crystallographic orientation of adjacent grains results in straight boundary segments with abrupt changes in orientation even if the boundary is occurring between two triple junctions forming a "zigzag" pattern. In addition, in diamond anisotropic grain growth results in triple junctions that rarely show 120° angles. Our results support the interpretation that carbonados may have undergone at least 2 or 3 stages of development with rapid nucleation, crystal plastic deformation to low strains and variable degrees of post-deformation annealing. Such a history is commonly observed in Earth's crustal or mantle rocks. Hence, for carbonados it is not necessary to invoke an extraordinary and/or extraterrestrial origin and history. The combination of methods utilized here, promises to help advance our understanding of diamond and diamond aggregates in the future.
Abstract: The Smithsonian’s National Gem Collection includes the Hope Diamond and an assortment of other significant fancy-colored diamonds, providing a unique opportunity to conduct detailed and sustained studies on an unprecedented selection of these rare and valuable stones. We present an overview and recent results from our work on pink, blue and chameleon diamonds. Boron causes the blue color of the Hope Diamond and other type IIb diamonds, but scarcity, high value, and the low concentration of B has inhibited B analyses of natural IIb diamonds. We used FTIR and ToF-SIMS to measure concentrations and distributions of B in the Hope and other blue diamonds. ToF-SIMS analyses gave spot B concentrations as high as 8.4 ± 1.1 ppm for the Hope Diamond to less than 0.08 ppm in other blue diamonds and revealed strong zoning of B in some diamonds, which was confirmed by mapping using synchrotron FTIR. Boron is also responsible for the phosphorescence emissions of IIb diamonds, at 660 nm and 500 nm; the emissions are likely caused by donor-acceptor pair recombination processes involving B and other defects. Approximately 50 type I natural pink diamonds were compared using UV-Vis, FTIR, and CL spectroscopies. All stones exhibit pink color zoning, ~1µm thick [111] lamellae, in otherwise colorless diamond. The pink diamonds fall into two groups: 1) those from Argyle in Australia and Santa Elena in Venezuela, and 2) those from other localities. TEM imaging from FIB sections revealed that twinning is the likely mechanism by which plastic deformation is accommodated for the pink diamonds. The deformation creates new centers, including the one responsible for the pink color, which remains unidentified. The differences in the plastic deformation features for the two groups might correlate to the particular geologic conditions under which the diamonds formed. Fluorescence and thermoluminescence experiments on natural chameleon diamonds reveal that an emission band, peaking near 556nm, may be stimulated via a number of different mechanisms. We discuss the implications of our observations for the electronic structure of the 556nm-fluorescing defect center, and the connections to the unidentified color center responsible for chameleon color changes.
Abstract: Many of the world’s largest and most valuable diamonds (e.g. Cullinan, Lesedi La Rona, Star of Sierra Leone, Lesotho Promise, Koh-i-Noor) have an unusual set of physical characteristics, suggesting they may form by a unique and common mechanism. The most often noted characteristic is their nitrogen-deficient character, classifying them as Type II. In addition, these large diamonds are generally inclusion poor, irregularly shaped, and highly resorbed. The famous 3106 carat Cullinan diamond, discovered in 1905, is a prime example. These Cullinan-like Type II diamonds are especially valuable as gemstones and difficult to access for research. Furthermore, they very rarely contain any inclusions that might shed light on their geological origin. For these reasons the paragenesis of such diamonds has long remained so enigmatic that they have not been connected to the processes that form more common Type I diamonds or even any other Type II diamonds. Here we report the findings of a systematic search for inclusions among thousands of high-quality Type II diamonds, both polished gemstones and offcuts. Not only was the search successful in finding inclusions in 70 diamonds, it also revealed a recurring set of inclusions that are distinct from those of more familiar lithospheric/sublithospheric diamonds. The most abundant inclusion encountered was a metallic, Fe-Ni-C-S multi-phase assemblage, which was observed in 35 diamonds. The second most abundant inclusion type is former CaSiO3 perovskite, now retrogressed to lower-pressure minerals. The CaSiO3 phases constrain the depth of formation to deeper than 300 km. Two additional Cullinan-like Type IIa diamonds were found to have inclusions of low-Cr majoritic garnet, also indicative of a sublithospheric origin. Overall, the inclusions suggest that Cullinan-like, large, high-quality diamonds belong to a unique paragenesis with an intimate link to Fe-Ni metal in the deep mantle.
Mathematical Geosciences, Vol. 48, 7, pp. 767-789.
Technology
Trend modelling - not specific to diamonds
Abstract: Characterization of spatial variability in earth science commonly requires random fields which are stationary within delineated domains. This contribution presents an alternative approach for simulating attributes in combination with a non-stationary first-order moment. A new procedure is presented to unambiguously decompose the observed behaviour into a deterministic trend and a stochastic residual, while explicitly controlling the modelled uncertainty. The practicality of the approach resides in a straightforward and objective inference of the variogram model and neighborhood parameters. This method does not require a prior removal of the trend. The inference principle is based on minimizing the deviation between empirical and theoretical errors calculated for increasingly distant neighborhood shells. Further, the inference is integrated into a systematic simulation framework and accompanying validation guidelines are formulated. The effort results in a characterization of the resource uncertainty of an existing heavy mineral sand deposit.
Abstract: [Si-V]- is a well-known defect in diamond. It has a great potential in electronics application and also is a very important feature for gem diamond identification in separating natural from synthetic. It is common in CVD diamonds (Martineau et al., 2004), can be doped into HPHT synthetic diamonds (Sittas, et al., 1996), and also occurs in natural type IIa diamonds (Breeding and Wang, 2008). Recent study of [Si-V]- distribution (emissions at 736.6 and 736.9 nm) in HPHT synthetic diamonds confirmed that it was concentrated in the {111} growth sectors. Identical distribution pattern of Nii+, which has doublet emissions at 882.1 and 883.7 nm, was observed (Johnson et al., 2015), strongly indicating that [Si-V]- and Nii+ have the same behavior during HPHT diamond growth. However, little is known how [Si-V]- is incorporated in natural diamond lattice. In this report, we studied the distribution of [Si-V]- defect in natural diamonds and its correlation with other emissions (defects). Seven natural type IIa gem diamonds were analyzed in this study. A common feature of this group of diamonds is occurrence of euhedral olivine inclusions, which is very rare among natural type IIa diamonds and good evidence that these IIa diamonds were formed in the lithospheric mantle. Occurrence of [Si-V]- in these stones were detected among enormous natural type IIa diamonds routinely analyzed in GIA laboratories. Distribution of [Si-V]-, Nii+ and many other emissions were mapped over the table faces using various laser excitations at liquid nitrogen temperature. It was found that intensities of [Si-V]- emission varied significantly over a small area. The distribution patterns were irregular and changed from stone to stone. Distribution of Nii+ emissions showed irregular patterns, but entirely different from that of [Si-V]-. There is no correlation in spatial distribution of these two defects in natural type IIa diamonds, in drastic contract to that observed in HPHT synthetics. Possible causes of the contrast behaviors of [Si-V]- distributions in natural and HPHT synthetic diamonds, and their implications in diamond formation and gem diamond identification will be discussed.
Geochemistry International, Vol. 54, 10, pp. 992-927.
Technology
Synthetics
Abstract: The IR-peak 1450 cm-1 (H1a-center) associated with nitrogen interstitials have been studied in nitrogen-bearing diamonds synthesized at high P-T parameters in the Fe-Ni-C system. FTIR study shows that manifestation of this nitrogen form is restricted to the regions of active transformation of C-defects into A-defects, which confirms the connection of its formation with C => A aggregation process. An examination of the dependence of the 1450 cm-1 peak on the degree of nitrogen aggregation indicates that H1a-centers are not only formed during C/A aggregation but also disappear simultaneously with the end of C => A transformation. Established facts suggest direct involving of nitrogen as interstitials in the C => A aggregation and serve as strong experimental argument in support of the "interstitial" mechanism of nitrogen migration during aggregation in diamonds containing transition metals.
Abstract: The possible presence of the high-density carbon polymorph with hexagonal symmetry known as "lonsdaleite" provides an important marker for shock impact events. It is typically considered to form as a metastable phase produced from graphite or other carbonaceous precursors. However, its existence has recently been called into question. Here we collected high-resolution synchrotron X-ray diffraction data for laboratory-shocked and natural impact diamonds that both show evidence for deviations from cubic symmetry, that would be consistent with the appearance of hexagonal stacking sequences. These results show that hexagonality can be achieved by shocking diamond as well as from graphite precursors. The diffraction results are analyzed in terms of a general model that describes intermediate stacking sequences between pure diamond (fully cubic) and "lonsdaleite" (fully hexagonal) phases, with provision made for ordered vs disordered stacking arrangements. This approach provides a "hexagonality index" that can be used to characterize and distinguish among samples that have experienced different degrees of shock or static high pressure-high temperature treatments. We have also examined the relative energetics of diamond and "lonsdaleite" structures using density functional theoretical (DFT) methods. The results set limits on the conditions under which a transformation between diamond and "lonsdaleite" structures can be achieved. Calculated Raman spectra provide an indicator for the presence of extended hexagonal stacking sequences within natural and laboratory-prepared samples. Our results show that comparable crystallographic structures may be developed by impact-generated shockwaves starting from ambient conditions using either of the two different allotropes of carbon (diamond, graphite). This broadens the scope for its occurrence in terrestrial and planetary systems.
Abstract: Although kimberlite magma carries large amounts of mantle-derived xenocrysts and xenoliths (with sizes up to meters), this magma ascends from the Earth's mantle (> 150-250 km) to the surface in a matter of hours or days, which enables diamonds to survive. The recently proposed assimilation-fuelled buoyancy model for kimberlite magma ascent emphasizes the importance of fluid CO2 that is produced via the reactive dissolution of mantle-derived orthopyroxene xenocrysts into kimberlite melt, which initially has carbonatitic composition. Here, we use a series of high-pressure experiments to test this model by studying the interaction of orthopyroxene (Opx) with an alkali-dolomitic melt (simplified to 0.7Na2CO3 + 0.3K2CO3 + 2CaMg(CO3)2), which is close to the melt that is produced by the partial melting of a kimberlite source, at P = 3.1-6.5 GPa and T = 1200-1600 °C, i.e., up to pressures that correspond to depths (~ 200 km) from where the ascent of kimberlite magma would start. During the first set of experiments, we study the reaction between powdered Opx and model carbonate melt in a homogeneous mixture. During the second set of experiments, we investigate the mechanism and kinetics of the dissolution of Opx crystals in alkali-dolomitic melt. Depending on the P-T conditions, Opx dissolves in the alkali-dolomitic melt (CL) either congruently or incongruently via the following reactions: Mg2Si2O6 (Opx) + CaMg(CO3)2 (CL) = CaMgSi2O6 (clinopyroxene) + 2MgCO3 (CL) and Mg2Si2O6 (Opx) = Mg2SiO4 (olivine) + SiO2 (CL). The experiments confirm that the dissolution of Opx causes gradual SiO2 enrichment in the initial carbonate melt, as previously suggested. However, the assimilation of Opx by carbonate melt does not produce fluid CO2 in the experiments because the CO2 is totally dissolved in the evolved melt. Thus, our results clearly demonstrate the absence of exsolved CO2 fluid at 3.1-6.5 GPa in ascending kimberlite magma and disprove the assimilation-fuelled buoyancy model for kimberlite magma ascent in the lithospheric mantle. We alternatively suggest that the extreme buoyancy of kimberlite magma at depths of 100-250 km is an exclusive consequence of the unique physical properties (i.e., low density, ultra-low viscosity and, thus, high mobility) of the kimberlite melt, which are dictated by its carbonatitic composition.
Abstract: As the most abundant solid phase at depths of 410-525 km, wadsleyite constitutes a large geochemical reservoir in the Earth. To better understand the implications of minor element substitution and cation ordering in wadsleyite, we have synthesized wadsleyites coexisting with pyroxenes with 2-3 wt% of either TiO2, Cr2O3, V2O3, CoO, NiO, or ZnO under hydrous conditions in separate experiments at 1300 °C and 15 GPa. We have refined the crystal structures of these wadsleyites by single-crystal X-ray diffraction, analyzed the compositions by electron microprobe, and estimated M3 vacancy concentration from b/a cell-parameter ratios. According to the crystal structure refinements, Cr and V show strong preferences for M3 over M1 and M2 sites and significant substitution up to 2.9 at% at the tetrahedral site (T site). Ni, Co, and Zn show site preferences similar to those of Fe with M1? M3 > M2 > T. The avoidance of Ni, Co, and Fe for the M2 site in both wadsleyite and olivine appears to be partially controlled by crystal field stabilization energy (CFSE). The estimated CFSE values of Ni2+, Co2+, and Zn2+ at three distinct octahedral sites show a positive correlation with octahedral occupancy ratios [M2/(M1+M3)]. Ti substitutes primarily into the M3 octahedron, rather than M1, M2, or T sites. Ti, Cr, and V each have greater solubility in wadsleyite than in olivine. Therefore these transition metal cations may be enriched in a melt or an accessory phase if hydrous melting occurs on upward convection across the wadsleyite-olivine boundary and may be useful as indicators of high-pressure origin.
Geophysical Journal International, Vol. 205, 3, pp. 1874-1885.
Technology
Alteration
Abstract: The influx of groundwater into hot kimberlite deposits results in the reaction of water with olivine-rich rocks. The products of the reaction are serpentine and release of latent heat. The rise of temperature due to the heat release increases the rate of the reaction. Under certain conditions, this self-speeding up of the reaction can result in instabilities associated with a significantly higher final serpentinisation in slightly warmer regions of the kimberlite deposit. We conduct linear stability analysis of serpentinisation in an isolated volume of porous kimberlitic rocks saturated with water and an inert gas. There is a counteracting interplay between the heat release tending to destabilise the uniform distribution of parameters and the heat conduction tending to stabilise it by smoothing out temperature perturbations. We determine the critical spatial scale separating the parameters where one phenomenon dominates over another. The perturbations of longer-than-critical length grow, whereas the perturbations of shorter-than-critical length fade. The analytical results of the linear stability analysis are supported by direct numerical simulations using a full nonlinear model.
Abstract: New versions of the universal Jd-Di exchange clinopyroxene barometer for peridotites, pyroxenites and eclogites, and also garnet barometer for eclogites and peridotites were developed. They were checked using large experimental data sets for eclogitic (?530) and peridotitic systems (>650). The precision of the universal Cpx barometer for peridotites based on Jd-Di exchange is close to Cr-Tschermakite method produced by Nimis and Taylor (2000). Cpx barometer was transformed by the substitution of major multiplier for KD by the equations dependent from Al-Na-Fe. Obtained equation in combination with the thermometer of Nimis and Taylor (2000) allow to reconstruct position of the magma feeder systems of the alkali basaltic magma within the mantle diapirs in modern platforms like in Vitim plateau and other Southern Siberia localities and several localities worldwide showing good agreement of pressure ranges for black and green suites. These equations allow construct PTX diagrams for the kimberlite localities in Siberia and worldwide calculating simultaneously the PT parameters for different groups of mantle rocks. They give very good results for the concentrates from kimberlite lamproites and placers with mantle minerals. They are useful for PT estimates for diamond inclusions. The positions of eclogite groups in mantle sections are similar to those determined with new Gar-Cpx barometer produced by C. Beyer et al. (2015). The Fe rich eclogites commonly trace the boundary between the lower upper parts of subcontinental lithospheric mantle (SCLM) at 3-4 GPa marking pyroxenite eclogites layer. Ca-rich eclogites and especially grospydites in SCLM beneath Precambrian kimberlites occurs near pyroxenite layer but in younger mantle sections they became common in the lower parts. The diamondiferous Mg Cr-less group eclogites referring to the ancient island arc complexes are also common in the middle part of mantle sections and near 5-6 GPa. Commonly eclogites in lower apart of mantle sections are remelted and trace the high temperature convective branch. The Mg- and Fe-rich pyroxenites also show the extending in pressure trends which suggest the anatexic melting under the influence of volatiles or under the interaction with plums.
Contributions to Mineralogy and Petrology, Vol. 171, pp. 95-121.
Technology
Melting - peridotite
Abstract: Melting experiments have been performed at 3 GPa, between 1150 and 1450 °C, on a phlogopite-peridotite source in the garnet stability field. We succeeded to extract and determine the melt compositions of both phlogopite-bearing lherzolite and harzburgite from low to high degrees of melting (? = 0.008-0.256). Accounting for the presence of small amounts of F in the mantle, we determined that phlogopite coexists with melt >150 °C above the solidus position (1150-1200 °C). Fluorine content of phlogopite continuously increases during partial melting from 0.2 to 0.9 wt% between 1000 and 1150 °C and 0.5 to 0.6 wt% between 1150 and 1300 °C at 1 and 3 GPa, respectively. The phlogopite continuous breakdown in the lherzolite follows the reaction: 0.59 phlogopite + 0.52 clinopyroxene + 0.18 garnet = 0.06 olivine + 0.23 orthopyroxene + 1.00 melt. In the phlogopite-harzburgite, the reaction is: 0.93 phlogopite + 0.46 garnet = 0.25 olivine + 0.14 orthopyroxene + 1.00 melt. Melts from phlogopite-peridotite sources at 3 GPa are silica-undersaturated and are foiditic to trachybasaltic in composition from very low (0.8 wt%) to high (25.6 wt%) degrees of melting. As observed at 1 GPa, the potassium content of primary mantle melts is buffered by the presence of phlogopite, but the buffering values are higher, from 6.0 to 8.0 wt% depending on the source fertility. We finally show that phlogopite garnet-peridotite melts are very close to the composition of the most primitive post-collisional lavas described worldwide.
Abstract: This article presents statistical data and distinctive features from several hundred faceted CVD-grown synthetic diamonds examined by GIA researchers from 2003 through June 2016. This study, the first comprehensive summary published on such a large number of gem-quality CVD synthetics, describes the reliable means of identifying them, with a focus on material currently marketed for jewelry use. Most CVD synthetic diamonds analyzed by GIA have been in the near-colorless or pink color ranges, with clarity grades comparable to those of their natural counterparts. Faceted CVD samples are generally 2 ct or less, though the sizes are increasing. They can be identified by their distinctive fluorescence pattern using the DiamondView imaging instrument, and by the detection of the silicon-vacancy defect using photoluminescence (PL) spectroscopy. Some visual gemological characteristics provide indicators, but not definitive proof, of CVD origin.
Abstract: Raman spectral characteristics of a range of diamond-based abrasives (powders and sprays) and drilling and cutting tools, originating from preparation laboratories worldwide, are presented. Some abrasives show strong broadening of the main diamond band [FWHM (full width at half band-maximum) > 5 cm? 1] accompanied by strong band-downshift (View the MathML source?˜ = 1316-1330 cm? 1). Others are characterised by moderate band broadening (FWHM = 1.8-5 cm? 1) at rather regular band position (View the MathML source?˜ = 1331-1333 cm? 1). In addition we found that a "fresh" abrasive and its used analogue may in some cases show vast differences in their Raman spectra. The Raman parameters of diamond-based abrasives overlap widely with Raman parameters of UHP (ultra-high pressure) microdiamond. It is hence impossible to assign diamond detected in a geological specimen to either an introduced artefact or a genuine UHP relict, from the Raman spectrum alone. Raman is an excellent technique for the detection of minute amounts of diamond; however it does not provide conclusive evidence for the identification of UHP microdiamond. The latter requires thorough verification, for instance by optical microscopy or, if doubts cannot be dispelled, transmission electron microscopy.
Abstract: Lonsdaleite, also called hexagonal diamond, has been widely used as a marker of asteroidal impacts. It is thought to play a central role during the graphite-to-diamond transformation, and calculations suggest that it possesses mechanical properties superior to diamond. However, despite extensive efforts, lonsdaleite has never been produced or described as a separate, pure material. Here we show that defects in cubic diamond provide an explanation for the characteristic d-spacings and reflections reported for lonsdaleite. Ultrahigh-resolution electron microscope images demonstrate that samples displaying features attributed to lonsdaleite consist of cubic diamond dominated by extensive {113} twins and {111} stacking faults. These defects give rise to nanometre-scale structural complexity. Our findings question the existence of lonsdaleite and point to the need for re-evaluating the interpretations of many lonsdaleite-related fundamental and applied studies.
Geochemistry: Exploration, Environment, Analysis, Vol. 16, 3-4, pp. 181-192.
Technology
Geochemistry
Abstract: Three portable X-ray fluorescence (pXRF) methods were compared and tested in an exploration program using till in Sinoselkä, northern Finland. The use of one truck-mounted XRF unit and two handheld pXRF analysers were tested for basal till samples gathered using percussion drilling with a flow-through sampling bit. The datasets were compared to both conventional aqua regia based analyses and each other. The results prove that a correlation between the data generated by different pXRF methods was acceptable for some major (Ca, Fe) and most of the base metal elements (like As, Cr, Cu, Mn, Ni, Pb, Zn) in the Sinoselkä area. The pXRF analyses also correlate well with the aqua regia geochemical data of the same elements. Distribution of the elements was comparable to the lithological changes in the underlying bedrock that indicates a short glacial transport distance. It is also demonstrated that more than absolute values, the relative values and their changes are those which should be considered and carefully examined. The results reported here emphasize the usefulness of pXRF analysers in till geochemical exploration and demonstrate that they involve easy and fast methods to collect geochemical data for tracing sources of multi-metal mineralization. Furthermore, pXRF is applicable in gold exploration, although indicator elements like As, Bi, Cu, Mn and Sb have to be used instead of Au.
Geostandards and Geoanalytical Research, in press available
Technology
REE mass fractions
Abstract: Olivine offers huge, largely untapped, potential for improving our understanding of magmatic and metasomatic processes. In particular, a wealth of information is contained in rare earth element (REE) mass fractions, which are well studied in other minerals. However, REE data for olivine are scarce, reflecting the difficulty associated with determining mass fractions in the low ng g?1 range and with controlling the effects of LREE contamination. We report an analytical procedure for measuring REEs in olivine using laser ablation quadrupole-ICP-MS that achieved limits of determination (LOD) at sub-ng g?1 levels and biases of ~ 5-10%. Empirical partition coefficients (D values) calculated using the new olivine compositions agree with experimental values, indicating that the measured REEs are structurally bound in the olivine crystal lattice, rather than residing in micro-inclusions. We conducted an initial survey of REE contents of olivine from mantle, metamorphic, magmatic and meteorite samples. REE mass fractions vary from 0.1 to double-digit ng g?1 levels. Heavy REEs vary from low mass fractions in meteoritic samples, through variably enriched peridotitic olivine to high mass fractions in magmatic olivines, with fayalitic olivines showing the highest levels. The variable enrichment in HREEs demonstrates that olivine REE patterns have petrological utility.
Doklady Earth Sciences, Vol. 471, 1, pp. 1144-1148.
Technology
Petrology - experimental
Abstract: Experimental research in the Fe3C-(Fe,Ni)S system was carried out. The objective of the investigation was to model the reactions of carbide-sulfide interaction related to graphite (diamond) formation in reduced lithosphere mantle domains. T ? 1200°C is the formation temperature of the Ni-cohenite + graphite assemblage coexisting with two immiscible melts such as sulfide (Fe60-Ni3-S37)L and metal-sulfide (Fe71-Ni7-S21-C1)L containing dissolved carbon. T ? 1300°C is the generation temperature of a unified melt such as (Fe80-Ni6-S10-C4)L characterized by graphite crystallization and diamond growth. The extraction of carbide carbon during the interaction with the sulfide melt can be considered as one of the potential mechanisms of graphite and diamond formation in the reduced mantle.
Contributions to Mineralogy and Petrology, Vol. 171, pp. 101-
Technology
Eclogite
Abstract: Clinopyroxene is an essential mineral in eclogitic rocks. It commonly contains minor amounts of the defect-bearing Ca-Eskola (CaEs, Ca0.5?0.5AlSi2O6) component, with higher concentrations generally considered to indicate a high-pressure origin at least within the coesite stability field. Changes in pressure and temperature conditions can lead to exsolution of this component as a free SiO2 phase, which may have a number of petrological implications. This makes it important to understand the factors that maximize CaEs incorporation in clinopyroxene. We have undertaken a series of experiments at high pressures and temperatures (4-10 GPa and 1000-1350 °C) to further investigate the systematics of CaEs incorporation in eclogite-like clinopyroxene and the factors responsible for maximizing CaEs contents. Two simple chemical systems were chosen that allow unambiguous interpretation of the results: (1) CMAS + H2O and (2) two compositions in the NCMAS system. All experimental products contained clinopyroxene and garnet along with either a free SiO2 phase or a silicate melt. Coexisting garnet is grossular-rich, generally with Xgr ? 0.67. Compositional variations are attributable to the presence or absence of melt and changes in modal amounts of garnet at different pressure-temperature conditions. Even small amounts of H2O lower the solidus temperature and the presence of a melt reduces the SiO2 activity, which destabilizes the CaEs component in clinopyroxene. The CaEs and the Ca-Tschermaks (CaTs, CaAl2SiO6) components in clinopyroxene decrease with increasing jadeite mole fraction, which is also a function of pressure and bulk Al content. Modeling X-ray powder diffraction data yields a molar volume for the CaEs endmember of VCaEs = 60.87(63) cm3, which reasonably agrees with a literature value that was estimated from natural samples. In the presence of coexisting coesite, the CaEs and CaTs do not vary independently of each other, being controlled by the internal equilibrium 2CaEs = CaTs + 3SiO2 (coesite). This relation, observed in simple systems (i.e., CMAS ± Na), is also obeyed by clinopyroxene in more complex, natural analog bulk compositions. An assessment of available experimental data reveals a maximum of 15-18 mol% CaEs in eclogitic clinopyroxene at conditions corresponding to 130-180 km depth. CaEs contents are maximized at high temperatures; i.e., at or near the solidus in the presence of coesite. Thus, this study supports the role of CaEs exsolution in contributing to melt generation during upwelling of eclogite bodies in the mantle, albeit with some caveats. Somewhat higher maximum CaEs contents (~20 mol%) are found in Ca and Al-rich bulk compositions, such as grospydite xenoliths. Such bulk compositions also seem to require the coexistence of kyanite. Other Ca and Al-rich rock types, like rodingites, should have the potential of containing CaEs-rich clinopyroxenes, except that they are SiO2-undersaturated. This emphasizes the further role of bulk composition, in addition to high temperatures, in achieving maximum CaEs contents in high-pressure clinopyroxene.
Abstract: The possible presence of the high-density carbon polymorph with hexagonal symmetry known as “lonsdaleite” provides an important marker for shock impact events. It is typically considered to form as a metastable phase produced from graphite or other carbonaceous precursors. However, its existence has recently been called into question. Here we collected high-resolution synchrotron X-ray diffraction data for laboratory-shocked and natural impact diamonds that both show evidence for deviations from cubic symmetry, that would be consistent with the appearance of hexagonal stacking sequences. These results show that hexagonality can be achieved by shocking diamond as well as from graphite precursors. The diffraction results are analyzed in terms of a general model that describes intermediate stacking sequences between pure diamond (fully cubic) and “lonsdaleite” (fully hexagonal) phases, with provision made for ordered vs disordered stacking arrangements. This approach provides a “hexagonality index” that can be used to characterize and distinguish among samples that have experienced different degrees of shock or static high pressure-high temperature treatments. We have also examined the relative energetics of diamond and “lonsdaleite” structures using density functional theoretical (DFT) methods. The results set limits on the conditions under which a transformation between diamond and “lonsdaleite” structures can be achieved. Calculated Raman spectra provide an indicator for the presence of extended hexagonal stacking sequences within natural and laboratory-prepared samples. Our results show that comparable crystallographic structures may be developed by impact-generated shockwaves starting from ambient conditions using either of the two different allotropes of carbon (diamond, graphite). This broadens the scope for its occurrence in terrestrial and planetary systems.
Abstract: Experimental observations on the dissolution of elements in minerals and melts and the partitioning between the two materials show that the concentration (or the partition coefficient) of trace elements depends on the properties of elements as well as those of relevant materials (minerals and melts) and the thermochemical conditions. Previous models of element solubility in minerals contain a vague treatment of the role of the stiffness of the element and have a difficulty in explaining some observations including the solubility of the noble gases. A modified theory of element solubility in minerals is presented where the role of elasticity of both matrix mineral and the element is included using the continuum theory of point defects by Eshelby (1951, 1954, 1956). This theory provides a framework to explain the majority of observations and shows a better fit to the published results on the effective elastic constants relevant to element partitioning. However, the concept of “elasticity of the trace element” needs major modification when the site occupied by a trace element has large excess charge. The experimental data of the solubility coefficients of noble gases in melts show strong dependence on the atomic size that invalidates the “zero-charge” model for noble gas partitioning. A simple model of element solubility in melts is proposed based on the hard sphere model of complex liquids that provides a plausible explanation for the difference in the dissolution behavior between noble gases and other charged elements. Several applications of these models are discussed including the nature of noble gas behavior in the deep/early Earth and the water distribution in the lithosphere/asthenosphere system.
Physics and Chemistry of Minerals, in press available 9p.
Technology
Garnet morphology
Abstract: We present a systematic experimental study on the phase transition, lattice microstrain, and order-disorder of cations for garnets in the majorite-pyrope system. Polycrystalline gem-quality garnets were synthesized at high pressure and high temperature using a Kawai-type multi-anvil apparatus. A phase transition from a cubic to tetragonal structure is clearly observed for garnets with the majorite content of more than 74 mol % through X-ray diffraction (XRD) and Raman scattering studies. Microstrain of garnets, evaluated with the Williamson-Hall plot on XRD profiles, shows a nonlinear dependence of the garnet compositions. The variation of the XRD peak broadening suggests the lattice microstrain of these garnets may be associated with the local structural heterogeneities due to the substitution of different cations via the coupled substitution (Mg2+ + Si4+ = 2Al3+) in the garnet structure. The width variation of Raman scattering peaks indicates that cation disorder occurs in the garnet structure for intermediate compositions. It is found that intermediate garnets and end-members have a minimum of microstrain, while those between end-members and intermediate compositions possess a larger microstrain.
Abstract: One of the most controversial diamond types is carbonado, as its origin and geological history are still under debate. Here, we investigate selected carbonado samples using neutron diffraction and high resolution orientation mapping in combination with numerical simulations. Neutron diffraction analyses show that fine grained carbonado samples exhibit a distinct lack of crystallographic preferred orientation. Quantitative crystallographic orientation analyses performed on transmission electron microscope (TEM) sections reveal that the 2-10 ?m grains exhibit locally significant internal deformation. Such features are consistent with crystal plastic deformation of a grain aggregate that initially formed by rapid nucleation, characterized by a high number of nucleation sites and no crystallographic preferred orientation. Crystal plastic deformation resulted in high stress heterogeneities close to grain boundaries, even at low bulk strains, inducing a high degree of lattice distortion without significant grain size reduction and the development of a crystallographic preferred orientation. Observed differences in the character of the grain boundary network and internal deformation structures can be explained by significant post-deformation annealing occurring to variable degrees in the carbonado samples. Differences in intensity of crystal bending and subgrain boundary sharpness can be explained by dislocation annihilation and rearrangement, respectively. During annealing grain energy is reduced resulting in distinct changes to the grain boundary geometry. Grain scale numerical modelling shows that anisotropic grain growth, where grain boundary energy is determined by the orientation of a boundary segment relative to the crystallographic orientation of adjacent grains results in straight boundary segments with abrupt changes in orientation even if the boundary is occurring between two triple junctions forming a “zigzag” pattern. In addition, in diamond anisotropic grain growth results in triple junctions that rarely show 120° angles. Our results support the interpretation that carbonados may have undergone at least 2 or 3 stages of development with rapid nucleation, crystal plastic deformation to low strains and variable degrees of post-deformation annealing. Such a history is commonly observed in Earth's crustal or mantle rocks. Hence, for carbonados it is not necessary to invoke an extraordinary and/or extraterrestrial origin and history. The combination of methods utilized here, promises to help advance our understanding of diamond and diamond aggregates in the future.
Abstract: The Late Cretaceous (ca. 100 Ma) diamondiferous Fort à la Corne (FALC) kimberlite field in the Saskatchewan (Sask) craton, Canada, is one of the largest known kimberlite fields on Earth comprising essentially pyroclastic kimberlites. Despite its discovery more than two decades ago, petrological, geochemical and petrogenetic aspects of the kimberlites in this field are largely unknown. We present here the first detailed petrological and geochemical data combined with reconnaissance Nd isotope data on drill-hole samples of five major kimberlite bodies. Petrography of the studied samples reveals that they are loosely packed, clast-supported and variably sorted, and characterised by the presence of juvenile lapilli, crystals of olivine, xenocrystal garnet (peridotitic as well as eclogitic paragenesis) and Mg-ilmenite. Interclast material is made of serpentine, phlogopite, spinel, carbonate, perovskite and rutile. The mineral compositions, whole-rock geochemistry and Nd isotopic composition (Nd: + 0.62 to ? 0.37) are indistinguishable from those known from archetypal hypabyssal kimberlites. Appreciably lower bulk-rock CaO (mostly < 5 wt%) and higher La/Sm ratios (12-15; resembling those of orangeites) are a characteristic feature of these rocks. Their geochemical composition excludes any effects of significant crustal and mantle contamination/assimilation. The fractionation trends displayed suggest a primary kimberlite melt composition indistinguishable from global estimates of primary kimberlite melt, and highlight the dominance of a kimberlite magma component in the pyroclastic variants. The lack of Nb-Ta-Ti anomalies precludes any significant role of subduction-related melts/fluids in the metasomatism of the FALC kimberlite mantle source region. Their incompatible trace elements (e.g., Nb/U) have OIB-type affinities whereas the Nd isotope composition indicates a near-chondritic to slightly depleted Nd isotope composition. The Neoproterozoic (~ 0.6-0.7 Ga) depleted mantle (TDM) Nd model ages coincide with the emplacement age (ca. 673 Ma) of the Amon kimberlite sills (Baffin Island, Rae craton, Canada) and have been related to upwelling protokimberlite melts during the break-up of the Rodinia supercontinent and its separation from Laurentia (North American cratonic shield). REE inversion modelling for the FALC kimberlites as well as for the Jericho (ca. 173 Ma) and Snap Lake (ca. 537 Ma) kimberlites from the neighbouring Slave craton, Canada, indicate all of their source regions to have been extensively depleted (~ 24%) before being subjected to metasomatic enrichment (1.3-2.2%) and subsequent small-degree partial melting. These findings are similar to those previously obtained on Mesozoic kimberlites (Kaapvaal craton, southern Africa) and Mesoproterozoic kimberlites (Dharwar craton, southern India). The striking similarity in the genesis of kimberlites emplaced over broad geological time and across different supercontinents of Laurentia, Gondwanaland and Rodinia, highlights the dominant petrogenetic role of the sub-continental lithosphere. The emplacement of the FALC kimberlites can be explained both by the extensive subduction system in western North America that was established at ca. 150 Ma as well as by far-field effects of the opening of the North Atlantic ocean during the Late Cretaceous.
Journal of Mining Science, Vol. 52, 2, pp. 332-340.
Technology
Spectroscopy
Abstract: The lithosphere beneath the Western Canada Sedimentary Basin has potentially undergone Precambrian subduction and collisional orogenesis, resulting in a complex network of crustal domains. To improve the understanding of its evolutionary history, we combine data from the USArray and three regional networks to invert for P-wave velocities of the upper mantle using finite-frequency tomography. Our model reveals distinct, vertically continuous high (> 1%) velocity perturbations at depths above 200 km beneath the Precambrian Buffalo Head Terrane, Hearne craton and Medicine Hat Block, which sharply contrasts with those beneath the Canadian Rockies (
International Journal of Remote Sensing, Vol. 38, 3, pp. 827-849.
Technology
LIDAR
Abstract: In recent years lidar technology has experienced a noticeable increase in its relevance and usage in a number of scientific fields. Therefore, software capable of handling lidar data becomes a key point in those fields. In this article, we present GPU-based viewer lidar (GVLiDAR), a novel web framework for visualization and geospatial measurement of lidar data point sets. The design of the framework is focused on achieving three key objectives: performance in terms of real-time interaction, functionality, and online availability for the lidar datasets. All lidar files are pre-processed and stored in a lossless data structure, which minimizes transfer requirements and offers an on-demand lidar data web framework.
Abstract: This position statement sets out ICMM members’ approach to water stewardship. Water stewardship is the use of water in ways that are socially equitable, environmentally sustainable, and economically beneficial.1 Effective stewardship requires collaboration and concerted action from all parties, including government, civil society, business and local communities through inclusive stakeholder engagement.
Mineralogical Record, 2 Volumes 809;813pp., approx $400.00 US
Technology
Book - mineral discoveries
Abstract: It is no exaggeration to say that Moore’s Compendium of Mineral Discoveries 1960-2015 is the most important publication for mineral collectors since Dana’s System of Mineralogy. Think of it as a "What’s New in Minerals" covering the last 55 years, which has truly been a Golden Age of mineral collecting. Detailed information on mineral specimen discoveries made worldwide since 1960 has been gleaned from every major mineral collector magazine in English, German, French, Spanish and Italian, as well as books, mineral dealer catalogs and unpublished manuscripts - all meticulously referenced. The vast majority of the publications have never been indexed and are not available online, so this information has been inaccessible to all collectors lacking a personal library of such journals and the ability to read five languages. The description of each occurrence covers as many aspects as possible, beginning with the general appearance and style of specimens; the sizes, morphologies and habits of major crystals; associated species; geological settings; the histories of the localities; the circumstances of the discoveries, including the names of collectors; interesting or amusing collecting stories; marketing information (i.e. where, when and how specimens have been offered for sale); and whatever else may seem in some way noteworthy.
Doklady Earth Sciences, Vol. 471, 2, pp. 1303-1306.
Technology
Diamond crystallography
Abstract: The occurrence rates of combinatorial types of simple polyhedra {111} are analyzed for natural and artificial diamonds. The empirical occurrence rates of 14 possible polyhedra in an isotropic environment are obtained based on numeral simulation of growth forms of octahedral crystals by the Monte-Carlo method. The phenomenon of dissymmetrization by Curie’s principle related to the crystallization conditions is established for artificial and natural diamonds.
European Journal of Mineralogy, Vol. 28, pp. 915-930.
Technology
Mineral chemistry
Abstract: The crystal structures of the lamprophyllite-related minerals are based upon HOH modules consisting of a central octahedral O sheet sandwiched between two heteropolyhedral H sheets. The general crystal-chemical formula for these minerals can be written as [10-11]A2 [[6]M1[6]M22[6]2M3X2] [[5]L2(Si2O7)2O2], where the contents of the O and H sheets are given in square brackets in this order and A = Ba, Sr, K, Na,; M1 = Na, Mn2+; M2 = Na, Mn2+, Fe2+, Ca; M3 = Ti, Mn2+, Mg, Fe3+, Fe2+; L = Ti, Fe3+; X = OH, O, F. According to the unit-cell parameters and symmetry, lamprophyllite-related minerals can be subdivided into five structure types: I (monoclinic polytypes, C2/m); II (orthorhombic polytypes, Pnmn), III (nabalamprophyllite, BaNa[Na3Ti (OH)2][Ti2(Si2O7)2O2], monoclinic, P2/m, with an ordered arrangement of the interlayer Ba2+ and Na+ cations), IV (triclinic, P1) and V (triclinic, Embedded Image ). The triclinic members (types IV and V) include schüllerite and its analogues, which differ from the lamprophyllite-group minerals sensu stricto in their symmetry and topology of the HOH modules. The end-member formulae of lamprophyllite-related minerals and the position of schüllerite in the ranks of heterophyllosilicates are discussed.
Abstract: One of the main challenges of the mining industry is to ensure that produced tonnages and grades are aligned with targets derived from model-based expectations. Unexpected deviations, resulting from large uncertainties in the grade control model, often occur and strongly impact resource recovery and process efficiency. During operation, local predictions can be significantly improved when deviations are monitored and integrated back into the grade control model. This contribution introduces a novel realization-based approach to real-time updating of the grade control model by utilizing online data from a production monitoring network. An algorithm is presented that specifically deals with the problems of an operating mining environment. Due to the complexity of the material handling process, it is very challenging to formulate an analytical approximation linking each sensor observation to the grade control model. Instead, an application-specific forward simulator is built, translating grade control realizations into observation realizations. The algorithm utilizes a Kalman filter-based approach to link forward propagated realizations with real process observations to locally improve the grade control model. Differences in the scale of support are automatically dealt with. A literature review, following a detailed problem description, presents an overview of the most recent approaches to solving some of the practical problems identified. The most relevant techniques are integrated and the resulting mathematical framework is outlined. The principles behind the self-learning algorithm are explained. A synthetic experiment demonstrates that the algorithm is capable of improving the grade control model based on inaccurate observations on blended material streams originating from two extraction points.
Science China Earth Sciences, Vol. 60, 2, pp. 207-217.
Technology
Subduction
Abstract: Diamonds are renowned as the record of Earth’s evolution history. Natural diamonds on the Earth can be distinguished in light of genetic types as kimberlitic diamonds (including peridotitic diamonds and eclogitic diamonds), ultrahigh-pressure metamorphic diamonds and ophiolitic diamonds. According to the inclusion mineralogy, most diamonds originated from continental lithospheric mantle at depths of 140-250 km. Several localities, however, yield ultradeep diamonds with inclusion compositions that require a sublithospheric origin (>~250 km). Ultradeep diamonds exhibit distinctions in terms of carbon isotope composition, N-concentration, mineral inclusions and so on. The present study provides a systematic compilation concerning the features of ultradeep diamonds, based on which to expound their genesis affinity with mantle-carbonate melts. The diamond-parental carbonate melts are proposed to be stemmed from the Earth’s crust through subduction of oceanic lithosphere. Ultradeep diamonds are classified into a subgroup attaching to kimberlitic diamonds grounded by formation mechanism, and present connections in respect of carbon origin to eclogitic diamonds, ultrahigh-pressure metamorphic diamonds and ophiolitic diamonds.
Abstract: We have developed a synthetic multiparametric modeling and inversion exercise undertaken to study the robustness of inverting airborne time-domain electromagnetic (TDEM) data to extract Cole-Cole parameters. The following issues were addressed: nonuniqueness, ill posedness, dependency on manual processing and the effect of constraints, and a priori information. We have used a 1D layered earth model approximation and lateral constraints. Synthetic simulations were performed for several models and the corresponding Cole-Cole parameters. The possibility to recover these models by means of laterally constrained multiparametric inversion was evaluated, including recovery of chargeability distributions from shallow and deep targets based on analysis of induced polarization (IP) effects, simulated in airborne TDEM data. Different scenarios were studied, including chargeable targets associated with the conductive and resistive environments. In particular, four generic models were considered for the exercise: a sulfide model, a kimberlite model, and two generic models focusing on the depth of investigation.
Diamond and Related Materials, Vol. 72, pp. 87-93.
Technology
Diamonds - type 11b
Abstract: Precision admittance spectroscopy measurements were carried out over wide temperature and frequency ranges for a set of natural single crystal type IIb diamond samples. Peaks of conductance spectra vs. temperature and frequency were used to compute the Arrhenius plots, and activation energies were derived from these plots. The capacitance-voltage profiling was used to estimate the majority charge carrier concentration and its distribution into depth of the samples. Apparent activation energies between 315 and 325 meV and the capture cross section of about 10? 13 cm2 were found for samples with uncompensated boron concentrations in the range of 1 to 5 × 1016 cm? 3 (0.06-0.3 ppm). The obtained boron concentrations are in good coincidence with FTIR results for the samples. Also, a reason for the difference between the observed admittance activation energy and the previously reported ionization energy for the acceptor boron in diamond (0.37 eV) is proposed.
Abstract: Mining the deep seabed is fraught with challenges. Untapped mineral potential under the shallow, more accessible continental shelf could add a new dimension to offshore mining and help meet future mineral demand.
European Geosciences Union General Assembly 2017, Vienna April 23-28, 1p. 19147 Abstract
Technology
Diamond inclusions
Abstract: Trapping inclusions in diamonds has been used as a diagnostic to constrain diamond growth media (e.g. Navon et al., 1994; Weiss et al., 2015) in the Earth's upper mantle. Experimental works now generate inclusion-bearing diamonds from seeds in mixtures of carbonates, graphite, and silicates in the presence of excess of pure water or saline fluids (H2O-NaCl) and investigate in more details the conditions of natural diamond growth (Bureau et al., 2012; 2016). Experiments were carried at conditions compatible with the Earth's geotherm between 6-7 GPa (1300-1675°C) in multi-anvil presses at the Bayerisches Geoinstitut, Bayreuth from a few hours two a few days. Results show that within the timescale of the experiments diamond growth occurs on seeds if water and alkali-bearing carbonates are present. We show that water promotes fast diamond growth, which is favorable to the formation of inclusions. Thin sections of a few diamond seeds containing exposed inclusions were prepared using a Focus Ion Beam (about 2 to 5 µm thickness). These sections were deposited on silicon wafers and gold coated for micron-scale determination of the delta 13C isotopic compositions using the NanoSIMS 50 installed at the Muséum National d'Histoire Naturelle, Paris. Carbon isotope measurement with NanoSIMS were calibrated against a natural Ia and a synthetic IIa diamond used for diamond anvil cells, whose compositions were determined by gas-source mass spectrometry at IPGP at 3.6±0.1‰ and -20.9±0.1‰, respectively (Pinti et al., 2016). All the starting materials used for the experiments were also characterized for their delta 13C by the same technique at GEOTOP, Montréal. The isotopic composition of the new diamond grown areas were measured close to the inclusions. They exhibit a different isotopic signature than that of the starting seeds (starting diamond composition: -29.6 to -30.4±1.4‰). The new diamond signatures are falling into the range of signatures of the starting carbonates used for the experiments (- 4.8±0.1 to -16.2±0.1‰) when they are far away from the composition of the starting graphite (-26.4±0.1‰). This shows that the carbon source for diamond growth must be the carbonates present either as CO32- ions dissolved in the melt or as carbon dioxide species CO2 in the aqueous fluid and that diamond growth occurred from carbonate reduction rather that from graphite dissolved in the melt. We suggest that the presence of small discrete or isolated volumes of water-carbonate-rich fluids are necessary to grow inclusion-bearing peridotitic, eclogitic, fibrous, cloudy and coated diamonds, and may also be involved in the growth of ultrahigh pressure metamorphic diamonds.
Abstract: Extensive study has shown that these inclusions contain mantle-derived fluids (e.g. Navon et al., 1988, Izraeli et al., 2001, 2004 Tomlinson et al., 2009; Logvinova et al., 2011; Zedgenizov et al., 2011; Smith et al., 2012, Smith et al., 2015 Howell et al., 2012b Howell et al., , 2013 Weiss et al., 2013 Weiss et al., , 2015 Rakovan et al., 2014; Smit et al., in press), Here we use the term 'milky' to describe diamonds that contain zones of opalescent to brown or grey opaque appearance (Gaillou and Rossman, 2014). The exact cause of this opacity is yet to be defined, and forms the purpose of this paper.
Abstract: On the basis of extensive studies of synthetic perovskite-structured compounds it is possible to derive a hierarchy of hettotype structures which are derivatives of the arisotypic cubic perovskite structure (ABX3), exemplified by SrTiO3 (tausonite) or KMgF3 (parascandolaite) by: (1) tilting and distortion of the BX6 octahedra; (2) ordering of A- and B-site cations; (3) formation of A-, B- or X-site vacancies. This hierarchical scheme can be applied to some naturally-occurring oxides, fluorides, hydroxides, chlorides, arsenides, intermetallic compounds and silicates which adopt such derivative crystal structures. Application of this hierarchical scheme to naturally-occurring minerals results in the recognition of a perovskite supergroup which is divided into stoichiometric and non-stoichiometric perovskite groups, with both groups further divided into single ABX3 or double A2BB?X6 perovskites. Subgroups, and potential subgroups, of stoichiometric perovskites include: (1) silicate single perovskites of the bridgmanite subgroup; (2) oxide single perovskites of the perovskite subgroup (tausonite, perovskite, loparite, lueshite, isolueshite, lakargiite, megawite); (3) oxide single perovskites of the macedonite subgroup which exhibit second order Jahn-Teller distortions (macedonite, barioperovskite); (4) fluoride single perovskites of the neighborite subgroup (neighborite, parascandolaite); (5) chloride single perovskites of the chlorocalcite subgroup; (6) B-site cation ordered double fluoride perovskites of the cryolite subgroup (cryolite, elpasolite, simmonsite); (7) B-site cation ordered oxide double perovskites of the vapnikite subgroup [vapnikite, (?) latrappite]. Non-stoichiometric perovskites include: (1) A-site vacant double hydroxides, or hydroxide perovskites, belonging to the söhngeite, schoenfliesite and stottite subgroups; (2) Anion-deficient perovskites of the brownmillerite subgroup (srebrodolskite, shulamitite); (3) A-site vacant quadruple perovskites (skutterudite subgroup); (4) B-site vacant single perovskites of the oskarssonite subgroup [oskarssonite]; (5) B-site vacant inverse single perovskites of the cohenite and auricupride subgroups; (6) B-site vacant double perovskites of the diaboleite subgroup; (7) anion-deficient partly-inverse B-site quadruple perovskites of the hematophanite subgroup.
European Geosciences Union General Assembly 2017, Vienna April 23-28, 1p. 10193 Abstract
Technology
Book - carbon
Abstract: As an academic historian of science, I am writing a history of the discovery of the interior workings of our dynamic planet. I am preparing a book, titled Carbon from Crust to Core: A Chronicle of Deep Carbon Science, in which I will present the first history of deep carbon science. I will identify and document key discoveries, the impact of new knowledge, and the roles of deep carbon scientists and their institutions from the 1400s to the present. This innovative book will set down the engaging human story of many remarkable scientists from whom we have learned about Earth's interior, and particularly the fascinating story of carbon in Earth. I will describe a great journey of discovery that has led to a better understanding of the physical, chemical, and biological behaviour of carbon in the vast majority of Earth's interior. My poster has a list of remarkable Deep Carbon Explorers, from Georgius Agricola (1494-1555) to Claude ZoBell (1904-1989). Come along to my poster and add to my compilation: choose pioneers from history, or nominate your colleagues, or even add a selfie! As a biographer, I am keen to add researchers who may have been overlooked in the standard histories of geology and geophysics. And I am always on the lookout for standout stories and personal recollections. I am equipped to do oral history interviews. What's your story? Cambridge University Press will publish the book in 2019.
Rethinking laboratory reports for the geographical origin of gems.
Journal of Gemmology, Vol. 35, 5, pp. 416-423.
Technology
Reports - gem reports, tests, grades
Abstract: The proliferation of gemmological laboratory reports and the need for transparency to best protect against litigation suggest that some gem-testing laboratories should consider changes in the wording and content of their geographical origin reports. Based on the author's recent broader study of the legal aspects of the opinions provided by experts in the field of art and antiques, the main proposals presented here are that statements of opinion rather than fact should be clearly expressed as such where they are presented on a report, rather than relegating all mention of 'opinion' to the 'terms and conditions', and that the basic nature of the observational or analytical evidence on which any opinions are based should be noted. In addition, a laboratory might usefully provide some indication of the level of confidence in its opinion.
Geostandards and Geoanalytical Research, in press available
Technology
spectroscopy
Abstract: A broad suite of geological materials were studied a using a handheld laser-induced breakdown spectroscopy (LIBS) instrument. Because LIBS is simultaneously sensitive to all elements, the full broadband emission spectrum recorded from a single laser shot provides a ‘chemical fingerprint’ of any material - solid, liquid or gas. The distinguishing chemical characteristics of the samples analysed were identified through principal component analysis (PCA), which demonstrates how this technique for statistical analysis can be used to identify spectral differences between similar sample types based on minor and trace constituents. Partial least squares discriminant analysis (PLSDA) was used to distinguish and classify the materials, with excellent discrimination achieved for all sample types. This study illustrates through four selected examples involving carbonate minerals and rocks, the oxide mineral pair columbite-tantalite, the silicate mineral garnet and native gold how portable, handheld LIBS analysers can be used as a tool for real-time chemical analysis under simulated field conditions for element or mineral identification plus such applications as stratigraphic correlation, provenance determination and natural resources exploration.
Abstract: Experimental studies of phase relations in the oxide-silicate system MgO-FeO-SiO2 at 24 GPa show that the peritectic reaction of bridgmanite controls the formation of stishovite as a primary in situ mineral of the lower mantle and as an effect of the stishovite paradox. The stishovite paradox is registered in the diamond-forming system MgO-FeO-SiO2-(Mg-Fe-Ca-Na carbonate)-carbon in experiments at 26 GPa as well. The physicochemical mechanisms of the ultrabasic-basic evolution of deep magmas and diamondforming media, as well as their role in the origin of the lower mantle minerals and genesis of ultradeep diamonds, are studied.
Abstract: Chromium valence ratios in igneous olivine may hold a wealth of redox information about the melts from which they crystallized. It has been experimentally shown that the Cr2+/?Cr of olivine varies systematically with fO2, therefore measurements of Cr valence in olivine could be employed as a quantitative oxybarometer. In situ synchrotron ?-XANES analyses of Cr valence ratios of individual olivine phenocrysts in thin section have the potential to unlock this stored magmatic redox information on a fine spatial scale. However, there are still obstacles to obtaining accurate XANES measurements of cation valence in crystalline materials, as the results from these measurements can be compromised by anisotropic absorption effects related to the crystallographic orientation of the sample. Improving the accuracy of XANES measurements of Cr valence ratios in olivine by calibrating an anisotropy correction is a vital step in developing Cr valence measurements in olivine as a rigorous oxybarometer. To accomplish this goal, we have used an integrated approach that combined experiments, electron backscatter diffraction analysis, and XANES measurements in olivine to systematically examine how orientation affects the resultant Cr K-edge XANES spectra and the Cr valence ratios that are calculated from them. The data set generated in this work was used to construct a model that mitigates the effects of anisotropy of the calculated Cr2+/?Cr values. The application of this correction procedure as a part of spectral processing improves the overall accuracy of the resultant Cr2+/?Cr values by nearly a factor of five. The increased accuracy of the XANES measured Cr valence ratios afforded by the anisotropy correction reduces the error on calculated fO2 values from approximately ±1.2 to ±0.25
Abstract: Boris Choubert was a strong supporter of Wegener's continental drift theory. In 1935, he published a very accurate fit of the circum-Atlantic continents, which was based on continental edges instead of coastlines; in the same paper, he interpreted the Palaeozoic belts as the result of horizontal movements of the Precambrian blocks; so, he greatly expanded the role of continental drift through time. This original and very prophetic work was almost completely ignored by his contemporaries. Thirty years later (1965), Bullard, Everett and Smith published in turn a similar but more sophisticated fit; they did not acknowledge Choubert's initial work. Bullard's fit was met with immediate and tremendous success. The present paper analyses the reasons why Boris Choubert was frustrated of his pioneering role. This lack of recognition is related to: (1) a great evolution in the geological concepts between 1935 and 1965, and (2) a poor choice of Choubert, regarding the title of his 1935 article.
Geological Society of London, Special Publication: Monogenetic volcanism, no. 446, pp. 101-122.
Technology
diatremes
Abstract: Most kimberlite maar-diatreme volcanoes erupted during the Tertiary or earlier and therefore their tephra rings and, less often, their near-surface diatreme-filling deposits have usually been eliminated by erosion. Poorly eroded Quaternary non-kimberlite maar-diatreme volcanoes, especially those of mafic and ultramafic magma types, have the same diatreme size range (diameter and depth) as kimberlite pipes and show similar internal volcaniclastic diatreme lithofacies. In addition, these young volcanoes often have a more or less preserved tephra ring consisting of hundreds to perhaps a few thousand thin tephra beds. Volcanological analyses of the xenolith-rich primary volcaniclastic deposits both within these diatremes and in the tephra ring beds reflect phases of explosive pipe growth and are of convincingly phreatomagmatic origin. The similarities between non-kimberlite pipes and kimberlite pipes suggest to some researchers that phreatomagmatic processes were also responsible for pipe excavation processes in kimberlite maar-diatreme volcanoes. In contrast, other researchers have suggested that kimberlite maar-diatreme volcanoes were emplaced largely by magmatic processes as a consequence of exsolution and the explosive expansion of juvenile volatiles. We therefore analysed and compared some key geological features of kimberlite and ultrabasic to basic ‘basaltic’ maar-diatreme volcanoes to determine similarities and differences with respect to their emplacement behaviour.
Geological Society of London, Special Publication: Monogenetic volcanism, No. 446, pp. 29-59.
Technology
diatremes
Abstract: We report here a growth model for phreatomagmatic maar-diatreme volcanoes with respect to the number of eruptions documented in the tephra beds of maar tephra rings and the upper bedded diatreme facies. We show that the number of tephra beds in large diatremes is larger than that in maar tephra rings. Base surges that lack sufficient momentum to scale high maar crater walls deposit their tephra only inside the crater. Thus the total number of eruptions at large maar-diatreme volcanoes will be larger than the number recorded in maar tephra rings. As many maar-diatreme volcanoes erupt dominantly accidental clasts, an incremental mathematical model was applied to study the growth of diatremes. The model is based only on the ejection of distinct amounts of accidental clasts per unit eruption and the chosen number of eruptions is assumed to be identical. The incremental growth of cone-shaped diatremes follows cube-root functions with respect to diameter and depth and slows down with ongoing eruptions. In nature, small and large maar-diatreme volcanoes are formed and filled syn-eruptively, mostly by tephra, depending on the duration and quantity of magma involved in phreatomagmatic eruptions. In our opinion, this mathematical model is the only current method able to model the growth of diatremes.
Geochemistry: Exploration, Environment, Analysis, Vol. 17, 2, pp. 63-91.
Technology
classification
Abstract: Mineral deposit models strategically guide exploration. The lithologies from which these models are built have genetic connotations. Thus, rock classification must be accurate to ensure that mineral exploration is effective and successful. Rock classification is based on mineral proportions, and these are commonly determined by: (1) visual inspection, which is subject to large errors; (2) point counting, which is tedious and time-consuming; (3) image analysis of stained slabs or polished thin sections, which is expensive and constrained by the availability of appropriate stains; and (4) image analysis of spectrometric data, which is expensive. These features make rock classification difficult and undermine its quality, thereby negatively impacting geological conclusions and mineral exploration results. A novel alternative procedure for igneous rock classification involves using whole rock lithogeochemical data for classification on Streckeisen ternary diagrams. This approach employs several calculations that transform: (1) mass-based element concentrations (the original lithogeochemical data produced by the laboratory) sequentially into (2) unstandardized (do not sum to unity) molar element numbers; (3) unstandardized molar mineral numbers; (4) unstandardized volume mineral numbers; and finally (5) standardized (closed; sum to unity) volume mineral concentrations that estimate the mineral modes in rocks. These mineral mode estimates can then be plotted on (projected onto) Streckeisen ternary diagrams, to classify the rocks in the normal manner. This new approach has advantages over conventional classification strategies, in that it is relatively inexpensive, adaptable to all forms of igneous rocks, quantitative, accurate, and precise. Required petrographic information necessary to conduct such a classification includes only knowledge of chemical formulae of the ‘essential’ mineral assemblage. Essential minerals are, here, considered those minerals having concentrations exceeding 5% in 5% of the rocks under consideration. This criterion allows this lithogeochemical classification procedure to be applicable to a wide variety of igneous rocks. This lithogeochemical classification procedure has additional applications beyond the classification of plutonic igneous rocks. For example, if an essential mineral assemblage can be identified or hypothesized, classification of felsic or mafic volcanic rocks can also be achieved. Additionally, an essential mineral assemblage does not have to consist exclusively of igneous minerals. As a result, conversion from molar element numbers to molar mineral numbers can be undertaken using many mineral assemblages. This allows analogous lithogeochemical classification to be undertaken for almost any rock type (e.g. clastic sedimentary rocks, using the calculated proportions of quartz, feldspar, and clay minerals). Consequently, lithogeochemical calculation of the essential mineral modes in rocks can be used to establish mineral zoning maps in space or time, allowing exploration geoscientists to create down-hole logs depicting hydrothermal alteration mineral abundances, or surface maps of hydrothermal alteration zones on a mineral property. To demonstrate this new procedure, results from classifications of metaluminous, peraluminous, and alkaline felsic plutonic and volcanic rocks, and mafic and ultramafic plutonic and volcanic rocks are compared with mineral modes acquired by independent means (visual estimates, point counts, image analysis, spectrometry). These case studies demonstrate that the proposed lithogeochemical classification procedure is as or more accurate than conventional classification methods. Furthermore, because lithogeochemical samples are far larger, and thus more representative than the surfaces used to estimate mineral modes by conventional means, this lithogeochemical classification procedure is also far more precise. The resulting classification is thus especially effective when working with fine-grained rocks where mineral identification and volume estimation is difficult.
Abstract: Monticellite is a magmatic and/or deuteric mineral that is often present, but widely varying in concentrations in Group-I (or archetypal) kimberlites. To provide new constraints on the petrogenesis of monticellite and its potential significance to kimberlite melt evolution, we examine the petrography and geochemistry of the minimally altered hypabyssal monticellite-rich Leslie (Canada) and Pipe 1 (Finland) kimberlites. In these kimberlites, monticellite (Mtc) is abundant (25–45 vol%) and can be classified into two distinct morphological types: discrete and intergrown groundmass grains (Mtc-I), and replacement of olivine (Mtc-II).
Monticellite in group-I kimberlites: Implications for evolution of parental melts and post-emplacement CO 2 degassing (PDF Download Available). Available from: https://www.researchgate.net/publication/318032868_Monticellite_in_group-I_kimberlites_Implications_for_evolution_of_parental_melts_and_post-emplacement_CO_2_degassing [accessed Aug 10, 2017].
Abstract: Diamond inclusions are potentially fundamental to understanding the formation conditions of diamond and the volatile cycles in the deep mantle. In order to fully understand the implications of the compositional information recorded by inclusions it is vital to know whether the inclusions are proto-, syn-, or epigenetic and the extent to which they have equilibrated with diamond forming fluids. In previous studies, the widespread assumption was made that the majority of diamond inclusions are syngenetic, based upon observation of cubo-octahedral morphology imposed on the inclusions. Recent work has reported the crystallographic relationship between inclusions and the host diamond to be highly complex and the lack of crystallographic relationships between inclusions and diamonds has led some to question the significance of imposed cubo-octahedral morphology. This study presents an integrated EBSD and CL study of 9 diamonds containing 20 pyropes, 2 diopsides, 1 forsterite and 1 rutile from the Jwaneng and Letlhakane kimberlite clusters, Botswana. A new method was developed to analyze the crystallographic orientation of the host diamond and the inclusions with EBSD. Diamonds plates were sequentially polished to expose inclusions at different levels in the diamond. CL imaging at different depths was performed in order to produce a 3D view of diamond growth zones around the inclusions. Standard diamond polishing techniques proved too aggressive for silicate inclusions as they were damaged to such a degree that EBSD measurements on the inclusions were impossible. The inclusions were milled with a Ga+ focused ion beam (FIB) at a 12° angle to clean the surface for EBSD measurements. Of the 24 inclusions, 9 have an imposed cubo-octahedral morphology. Of these inclusions, 6 have faces orientated parallel to diamond growth zones and/or appear to have nucleated on a diamond growth surface, implying syngenesis. In contrast, other diamonds record resorption events such that inclusions now cut diamond growth zones. In most cases, the growth zonation around inclusions is not well defined due to CL haloes but some inclusions clearly disrupt diamond growth. Crystallographic orientations of diamond and the inclusions, determined using EBSD, revealed that each inclusion has a homogeneous orientation and record no compositional zonation. The diamonds also showed no angular deviations despite many having multiple growth and resorption zones; implying epitaxial growth of diamond. Crystallographic alignment between diamond and inclusions was not recorded for the principle planes and limited to 3 possible coincidences on minor planes from the 24 inclusions studied. The CL data show no evidence of syngenesis for these 3 inclusions. Analyses of two diamonds with inclusion clusters in different growth zones, 400 µm apart, revealed the same chemical composition and orientation, potentially implying they originated from an original larger inclusion. Combined EBSD and CL data suggest that there is no direct orientational correlation (epitaxial growth) between silicate inclusions and the host diamond, even when the mineral phases are of the same symmetry group. The presentation will provide a detailed evaluation of the genesis of individual inclusions.
Diamond and Related Materials, Vol. 77, pp. 159-170.
Technology
diamond morphology
Abstract: Low-pressure, high-temperature (LPHT) annealing of yellow-to-brown type Ia natural diamonds was performed to monitor its effects on optical centers within diamond, changes in the observed color, and to assess the process's viability as a commercial gem treatment. With LPHT annealing only, the mostly brown diamonds showed a shift towards yellow coloration; Vis-NIR absorption spectra showed this change was due to a modest increase in H3 intensity. Even at long annealing times (24 h at 1800 °C) or annealing at high temperatures (2000 °C for five minutes), the diamonds did not significantly lose brown coloration. LPHT annealing showed itself as an ineffective means to break apart the vacancy clusters causing the brown color or causing nitrogen disaggregation, which resulted in only a small H3 generation. With LPHT annealing, “amber centers”—a group of several independent bands in the IR between 4200 and 4000 cm? 1 that disappear with HPHT annealing—were seen to anneal out gradually at various temperatures from 1700 to 2000 °C. In contrast, high-pressure, high-temperature (HPHT) annealing effectively removes brown color at similar time/temperature conditions. Without the high stabilizing pressure provided by HPHT annealing techniques, the LPHT annealing showed pronounced damage on inclusions and dramatic surface etching. In subsequent experiments, LPHT annealing was used as a follow-up to laboratory irradiation. The irradiation-related vacancies created greater concentrations of H3 and the vacancy-assisted disaggregation of nitrogen created donors which led to a high concentration of H2 centers. This combination of defects resulted in a pronounced and favorable shift towards saleable yellow colors due to an increase in H3 and a dramatic increase in the H2 center, which led to the suppression of the remaining brownish component. The annealing characteristics for many centers detected by Vis-NIR absorption spectroscopy, FTIR absorption spectroscopy, and photoluminescence spectroscopy were chronicled throughout the study and compared with other LPHT annealing studies and HPHT annealing experiments.
Abstract: Kimberlite magmas, the primary source of diamonds, have many features indicative of explosive eruptions and high volatile contents. The main approaches used to establish exsolution of fluid during magma ascent include theoretical modeling and experimental estimates of volatile solubility in kimberlite-like melts. Both approaches are hampered by the poorly constrained composition of kimberlite melts. Resorption features on diamonds are very sensitive to the presence and composition of the kimberlite fluid as well as to temperature and pressure. Here, we use direct evidence from diamond resorption features as a new method for investigating the parameters of fluid exsolution. The method is based on experimental reproduction of diamond resorption in kimberlite melts with and without an exsolved fluid phase. We studied 802 diamonds from two kimberlites (BK1 and AK15) from the Orapa cluster, Botswana. Samples from the BK1 pipe include three lithologies: two coherent kimberlites (CK-A and CK-B) and a pyroclastic kimberlite (massive volcaniclastic kimberlite, MVK). The known depth of diamond samples in each kimberlite lithology allows us to demonstrate an increase in the intensity of kimberlite-induced resorption with depth of diamond recovery in the drill holes. Each kimberlite lithology has a different proportion of diamonds with kimberlite-induced resorption, which is unique in style in each lithology: glossy surfaces in MVK due to reaction with C-O-H fluid, rough corroded surfaces in CK-B due to reaction with volatile-undersaturated melt, and a combination of glossy surfaces with corroded features in CK-A due to an overprint of melt resorption after fluid resorption. Both diamond resorption and kimberlite textures in the BK1 kimberlite show evidence of fluid exsolution only in CK-A and MVK lithologies, but no fluid presence in CK-B. The observed diamond resorption features may be controlled by (1) a temporary separation of the rising magma column into a bubblerich head and bubble-poor volatile-depleted tail and (2) fluid exsolution at depths greater than decompressional degassing. We discuss how the depth of fluid exsolution from kimberlite melt may affect the diamond grade and the resorption of diamond populations in a kimberlite.
The Canadian Mineralogist, Vol. 55, 4, pp. 521-533.
Technology
Deposit - Renard 2
Abstract: The purpose of this work is to investigate the crystal growth parameters necessary or sufficient to obtain a crystal specifically of gem quality. We assume adequate chemistry is available. First, nucleation must occur with only a limited number of nuclei, otherwise too many crystals will be produced, and they will be too small to be faceted into a gem. Two growth mechanisms are readily documented for gems: Most commonly there is slow growth, driven by a spiral growth mechanism, leading to large single individuals. There are only a few examples of fast growth leading to gem-quality edifices: examples include “gota de aceite” Colombian emerald or the dendritic “pseudo cube” for gem diamonds. We have not documented the intermediate conditions between these two extremes in the Sunagawa diagram, which would correspond to 2D nucleation growth. The presence of inclusions is to be limited to desirable ones. Thus, in general, a good stability of the growth interface is the best guarantee of good clarity in the final gem. As for the interface, in general, growth conditions must be relatively stable over the period necessary to achieve growth. Perhaps surprisingly, it has become well documented that gem-quality near-colorless diamonds may have experienced quite a complex growth history. Therefore, the term stability has to be re-defined for each system producing a given gem. The length of time it takes to achieve crystallization of the gem has rarely been studied or estimated. Scientific evidence from experimental petrology and the growth of synthetic gems indicates that it does not take millions of years to grow a gem, but that this exercise may be achieved in a week to, arguably, a few years at the most. Available free space to grow does not appear always necessary, but it helps. Otherwise deformation, inclusions, and other negative effects may occur. Finally, no dramatic post-growth events, such as fracturing or etching, should affect the gem crystal.
DiaMap: new applications for processing IR spectra of fluid rich diamonds and mapping diamonds containing isolated nitrogen ( type Ib) and boron ( type II b)
Kimberlite intrusions, Kimberlitic as dispersal, diamond transport and diamond deposition: the potential role of Earth Systems Modelling in diamond exploration.
Abstract: On the basis of extensive studies of synthetic perovskite-structured compounds it is possible to derive a hierarchy of hettotype structures which are derivatives of the arisotypic cubic perovskite structure (ABX3), exemplified by SrTiO3 (tausonite) or KMgF3 (parascandolaite) by: (1) tilting and distortion of the BX6 octahedra; (2) ordering of A- and B-site cations; (3) formation of A-, B- or X-site vacancies. This hierarchical scheme can be applied to some naturally-occurring oxides, fluorides, hydroxides, chlorides, arsenides, intermetallic compounds and silicates which adopt such derivative crystal structures. Application of this hierarchical scheme to naturally-occurring minerals results in the recognition of a perovskite supergroup which is divided into stoichiometric and non-stoichiometric perovskite groups, with both groups further divided into single ABX3 or double A2BB?X6 perovskites. Subgroups, and potential subgroups, of stoichiometric perovskites include: (1) silicate single perovskites of the bridgmanite subgroup; (2) oxide single perovskites of the perovskite subgroup (tausonite, perovskite, loparite, lueshite, isolueshite, lakargiite, megawite); (3) oxide single perovskites of the macedonite subgroup which exhibit second order Jahn-Teller distortions (macedonite, barioperovskite); (4) fluoride single perovskites of the neighborite subgroup (neighborite, parascandolaite); (5) chloride single perovskites of the chlorocalcite subgroup; (6) B-site cation ordered double fluoride perovskites of the cryolite subgroup (cryolite, elpasolite, simmonsite); (7) B-site cation ordered oxide double perovskites of the vapnikite subgroup [vapnikite, (?) latrappite]. Non-stoichiometric perovskites include: (1) A-site vacant double hydroxides, or hydroxide perovskites, belonging to the söhngeite, schoenfliesite and stottite subgroups; (2) Anion-deficient perovskites of the brownmillerite subgroup (srebrodolskite, shulamitite); (3) A-site vacant quadruple perovskites (skutterudite subgroup); (4) B-site vacant single perovskites of the oskarssonite subgroup [oskarssonite]; (5) B-site vacant inverse single perovskites of the cohenite and auricupride subgroups; (6) B-site vacant double perovskites of the diaboleite subgroup; (7) anion-deficient partly-inverse B-site quadruple perovskites of the hematophanite subgroup.
Physics and Chemistry of Minerals, in press available, 19p.
Technology
diamond inclusions
Abstract: Elasticity is a key property of materials, not only for predicting volumes and densities of minerals at the pressures and temperatures in the interior of the Earth, but also because it is a major factor in the energetics of structural phase transitions, surface energies, and defects within minerals. Over the 40 years of publication of Physics and Chemistry of Minerals, great progress has been made in the accuracy and precision of the measurements of both volumes and elastic tensors of minerals and in the pressures and temperatures at which the measurements are made. As an illustration of the state of the art, all available single-crystal data that constrain the elastic properties and pressure–volume–temperature equation of state (EoS) of mantle-composition olivine are reviewed. Single-crystal elasticity measurements clearly distinguish the Reuss and Voigt bulk moduli of olivine at all conditions. The consistency of volume and bulk modulus data is tested by fitting them simultaneously. Data collected at ambient pressure and data collected at ambient temperature up to 15 GPa are consistent with a Mie–Grünesien–Debye thermal-pressure EoS in combination with a third-order Birch–Murnaghan (BM) compressional EoS, the parameter V0 = 43.89 cm3 mol?1, isothermal Reuss bulk modulus KTR,0=126.3(2) GPaKTR,0=126.3(2) GPa, K?TR,0=4.54(6)KTR,0?=4.54(6), a Debye temperature ?D=644(9)K?D=644(9)K, and a Grüneisen parameter ?0 = 1.044(4), whose volume dependence is described by q = 1.9(2). High-pressure softening of the bulk modulus at room temperature, relative to this EoS, can be fit with a fourth-order BM EoS. However, recent high-P, T Brillouin measurements are incompatible with these EoS and the intrinsic physics implied by it, especially that (?K?TR?T)P>0(?KTR??T)P>0. We introduce a new parameterisation for isothermal-type EoS that scales both the Reuss isothermal bulk modulus and its pressure derivative at temperature by the volume, KTR(T,P=0)=KTR,0[V0V(T)]?TKTR(T,P=0)=KTR,0[V0V(T)]?T and K?TR(T,P=0)=K?TR,0[V(T)V0]??KTR?(T,P=0)=KTR,0?[V(T)V0]??, to ensure thermodynamic correctness at low temperatures. This allows the elastic softening implied by the high-P, T Brillouin data for mantle olivine to be fit simultaneously and consistently with the same bulk moduli and pressure derivatives (at room temperature) as the MGD EoS, and with the additional parameters of ?V0 = 2.666(9) × 10?5 K?1, ?E=484(6)?E=484(6), ?T?T = 5.77(8), and ???? = ?3.5(1.1). The effects of the differences between the two EoS on the calculated density, volume, and elastic properties of olivine at mantle conditions and on the calculation of entrapment conditions of olivine inclusions in diamonds are discussed, and approaches to resolve the current uncertainties are proposed.
South African Institute of Mining and Metallurgy, Vol. 116, 8, pp. 737-745.
Technology
microdiamond
Abstract: Estimating the size frequency distribution of the macrodiamonds on a new deposit is important for both economic reasons and for the design of the processing plant. Millions of dollars can be lost due to incorrectly sized comminution circuits. This report analyses an alternative methodology for macrodiamond grade estimation using the cumulative results from small parcels of microdiamonds and plotting them on a log-log scale. The method was first evaluated mathematically for diamond populations to assess the confidence for data extrapolation. Macrodiamond size distributions and grades were predicted using microdiamond data from three kimberlites, and the actual macrodiamond grades compared to the the predicted grades. The predicted grades were found to replicate the actual grades closely, showing that a high degree of confidence can be ascribed to the results from this method of analysis. This analysis can be used both for resource estimates and for predicting the diamond size distribution information needed for designing a new operation.
Abstract: Images of diamonds appear everywhere in American culture. And everyone who has a diamond has a story to tell about it. Our stories about diamonds not only reveal what we do with these tiny stones, but also suggest how we create value, meaning, and identity through our interactions with material culture in general. Things become meaningful through our interactions with them, but how do people go about making meaning? What can we learn from an ethnography about the production of identity, creation of kinship, and use of diamonds in understanding selves and social relationships? By what means do people positioned within a globalized political-economy and a compelling universe of advertising interact locally with these tiny polished rocks? This book draws on 12 months of fieldwork with diamond consumers in New York City as well as an analysis of the iconic De Beers campaign that promised romance, status, and glamour to anyone who bought a diamond to show that this thematic pool is just one resource among many that diamond owners draw upon to engage with their own stones. The volume highlights the important roles that memory, context, and circumstance also play in shaping how people interpret and then use objects in making personal worlds. It shows that besides operating as subjects in an ad-burdened universe, consumers are highly creative, idiosyncratic, and theatrical agents.
Geochemistry, Geophysics, Geosystems: G3, in press available
Technology
geophsyics - magnetics
Abstract: Remanent magnetization in geological samples may record the past intensity and direction of planetary magnetic fields. Traditionally, this magnetization is analyzed through measurements of the net magnetic moment of bulk millimeter to centimeter sized samples. However, geological samples are often mineralogically and texturally heterogeneous at submillimeter scales, with only a fraction of the ferromagnetic grains carrying the remanent magnetization of interest. Therefore, characterizing this magnetization in such cases requires a technique capable of imaging magnetic fields at fine spatial scales and with high sensitivity. To address this challenge, we developed a new instrument, based on nitrogenvacancy centers in diamond, which enables direct imaging of magnetic fields due to both remanent and induced magnetization, as well as optical imaging, of room-temperature geological samples with spatial resolution approaching the optical diffraction limit. We describe the operating principles of this device, which we call the quantum diamond microscope (QDM), and report its optimized image-area-normalized magnetic field sensitivity (20 µT?µm/Hz½), spatial resolution (5 µm), and field of view (4 mm), as well as trade-offs between these parameters. We also perform an absolute magnetic field calibration for the device in different modes of operation, including three-axis (vector) and single-axis (projective) magnetic field imaging. Finally, we use the QDM to obtain magnetic images of several terrestrial and meteoritic rock samples, demonstrating its ability to resolve spatially distinct populations of ferromagnetic carriers.
Abstract: Photoluminescence (PL) mapping provides a means to identify the distribution of optical centers in diamond. To demonstrate the impact of this method on the field of gemology and the study of diamonds, photoluminescence maps were acquired from a laboratory-irradiated brownish orange HPHT synthetic diamond of mixed diamond type. Acquisition time for each PL map was less than four minutes. Analysis of the maps confirmed that optical centers are incorporated in diamond growth sectors, such as {111} octahedral, {100} cubic, {110} dodecahedral, and {113} trapezohedral. The remarkable correlation between optical defects and growth sectors in the sample demonstrates that high-speed photoluminescence mapping is ideal for rapidly determining the distribution of optical defects resulting from both diamond growth and treatments. We anticipate that this technique will allow gemological labs to continue to identify increasingly sophisticated synthetic diamonds and color treatments, helping to ensure consumer confidence in the diamond industry.
Geochimica et Cosmochimica Acta, in press available, 23p.
Technology
diamond inclusions
Abstract: Base metal sulphide (BMS) inclusions in diamonds provide a unique insight into the chalcophile and highly siderophile element composition of the mantle. Entombed within their diamond hosts, these provide a more robust (closed system) sample, from which to determine the trace element, Re-Os and S-isotopic compositions of the mantle than mantle xenoliths or orogenic peridotites, as they are shielded from alteration during ascent to the Earth’s crust and subsequent surface weathering. However, at temperatures below 1100 °C some BMS inclusions undergo subsolidus re-equilibration from an original monosulphide solid solution (Mss) and this causes fractionation of the major and trace elements within the inclusions. Thus to study the subjects noted above, current techniques require the entire BMS inclusion to be extracted for analyses. Unfortunately, ‘flaking’ of inclusions during break-out is a frequent occurrence and hence the risk of accidentally under-sampling a portion of the BMS inclusion is inherent in current practices. This loss may have significant implications for Re-Os isotope analyses where incomplete sampling of a Re-rich phase, such as chalcopyrite that typically occurs at the outer margins of BMS inclusions, may induce significant bias in the Re-Os and 187Os/188Os measurements and resulting model and isochron ages. We have developed a method for the homogenisation of BMS inclusions in diamond prior to their break-out from the host stone. Diamonds are heated to 1100 °C and then quenched to chemically homogenise any sulphide inclusions for both major and trace elements. Using X-ray Computed Microtomography (µCT) we determine the shape and spatial setting of multiple inclusions within a host stone and crucially show that the volume of a BMS inclusion is the same both before and after homogenisation. We show that the homogenisation process significantly reduces the inherent variability of in situ analysis when compared with unhomogenised BMS, thereby widening the scope for multiple methods for quantitative analysis, even on ‘flakes’ of single BMS inclusions. Finally we show that the trace elements present in peridotite (P-type) and eclogitic (E-type) BMS are distinct, with P-type diamonds having systematically higher total platinum-group element (particularly Os, Ir, Ru) and Te and As concentrations. These distinctions suggest that the PGE and semi-metal budgets of mantle-derived partial melts will be significantly dependent upon the type(s) and proportions of sulphides present in the mantle source.
Abstract: A fundamental goal of mineralogy and petrology is the deep understanding of mineral phase relationships and the consequent spatial and temporal patterns of mineral coexistence in rocks, ore bodies, sediments, meteorites, and other natural polycrystalline materials. The multi-dimensional chemical complexity of such mineral assemblages has traditionally led to experimental and theoretical consideration of 2-, 3-, or n-component systems that represent simplified approximations of natural systems. Network analysis provides a dynamic, quantitative, and predictive visualization framework for employing “big data” to explore complex and otherwise hidden higher-dimensional patterns of diversity and distribution in such mineral systems. We introduce and explore applications of mineral network analysis, in which mineral species are represented by nodes, while coexistence of minerals is indicated by lines between nodes. This approach provides a dynamic visualization platform for higher-dimensional analysis of phase relationships, because topologies of equilibrium phase assemblages and pathways of mineral reaction series are embedded within the networks. Mineral networks also facilitate quantitative comparison of lithologies from different planets and moons, the analysis of coexistence patterns simultaneously among hundreds of mineral species and their localities, the exploration of varied paragenetic modes of mineral groups, and investigation of changing patterns of mineral occurrence through deep time. Mineral network analysis, furthermore, represents an effective visual approach to teaching and learning in mineralogy and petrology.
Mineralogy and Petrology, Vol. 111, 4, pp. 431-433.
Technology
mineralogy
Abstract: Accessory minerals are a common species in igneous and metamorphic rocks that are not considered characteristic of the host rock and hence do not affect its root name. Accessories tend to be complex in terms of their chemical and isotopic composition and their structural state. In spite of not being major rock constituents, they are, however, of enormous petrologic interest as they contain a record of the formation and post-formation history of their host rock. The study of accessory minerals hence has increased continuously during the past years, and still increases (Fig. 1). Recent progress is driven by new analytical opportunities of (in situ) micro-techniques. More and more the internal textures, that is, elemental, isotopic, and/or structural distribution patterns within individual grains, have come into the focus of researchers; a few examples are compiled in Fig. 2.
Abstract: Nicole Januszczak, part of De Beers’ Canadian exploration team, and Stephan Kurszlaukis, a kimberlite petrologist working at De Beers Canada’s Calgary Operational Support Centre, volunteered their time to participate in the Student-Industry Mineral Exploration Workshop organized by the Prospectors and Developers Association of Canada in Sudbury, ON. Twenty-six senior geoscience students from across Canada were hand-picked from post-secondary institutions across the country to take part in the event designed to provide a unique opportunity to experience many facets of the mineral exploration industry. Two of the students who took part in the event are working as summer employees for De Beers Exploration in Canada.
Abstract: Despite the advanced stage of diamond thin-film technology, with applications ranging from superconductivity to biosensing, the realization of a stable and atomically thick two-dimensional diamond material, named here as diamondene, is still forthcoming. Adding to the outstanding properties of its bulk and thin-film counterparts, diamondene is predicted to be a ferromagnetic semiconductor with spin polarized bands. Here, we provide spectroscopic evidence for the formation of diamondene by performing Raman spectroscopy of double-layer graphene under high pressure. The results are explained in terms of a breakdown in the Kohn anomaly associated with the finite size of the remaining graphene sites surrounded by the diamondene matrix. Ab initio calculations and molecular dynamics simulations are employed to clarify the mechanism of diamondene formation, which requires two or more layers of graphene subjected to high pressures in the presence of specific chemical groups such as hydroxyl groups or hydrogens.
Abstract: Experimental studies of phase relations in the oxide–silicate system MgO–FeO–SiO2 at 24 GPa show that the peritectic reaction of bridgmanite controls the formation of stishovite as a primary in situ mineral of the lower mantle and as an effect of the stishovite paradox. The stishovite paradox is registered in the diamond-forming system MgO–FeO–SiO2–(Mg–Fe–Ca–Na carbonate)–carbon in experiments at 26 GPa as well. The physicochemical mechanisms of the ultrabasic–basic evolution of deep magmas and diamondforming media, as well as their role in the origin of the lower mantle minerals and genesis of ultradeep diamonds, are studied.
Nuclear instruments and methods in Physics Research Section B , Vol. 123 ( 1-4) pp. 579-582.
Technology
spectrometry
Abstract: A brief overview is provided of the uses of AMS in mineral analysis, emphasizing the selection of appropriate samples. Simple guidelines are given for judging the suitability of a set of samples (and the type of problem that they pose) for AMS, as opposed to other methods of in-situ analysis. Optimal interpretation of the AMS data requires that the method be employed in conjunction with a range of other types of information. These include textural and mineralogical observations obtained with petrographic or scanning electron microscopes, plus in-situ chemical data for areas of the target typically 1–250 ?m in diameter, obtained by some combination of complementary techniques, such as electron, proton or ion microprobe analysis (EPM, PIXE and SIMS, respectively).
Geochimica et Cosmochimica Acta, Vol. 216, pp. 335-357.
Technology
diamond inclusions - microtomography
Abstract: Base metal sulphide (BMS) inclusions in diamonds provide a unique insight into the chalcophile and highly siderophile element composition of the mantle. Entombed within their diamond hosts, these provide a more robust (closed system) sample, from which to determine the trace element, Re-Os and S-isotopic compositions of the mantle than mantle xenoliths or orogenic peridotites, as they are shielded from alteration during ascent to the Earth’s crust and subsequent surface weathering. However, at temperatures below 1100 °C some BMS inclusions undergo subsolidus re-equilibration from an original monosulphide solid solution (Mss) and this causes fractionation of the major and trace elements within the inclusions. Thus to study the subjects noted above, current techniques require the entire BMS inclusion to be extracted for analyses. Unfortunately, ‘flaking’ of inclusions during break-out is a frequent occurrence and hence the risk of accidentally under-sampling a portion of the BMS inclusion is inherent in current practices. This loss may have significant implications for Re-Os isotope analyses where incomplete sampling of a Re-rich phase, such as chalcopyrite that typically occurs at the outer margins of BMS inclusions, may induce significant bias in the Re-Os and 187Os/188Os measurements and resulting model and isochron ages. We have developed a method for the homogenisation of BMS inclusions in diamond prior to their break-out from the host stone. Diamonds are heated to 1100 °C and then quenched to chemically homogenise any sulphide inclusions for both major and trace elements. Using X-ray Computed Microtomography (µCT) we determine the shape and spatial setting of multiple inclusions within a host stone and crucially show that the volume of a BMS inclusion is the same both before and after homogenisation. We show that the homogenisation process significantly reduces the inherent variability of in situ analysis when compared with unhomogenised BMS, thereby widening the scope for multiple methods for quantitative analysis, even on ‘flakes’ of single BMS inclusions. Finally we show that the trace elements present in peridotite (P-type) and eclogitic (E-type) BMS are distinct, with P-type diamonds having systematically higher total platinum-group element (particularly Os, Ir, Ru) and Te and As concentrations. These distinctions suggest that the PGE and semi-metal budgets of mantle-derived partial melts will be significantly dependent upon the type(s) and proportions of sulphides present in the mantle source.
Abstract: The eternity of the world and, correlatively, the cyclical nature of time were agreed upon by all Greek philosophical schools except the Platonists. As for matter, all of them posited that it was eternal so that the idea that something could be made from nothing was considered as pure absurdity. With the advent of Christianity, however, a matter coeternal with God raised fundamental theological difficulties. Toward the end of the second century, apologists such as Tatian the Assyrian, Theophilus of Antioch, Irenaeus of Lyons or Tertullian thus emphasized God's absolute freedom and power by claiming that Creation had been made from nothing. Along with the Passion of Christ and the Last Judgment, the initial moment defined by the Creation then conferred to time an irreversible, linear orientation and to history both a new sense and an obsessing concern for chronology. Unambiguously, the Creation became the reference point for the world's history. From Scripture analyses, one determined that it took place about 5500 years earlier within a framework where the History of man and that of the earth were not distinct. Having designed a consistent, universal time scale from chronological data recorded for all ancient peoples, Eusebius of Caesarea could thus attribute to the Great Flood the fossils found on the top of Mount Lebanon. The short Mosaic chronologies were eventually rejected during the 18th century, but Eusebius’ chronological procedure was unknowingly transposed when a relative geological timescale was then set up from the fossil record. The close association of Creation with Christian dogma in turn induced some circles to reject the second law of thermodynamics at the end of the 19th century and, a few decades later, the thesis of an expanding universe. In both cases, the reason was that continuously increasing entropy would imply some low-entropy initial state akin to a Creation.
Abstract: Zircon- and bulk-rock Zr-based thermometric parameters have become fundamental to petrogenetic models of magmatism, from which broader geochronological and tectonic implications are being made. In particular, petrogenetic models have become increasingly reliant on Ti concentration in zircon geothermometry (TZircTi) and zircon saturation temperature (TZircsat). A feature of many of these studies is an implicit assumption that all zircons present in the host igneous rock are autocrystic, that is, crystallised from the surrounding melt. However, it has long been recognised that zircons present in an igneous rock can be inherited either from the surrounding country rock or source region (xenocrysts), or from earlier phases of magmatism or the magmatic plumbing system (antecrysts). Distinguishing these different origins for zircon crystals or domains within crystals is not straightforward. Here, we first review the utility and reliability of zircon-based thermometers for petrogenetic studies and show that TZircsat is a theoretical temperature and cannot be used to constrain magmatic or partial melting temperatures. It is a dynamic variable that changes during magma crystallisation, and essentially increases as fractional crystallisation proceeds, whereas true magmatic temperatures (TMagma) decrease. Generally, in Temperature-SiO2 space, the cross-over point of these two temperatures is magmatic system dependent, and also affected by the type of calibration used for the TZircsat calculations. Consequently, each magmatic system needs to be evaluated independently to assess the validity and usefulness of TZircsat. A fundamental conclusion of TZircsat and TMagma relationships assessed here is that new zircon generally only crystallises in silicic (granitic/rhyolitic) melt compositions, and thus autocrystic zircons should not be assumed to be present in igneous rocks with bulk compositions < 64 wt% SiO2, although inherited and minor zircons crystallising from late-stage differentiated melt pockets can be present. This highlights the importance of discriminating autocrystic from inherited zircons in igneous rocks. We then review techniques available to discriminate autocrystic from inherited zircons, and propose a new methodology to assist in the identification of autocrystic zircons for emplacement age determination and separate evaluation of inherited zircon components. The approach uses two strands of data: 1) zircon data such as zircon morphologies, textures, compositions and U-Pb ages, and 2) whole-rock data, in particular SiO2 and coupled geothermometry (TZircsat and TMagma) to estimate whether the magma was zircon-saturated or undersaturated. To test this new protocol, we use as examples, several Phanerozoic granitic rocks intersected by drilling in Queensland where contextual information is limited, and show how antecrystic and xenocrystic zircons and monazites can be distinguished. In contrast, where zircons are metamict (for example, high U and Th-rich zircons), much of the ability to discriminate is impacted because such zircons have suffered Pb loss and have modified compositions (e.g., higher TZircTi). We recommend an integrated approach incorporating whole-rock chemistry, independent geothermometric constraints, zircon composition, textures and ages obtained by routine cathodoluminescence and LA-ICP-MS or ion microprobe analysis to provide increased confidence for the discrimination of inherited zircons from autocrystic zircons and determination of the emplacement age.
Abstract: Elastic geothermobarometry is a method of determining metamorphic conditions from the excess pressures exhibited by mineral inclusions trapped inside host minerals. An exact solution to the problem of combining non-linear Equations of State (EoS) with the elastic relaxation problem for elastically isotropic spherical host-inclusion systems without any approximations of linear elasticity is presented. The solution is encoded into a Windows GUI program EosFit-Pinc. The program performs host-inclusion calculations for spherical inclusions in elastically isotropic systems with full P-V-T EoS for both phases, with a wide variety of EoS types. The EoS values of any minerals can be loaded into the program for calculations. EosFit-Pinc calculates the isomeke of possible entrapment conditions from the pressure of an inclusion measured when the host is at any external pressure and temperature (including room conditions), and it can calculate final inclusion pressures from known entrapment conditions. It also calculates isomekes and isochors of the two phases.
Zeitschrfit fur Kristallographie, Vol. 231, pp. 467-473.
Technology
diamond inclusions
Abstract: We describe the experimental protocols necessary to measure the crystal structures of minerals trapped within diamonds by single-crystal X-ray diffraction to the same quality as obtained from minerals studied at ambient conditions. The results show that corrections for X-ray absorption in complex cases can be made with good precision. Comparison of the refined structure of a single-crystal olivine inclusion inside a diamond with the structure of a similar olivine held in a high-pressure diamond-anvil cell shows that data resolution, not the correction for absorption effects, is the dominant factor in influencing the quality of structures determined at high pressures by single-crystal X-ray diffraction.
Abstract: his article presents statistical data and distinctive features for several thousand HPHT-grown synthetic diamonds examined by GIA from 2007 through 2016. This study, the first comprehensive summary published on such a large number and wide variety of samples, describes the reliable means of identifying them, with a focus on material currently marketed for jewelry use. The color of HPHT synthetic diamonds analyzed by GIA has shifted noticeably during this time—in the early years, orange-yellow, yellow, and yellow-orange samples comprised the overwhelming majority, while colorless and blue samples are much more prevalent today. HPHT synthetics are making inroads into the large diamond market, with cut stones larger than 10 carats, as well as the colorless melee market, where small HPHT synthetics are being mass-produced in China. HPHT synthetics can be identified by their distinctive fluorescence patterns using the DiamondView luminescence imaging instrument, the lack of “strain” (anomalous birefringence) when viewed through crossed polarizers, and to a lesser extent by the detection of various features in photoluminescence (PL) spectroscopy. This material may also display magnetism and a short-wave fluorescence and phosphorescence reaction that are inconsistent with similarly colored natural diamonds.
Journal of Applied Crystallography, Vol. 49, pp. 1377-1382.
Technology
analyses
Abstract: EosFit7-GUI is a full graphical user interface designed to simplify the analysis of thermal expansion and equations of state (EoSs). The software allows users to easily perform least-squares fitting of EoS parameters to diffraction data collected as a function of varying pressure, temperature or both. It has been especially designed to allow rapid graphical evaluation of both parametric data and the EoS fitted to the data, making it useful both for data analysis and for teaching.
Abstract: Jeffbenite, ideally Mg3Al2Si3O8, previously known as tetragonal-almandine-pyrope-phase (‘TAPP’), has been characterized as a new mineral from an inclusion in an alluvial diamond from São Luiz river, Juina district of Mato Grosso, Brazil. Its density is 3.576 g/cm3 and its microhardness is ?7. Jeffbenite is uniaxial (-) with refractive indexes ??=?1.733(5) and ??=?1.721(5). The crystals are in general transparent emerald green. Its approximate chemical formula is (Mg2.62Fe2+0.27)(Al1.86Cr0.16)(Si2.82Al0.18)O12 with very minor amounts of Mn, Na and Ca. Laser ablation ICP-MS showed that jeffbenite has a very low concentration of trace elements. Jeffbenite is tetragonal with space group I4¯2d, cell edges being a?=?6.5231(1) and c?=?18.1756(3) Å. The main diffraction lines of the powder diagram are [d (in Å), intensity, hkl]: 2.647, 100, 2 0 4; 1.625, 44, 3 2 5; 2.881, 24, 2 1 1; 2.220, 19, 2 0 6; 1.390, 13, 4 2 4; 3.069, 11, 2 0 2; 2.056, 11, 2 2 4; 1.372, 11, 2 0 12. The structural formula of jeffbenite can be written as (M1)(M2)2(M3)2(T1)(T2)2O12 with M1 dominated by Mg, M2 dominated by Al, M3 dominated again by Mg and both T1 and T2 almost fully occupied by Si. The two tetrahedra do not share any oxygen with each other (i.e. jeffbenite is classified as an orthosilicate). Jeffbenite was approved as a new mineral by the IMA Commission on New Minerals and Mineral Names with the code IMA 2014-097. Its name is after Jeffrey W. Harris and Ben Harte, two world-leading scientists in diamond research. The petrological importance of jeffbenite is related to its very deep origin, which may allow its use as a pressure marker for detecting super-deep diamonds. Previous experimental work carried out on a Ti-rich jeffbenite establishes that it can be formed at 13 GPa and 1700 K as maximum P-T conditions.
Abstract: It is widely assumed that mineral inclusions and their host diamonds are ‘syngenetic’ in origin, which means that they formed simultaneously and from the same chemical processes. Mineral inclusions that, instead, were formed earlier with respect to diamonds are termed protogenetic. However, minerals can have the same age as the diamonds in that they become enclosed in and isolated from any further isotopic exchange. But this is termed ‘synchronous’ not ‘syngenetic’. Here we demonstrate conclusively the protogenesis of inclusions in diamonds, based upon data from an exceptional fragment of a diamond-bearing peridotite, its clinopyroxene and a gem-quality diamond. Clinopyroxenes in the xenolith had the same chemistry and crystallographic orientation as those for inclusions in the diamond. With our results with garnets, olivines and sulfides, we can state that a major portion of the mineral inclusions in non-coated, monocrystalline-lithospheric diamonds are protogenetic. Our discovery here presented has implications for all genetic aspects of diamond growth, including their ages.
Abstract: Zircon- and bulk-rock Zr-based thermometric parameters have become fundamental to petrogenetic models of magmatism, from which broader geochronological and tectonic implications are being made. In particular, petrogenetic models have become increasingly reliant on Ti concentration in zircon geothermometry (TZircTi) and zircon saturation temperature (TZircsat). A feature of many of these studies is an implicit assumption that all zircons present in the host igneous rock are autocrystic, that is, crystallised from the surrounding melt. However, it has long been recognised that zircons present in an igneous rock can be inherited either from the surrounding country rock or source region (xenocrysts), or from earlier phases of magmatism or the magmatic plumbing system (antecrysts). Distinguishing these different origins for zircon crystals or domains within crystals is not straightforward. Here, we first review the utility and reliability of zircon-based thermometers for petrogenetic studies and show that TZircsat is a theoretical temperature and cannot be used to constrain magmatic or partial melting temperatures. It is a dynamic variable that changes during magma crystallisation, and essentially increases as fractional crystallisation proceeds, whereas true magmatic temperatures (TMagma) decrease. Generally, in Temperature-SiO2 space, the cross-over point of these two temperatures is magmatic system dependent, and also affected by the type of calibration used for the TZircsat calculations. Consequently, each magmatic system needs to be evaluated independently to assess the validity and usefulness of TZircsat. A fundamental conclusion of TZircsat and TMagma relationships assessed here is that new zircon generally only crystallises in silicic (granitic/rhyolitic) melt compositions, and thus autocrystic zircons should not be assumed to be present in igneous rocks with bulk compositions < 64 wt% SiO2, although inherited and minor zircons crystallising from late-stage differentiated melt pockets can be present. This highlights the importance of discriminating autocrystic from inherited zircons in igneous rocks. We then review techniques available to discriminate autocrystic from inherited zircons, and propose a new methodology to assist in the identification of autocrystic zircons for emplacement age determination and separate evaluation of inherited zircon components. The approach uses two strands of data: 1) zircon data such as zircon morphologies, textures, compositions and U-Pb ages, and 2) whole-rock data, in particular SiO2 and coupled geothermometry (TZircsat and TMagma) to estimate whether the magma was zircon-saturated or undersaturated. To test this new protocol, we use as examples, several Phanerozoic granitic rocks intersected by drilling in Queensland where contextual information is limited, and show how antecrystic and xenocrystic zircons and monazites can be distinguished. In contrast, where zircons are metamict (for example, high U and Th-rich zircons), much of the ability to discriminate is impacted because such zircons have suffered Pb loss and have modified compositions (e.g., higher TZircTi). We recommend an integrated approach incorporating whole-rock chemistry, independent geothermometric constraints, zircon composition, textures and ages obtained by routine cathodoluminescence and LA-ICP-MS or ion microprobe analysis to provide increased confidence for the discrimination of inherited zircons from autocrystic zircons and determination of the emplacement age.
Abstract: Perovskite is one of the most common crystal structures on the planet, but why is it so interesting to researchers from many scientific disciplines? Science looks into the properties of this odd cube of atoms, and what cutting-edge research is being performed on its many varieties.
Geostandards and Geoanalyical Review, Nov. 17, in press available
Technology
review
Abstract: This bibliographic review covers the research contained in twenty-one scientific journals with important contributions to geoanalysis and related scientific fields (Table 1, Figure 1). The relevance of well characterised reference materials (RMs) used as calibration materials or quality control samples for precise and accurate analyses is widely known and has often been described, for example, by Jochum and Enzweiler (2014).
Abstract: We report on the quantum yield (?) and decay time (?) measurements at room temperature for the bright red-orange (602 nm) luminescence from new germanium-vacancy (Ge-V) centers in nano- and microcrystalline diamonds synthesized at high pressure and high temperature. The values ? = 3 ± 1% and ? = 6.2±0.2 ns were found. The Stokes shift measured as the energy difference between the maxima of the luminescence and luminescence excitation spectra is negligible. The relative intensity of the zero-phonon line constitutes up to 70% from the total intensity of the luminescence. Results of our ab initio DFT calculations for the ground-state electronic and vibrational structure of (Ge-V)? in diamond are presented and discussed.
Abstract: To date, the eponymous color-changing behavior of chameleon diamonds lacks an explanation in terms of an identified diamond defect structure or process. Well known, however, is that this color-change is driven by the influence of both light and heat. In this paper, we present observations of how luminescence emission in chameleon diamonds responds to temperature changes and optical pumping. Fluorescence, phosphorescence, and thermoluminescence experiments on a suite of natural chameleon diamonds reveal that a specific emission band, peaking near 550 nm, may be stimulated by several different mechanisms. We have observed thermal quenching of the 550 nm emission band with an activation energy of 0.135 eV. The 550 nm band is also observed in phosphorescence and thermoluminescence. Thermoluminescence spectra suggest the presence of low lying acceptor states at 0.7 eV above the valence band. When excited with 270 nm light, we observe emission of light in two broad spectral bands peaking at 500 and 550 nm. We suggest that the 550 nm emission band results from donor—acceptor pair recombination (DAPR) from low lying acceptor states at ca. 0.7 eV above the valence band and donor states approximately 2.5 to 2.7 eV above the valence band. We do not identify the structure of these defects. We propose a speculative model of the physics of the color change from ‘yellow’ to ‘green’ which results from increased broad-band optical absorption in the near-IR to visible due to transitions from the valence band into un-ionized acceptor states available in the ‘green’ state of the chameleon diamond. We report near-IR absorption spectra confirming the increased absorption of light in the near-IR to visible in the ‘green’ when compared to the ‘yellow’ state with a threshold at ca. 0.65 eV, supporting the proposed model.
Abstract: The graphite-to-diamond transformation under shock compression has been of broad scientific interest since 1961. The formation of hexagonal diamond (HD) is of particular interest because it is expected to be harder than cubic diamond and due to its use in terrestrial sciences as a marker at meteorite impact sites. However, the formation of diamond having a fully hexagonal structure continues to be questioned and remains unresolved. Using real-time (nanosecond), in situ x-ray diffraction measurements, we show unequivocally that highly oriented pyrolytic graphite, shock-compressed along the c axis to 50 GPa, transforms to highly oriented elastically strained HD with the (100)HD plane parallel to the graphite basal plane. These findings contradict recent molecular dynamics simulation results for the shock-induced graphite-to-diamond transformation and provide a benchmark for future theoretical simulations. Additionally, our results show that an earlier report of HD forming only above 170 GPa for shocked pyrolytic graphite may lead to incorrect interpretations of meteorite impact events.
Abstract: Observations of discordant ages, meaning that an age given by one mineral geochronometer is different from the age given by another geochronometer from the same rock, began in the early days of geochronology. In the late 1950s and 1960s, discordant U-Pb zircon ages were unquestioningly attributed to Pb diffusion at high temperature. Later, the mineralogical properties and the petrogenesis of the zircon crystals being dated was recognized as a key factor in obtaining concordant U-Pb ages. Advances in analytical methods allowed the analysis of smaller and smaller zircon multigrain fractions, then the analysis of individual grains, and even pieces of grains, with higher degrees of concordancy. Further advances allowed a higher analytical precision, a clearer perception of accuracy, and a better statistical resolution of age discordance. As for understanding the cause(s) of discordance, belief revision followed the coupling of imaging, cathodoluminescence (CL), and backscattered electrons (BSE), to in situ dating by secondary ion mass spectrometry (SIMS) or by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Discordant zircon and other accessory minerals (e.g., monazite, apatite, etc.) often consist of young rims accreted onto/into older cores. Age gradients are sharp, and no Pb diffusion gradients are observed. As U-Pb discordance in crystalline, non-radiation damaged grains is caused by diachronous, heterochemical mineral generations, interpretations of mineral ages, based on the exclusive role of diffusion, are superseded, and closure temperatures of zircon and monazite are irrelevant in geological reality. Other isotopic systems (Rb-Sr, K-Ar) were believed, since the 1960s, to be similarly controlled by the diffusivity of radiogenic daughters. When zircon and monazite discordance were recognized as zone accretion/reaction with sharp boundaries that showed little or no high-temperature diffusive re-equilibration, the other chronometric systems were left behind, and interpretations of mineral ages based on the exclusive role of diffusion survived. The evidence from textural-petrologic imaging (CL, BSE) and element mapping by electron probe microanalyzer (EPMA) or high spatial resolution SIMS or LA-ICP-MS provides the decisive constraints. All microcline and mica geochronometers that have been characterized in detail document patchy textures and evidence for mineral replacement reactions. It is important not to confuse causes and effects; hetero-chemical microstructures are not the cause of Ar and Sr loss; rather, they follow it. Ar and Sr loss by dissolution of the older mineral generation occurs first, heterochemical textures form later, when the replacive assemblage recrystallizes. Heterochemical mineral generations are identified and dated by their Ca/Cl/K systematics in 39Ar-40Ar. Replacive reactions adding or removing Cl, such as, e.g., sericite overgrowths on K-feldspar, retrograde muscovite intergrowths with phengite, etc. are detected by Cl/K vs. Ar/K isotope correlation diagrams. Ca-poor reaction products, such as, e.g., young biotite intergrown with older amphibole, adularia replacing microcline, etc., can be easily identified by Ca/K vs. Ar/K diagrams supported by EPMA analyses. Mixed mineral generations are observed to be the cause of discordant, staircase-shaped age spectra, while step-heating of crystals with age gradients produces concordant plateaus. Age gradients are therefore unrelated to staircase age spectra. There is a profound analogy between the U-Pb, Rb-Sr, and K-Ar systems. Pb and Ar diffusion rates are both much slower than mineral replacement rates for all T < 750 °C. Patchy retrogression textures are always associated with heterochemical signatures (U/Th ratios, REE patterns, Ca/Cl/K ratios). As a rule, single-generation minerals with low amounts of radiation damage give concordant ages, whereas discordance is caused by mixtures of heterochemical, resolvably diachronous, mineral generations in petrologic disequilibrium. This can also include (sub-)grains that have accumulated significant amounts of radiation damage. For accurate geochronology the petrologic characterization with the appropriate technique(s) of the minerals to be dated, and the petrologic context at large, are as essential as the mass spectrometric analyses.
Reviews in Mineralogy & Geochemistry, Vol. 83, Chap. 15, pp. 469-533.
Technology
geochronology
Abstract: Garnet could be the ultimate petrochronometer. Not only can you date it directly (with an accuracy and precision that may surprise some), but it is also a common rock-forming and porphyroblast-forming mineral, with wide ranging—yet thermodynamically well understood—solid solution that provides direct and quantitative petrologic context. While accessory phase petrochronology is based largely upon establishing links to the growth or breakdown of key rock-forming pressure–temperature–composition (P–T–X) indicators (e.g., Rubatto 2002; Williams et al. 2007), garnet is one of those key indicator minerals.
From subcalcic pyropes to uvarovites: experimental crystalllization of Cr-rich garnets in ultramafic systems with presence of Ca bearing hydrous fluid.
Reviews in Mineralogy & Geochemistry, Vol. 83, Chap. 1, pp. 1-12.
Technology
geochronology
Abstract: Question: Why "Petrochronology"? Why add another term to an already cluttered scientific lexicon? Answer: Because petrologists and geochronologists need a term that describes the unique, distinctive way in which they apply geochronology to the study of igneous and metamorphic processes. Other terms just won’t do.
Abstract: There are four main types of natural diamonds and related formation processes. The first type comprises the interstellar nanodiamond particles. The second group includes crustal nano- and micron-scale diamonds associated with coals, sediments and metamorphic rocks. The third one includes nanodiamonds and microndiamonds associated with secondary alteration and replacing of mafic and ultramafic rocks. The fourth one includes macro-, micron- and nano-sized mantle diamonds which are associated with kimberlites, mantle peridotites and eclogites. Each diamond type has its specific characteristics. Nano-sized diamond particles of lowest nanometers in size crystallize from abiotic organic matter at lower pressures and temperatures in space during the stages of protoplanetary disk formation. Nano-sized diamonds are formed from organic matter at P-T exceeding conditions of catagenesis stage of lithogenesis. Micron-sized diamonds are formed from fluids at P-T exceeding supercritical water stability. Macrosized diamonds are formed from metal-carbon and silicate-carbonate melts and fluids at P-T exceeding 1150 °C and 4.5 GPa. Nitrogen and hydrocarbons play an important role in diamond formation. Their role in the formation processes increases from macro-sized to nano-sized diamond particles. Introduction of nitrogen atoms into the diamond structure leads to the stabilization of micron- and nano-sized diamonds in the field of graphite stability.
Abstract: Large and relatively pure diamonds like the historic 3,106 ct Cullinan, found in South Africa in 1905, have long been regarded as unusual based on their physical characteristics. For example, they often exhibit exceptional color and clarity, while routinely qualifying as type IIa, a rare designation of chemical purity. A new research discovery about these Cullinan-like diamonds is that they contain heretofore unknown, deeply derived inclusions that originate below the continental mantle keel and are thus known as "superdeep" diamonds (Smith et al., 2016). Originating from a depth between 360 and 750 km, they reveal information about the conditions within the convecting mantle, beneath the earth’s rigid tectonic plates. Here we review the previously published findings, compare the Cullinan-like diamonds to the more abundant lithospheric diamond population, and offer evidence from some additional diamond samples that further verifies their superdeep origin. Cullinan-like diamonds contain minute and rare silicate and iron-rich metallic inclusions surrounded by a fluid jacket composed of methane and hydrogen. The inclusion compositions suggest that this deep mantle environment contains small pockets of oxygen-deficient metallic liquid out of which the diamonds crystallized. This new and unexpected observation made on the world’s most expensive diamonds is important for understanding the chemical reactions between mineral assemblages in the deep earth. It shows that deep regions of the mantle contain metallic iron, as opposed to the shallower, more oxidized mantle rocks actively participating in plate tectonics and its associated volcanism.
Abstract: Platelets in diamond are extended planar defects that are thought to be generated during the nitrogen aggregation process in type Ia diamonds. They were subjected to intensive research during the 1980s and 1990s but the techniques used for observation of defects in diamond have improved since that time and new insights can be gained by further study. This study combines high resolution Fourier Transform Infrared (FTIR) analysis, with an emphasis on the main platelet peak, and transmission electron microscopic (TEM) imaging. By performing TEM and FTIR analyses on volumes of diamond that were closely spatially related it is shown that the average platelet diameter, D, follows the relationship D=ax?b where x is the position of the platelet peak in the infrared spectrum, a is a constant and b is the minimum position of the platelet peak. The best fit to the data is obtained if a value of b=1360cm?1 is used, giving a fitted value of a=221. The observed variation in infrared (IR) peak width can also be explained in terms of this relationship. Additionally, platelet morphology was found to vary according to diameter with large platelets being more elongated. The tendency to become more elongated can be described by the empirical equation AR=11.9D+19.6+0.4 where AR is the aspect ratio. Using the relationships established here, it will be possible to study platelet abundance and size as a function of parameters such as nitrogen concentration, nitrogen aggregation and diamond residence time in the mantle. This work therefore will open up new methods for constraining the geological history of diamonds of different parageneses and from different localities.
Geochimica et Cosmochimica Acta, Vol. 225, pp. 1-16.
Technology
geobarometry
Abstract: Majoritic garnet [(Ca, Mg, Fe2+)3(Fe3+, Al, Si)2(SiO4)3] is one of the predominant and important constituents of upper mantle peridotite and ultra-deep subducted slabs. Majoritic substitution in garnet depends on pressure, and it has been used to estimate the formation pressure of natural majoritic garnet. Ferric iron (Fe3+) substitution occurs in natural majoritic garnets from mantle diamonds and shocked meteorites. However, available majorite geobarometers were developed without considering the effect of Fe3+ substitution in the structure. In this study, we systematically synthesized Fe3+- bearing majoritic garnets from 6.5?GPa to 15?GPa to evaluate the effect of Fe3+ on the majorite geobarometer. The Fe3+ contents of synthetic majoritic garnets were analyzed using the "Flank method" with the electron probe microanalyzer (EPMA). The results were compared with those based on the charge balance calculations. From the known synthesis pressures and measured Fe3+ contents, we developed a new majorite geobarometer for Fe3+-bearing majoritic garnets. Our results show that the existing majorite geobarometer, which does not take into account the Fe3+ substitution, could underestimate the formation pressure of majoritic garnets, especially for samples with a high majoritic component.
Diamond & Related Materials, Vol. 83, pp. 104-108.
Technology
luminescence
Abstract: The luminescence of triboplasma during diamond polishing was investigated. The main luminescence in the ultraviolet range came from N2 molecules in the air. The colors of the visible range of triboplasma were the same as those observed in the photoluminescence images, excited by the ultraviolet light. The color of the triboplasma luminescence was green for type Ib diamond, which was mainly from the H3 center. The blue luminescence for type IIa diamond was mainly from Band A. The correlation between the diamond temperature and periphery speed indicate that that the mechanical abrasion component also increased linearly. However the polishing rate showed a threshold at the periphery speed of 26?km/h which corresponds well with the threshold of the triboplasma generation. These results imply that the electrical and optical energy of the triboplasma excited the defect level at the diamond surface and enhanced the chemical polishing rate of the diamond.
Abstract: In this study, we show how veined lithospheric mantle is involved in the genesis of ultrapotassic magmatism in cratonic settings. We conducted high pressure experiments to simulate vein + wall rock melting within the Earth's lithospheric mantle by reacting assemblages of harzburgite and phlogopite-rich hydrous mantle xenoliths. These comprised a mica-, amphibole-, rutile-, ilmenite-, diopside (MARID) assemblage at 3-5 GPa and 1325-1450 °C. Melting of the MARID assemblages results in infiltration of melt through the harzburgite, leading to its chemical alteration. At 3 and 4 GPa, melts are high in K2O (> 9 wt%) with K2O/Na2O > > 2 comparable to anorogenic lamproites. Higher pressures and temperatures (5 GPa/1450 °C) lead to increasing MgO contents of the melt and to some extent lower K2O contents (5-7 wt%) at equally high K2O/Na2O ratios. Our experiments provide insights into the role of alkalis in nickel-partitioning (DNi) between olivine and ultrapotassic melt. We observe that the high contents of Na, K, and Al are indicative of high DNi values, implying that the melt polymerization is the dominant factor influencing the olivine/melt nickel partitioning. The change of DNi as a function of melt composition results in a pressure independent, empirical geothermometer: Element oxides represent the composition of the glass (in wt%), and DNi is the liquid/olivine Ni-partitioning coefficient. We propose that this geothermometer is applicable to all natural silicate melts that crystallized olivine in a temperature interval between 1000 and 1600 °C. Application to glass-olivine pairs from calc-alkaline settings (Mexico), MORB (East Pacific Rise), and OIB (Hawaii) yielded reasonable values of 996-1199 °C, 1265 °C, and 1330 °C, respectively.
Abstract: Perovskite mineral oxides commonly exhibit extensive solid-solution, and are therefore classified on the basis of the proportions of their ideal end-members. A uniform sequence of calculation of the end-members is required if comparisons are to be made between different sets of analytical data. A Microsoft Excel spreadsheet has been programmed to assist with the classification and depiction of the minerals of the perovskite- and vapnikite-subgroups following the 2017 nomenclature of the perovskite supergroup recommended by the International Mineralogical Association (IMA). Compositional data for up to 36 elements are input into the spreadsheet as oxides in weight percent. For each analysis, the output includes the formula, the normalized proportions of 15 end-members, and the percentage of cations which cannot be assigned to those end-members. The data are automatically plotted onto the ternary and quaternary diagrams recommended by the IMA for depiction of perovskite compositions. Up to 200 analyses can be entered into the spreadsheet, which is accompanied by data calculated for 140 perovskite compositions compiled from the literature.
Abstract: This paper presents a method for determination of the size distribution for diamond nanocrystals containing luminescent nitrogen-vacancy (NV) centers using the luminescence intensity only. We also revise the basic photo physical properties of NV centers and conclude that the luminescence quantum yield of such centers is significantly smaller than the frequently stated 100\%. The yield can be as low as 5\% for centers embedded in nanocrystals and depends on their shape and the refractive index of the surrounding medium. The paper also addresses the value of the absorption cross-section of NV centers.
Abstract: Facets that are nearly parallel to a diamond’s octahedral crystal plane often develop a wavy, rippled appearance called "lizard skin" during polishing (e.g., J.I. Koivula, The MicroWorld of Diamonds, Gemworld International, Northbrook, Illinois, 2000, p. 63). The term is also used more broadly to describe any bumpy, uneven surface texture that develops on polished diamond facets. It is often attributed to polishing off-grain. Recently, GIA’s New York lab encountered a 2.67 ct type IIa diamond (figure 1, left) with especially prominent lizard skin texture on multiple facets (figure 1, center and right). In this case, the texture appears to have developed due to a preexisting deformation fabric or structure inherent to the diamond itself, rather than merely as a consequence of poor polishing technique.
Abstract: An experimental study of the dissolution of natural and synthetic diamonds in a sulfur-bearing iron melt (Fe0.7S0.3) with high P-T parameters (4 GPa, 1400°?) 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.
Diamond & Related Materials, Vol. 81, pp. 161-167.
Technology
microdiamonds
Abstract: Polylactic acid (PLA)-based composites filled with 20 or 50 ?m-diameter microdiamond are synthesized by hot pressing. Through improving the interface compatibility between the filler and the matrix enabled by octadecylamine (ODA) coating on the microdiamond particles, the maximum thermal conductivity of the composites is 2.22 Wm? 1 K? 1, which is a ~ 10-fold increase in comparison with that of pure PLA. According to the analysis on the glass transmission of the composites and the surface chemistry of the fillers using DSC, FI-IR, and Raman microscopy, it is found out that ODA is connected with the -OH group on the microdiamond surface through hydrogen bonding and an interfacial structure of PLA/ODA/microdiamond is formed. Thus, the interfacial thermal transport between PLA and microdiamond is significantly improved, leading to the enhancement of the thermal conductivity of the composites. Our work presents a simple method to modify the surface chemistry of microdiamond and to improve the interface compatibility between microdiamond and PLA. The microdiamond/PLA composites with large thermal conductivity are promising thermal management materials used for modern electronic products.
Gems & Gemology Lab Notes, Vol. 53, 4, pp. 476-478.
Technology
fluoresecence
Abstract: Strong phosphorescence under UV excitation is rarely seen in natural diamond and normally limited to hydrogen-rich type Ia or type IaA/Ib chameleons and type IIb diamonds (T. Hainschwang et al., "A gemological study of a collection of chameleon diamonds," Spring 2005 G&G, pp. 20-35; S. Eaton-Magaña and R. Lu, "Phosphorescence in type IIb diamonds," Diamond and Related Materials, Vol. 20, No. 7, 2011, pp. 983-989). When seen in other diamond types, an even rarer occurrence, it is shorter and less intense. Recently, the National Gemstone Testing Center (NGTC) in Beijing encountered two natural diamonds that showed extraordinarily strong blue phosphorescence and uncommon fluorescence colors under the DiamondView.
Bulletin of the American Physical Society, Mar. 7, 2p.
Technology
meteorites
Abstract: Previous studies have shown that meteorites can contain unusual natural phases, such as quasicrystals, that have otherwise been found only in synthetic samples [1]. Because of this, meteorites are good candidates to search for natural superconductivity, which has only been found in Covellite [2]. Because natural samples are inhomogeneous and superconducting phases can be very small, we used Magnetic Field Modulated Microwave Spectroscopy (MFMMS), which can detect 10-12 cc of superconducting material, three orders of magnitude better than Vibrating Sample Magnetometry (VSM). We measured a series of meteorites, surveying representative samples from most major categories of meteorites. In two of the meteorites, we discovered superconducting phases above 5 K using MFMMS, and verified this using VSM. We characterized these phases using Energy-dispersive X-ray spectroscopy and Inductively Coupled Plasma Mass Spectroscopy. To our knowledge, these samples are the first identification of extraterrestrial superconducting phases. They are particularly significant because these materials could be superconducting in extraterrestrial environments.
Abstract: Alkaline lavas occur globally in subduction-related volcanic arcs. Conventional models for the origin of these lavas typically invoke a multi-stage process in which mantle wedge peridotite, enriched in phlogopite and/or amphibole due to prior metasomatism, partially melts during infiltration by fluids and melts derived from subducted oceanic lithosphere. However, geochemical systematics in the majority of subduction-related alkaline lavas require physical mixing of subducted components and peridotite prior to partial melting. This can be explained by the mélange diapir model, which predicts the generation of arc magmas during advection of buoyant material from the slab-wedge interface into the mantle wedge below arcs. Here we report results from experiments in which natural mélange materials were partially melted at upper mantle conditions to produce alkaline magmas. Partial melts produced in our experiments have trace-element abundance patterns that are typical of alkaline arc lavas, such as enrichment in large ion lithophile elements (LILEs) and depletion in Nb and Ta. These results favor generation of alkaline magmas in the arc and backarc regions of subduction zones by partial melting of mélange materials rather than previously metasomatized peridotite.
Abstract: All living things contain carbon in some form, as it is the primary component of macromolecules including proteins, lipids, nucleic acids (RNA and DNA), and carbohydrates. As a matter of fact, it is the backbone of all organic (chemistry) compounds forming different kinds of bonds. Carbon: The Black, the Gray and the Transparent is not a complete scientific history of the material, but a book that describes key discoveries about this old faithful element while encouraging broader perspectives and approaches to its research due to its vast applications. All allotropes of carbon are described in this book, along with their properties, uses, and methods of procurement or manufacturing. Black carbon is represented by coal, gray carbon is represented by graphite, and transparent carbon is represented by diamond.
Nature Communications, doe:10.1038/ s41467-018- 030808-6 6p. Pdf
Technology
ureilite
Abstract: Planetary formation models show that terrestrial planets are formed by the accretion of tens of Moon- to Mars-sized planetary embryos through energetic giant impacts. However, relics of these large proto-planets are yet to be found. Ureilites are one of the main families of achondritic meteorites and their parent body is believed to have been catastrophically disrupted by an impact during the first 10 million years of the solar system. Here we studied a section of the Almahata Sitta ureilite using transmission electron microscopy, where large diamonds were formed at high pressure inside the parent body. We discovered chromite, phosphate, and (Fe,Ni)-sulfide inclusions embedded in diamond. The composition and morphology of the inclusions can only be explained if the formation pressure was higher than 20?GPa. Such pressures suggest that the ureilite parent body was a Mercury- to Mars-sized planetary embryo.
Physics and Chemistry of Minerals, Vol. 45, 3, pp. 237-247.
Technology
xenolths
Abstract: We determined elastic constants of a single-crystal chromian spinel at temperatures from ?15 to 45 °C through the Rectangular Parallelepiped Resonance method. The sample is a natural chromian spinel, which was separated from a mantle xenolith. Elastic constants at an ambient temperature (T = 24.0 °C) are C 11 = 264.8(1.7) GPa, C 12 = 154.5(1.8) GPa and C 44 = 142.6(0.3) GPa. All the elastic constants decrease linearly with increasing temperature. The temperature derivatives are dC 11/dT = ?0.049(2) GPa/°K, dC 12/dT = ?0.019(1) GPa/°K and dC 44/dT = ?0.020(1) GPa/°K. As an implication of the elastic constants, we applied them to the correction of a fluid inclusion geobarometry, which utilizes residual pressure of fluid inclusion as a depth scale. Before entrainment by a magma, the fluid inclusions must have the identical fluid density in constituent minerals of a xenolith. It has been, however, pointed out that fluid density of fluid inclusions significantly varies with host mineral species. The present study elucidates that elastic constants and thermal expansion coefficients cannot explain the difference in fluid density among mineral species. The density difference would reflect the difference in the degree of plastic deformation in the minerals.
Abstract: We present Microsoft Excel spreadsheets for calculation of thermodynamic functions and P-V-T properties of MgO, diamond and 9 metals, Al, Cu, Ag, Au, Pt, Nb, Ta, Mo, and W, depending on temperature and volume or temperature and pressure. The spreadsheets include the most common pressure markers used in in situ experiments with diamond anvil cell and multianvil techniques. The calculations are based on the equation of state formalism via the Helmholtz free energy. The program was developed using Visual Basic for Applications in Microsoft Excel and is a time-efficient tool to evaluate volume, pressure and other thermodynamic functions using T-P and T-V data only as input parameters. This application is aimed to solve practical issues of high pressure experiments in geosciences and mineral physics.
Geochimica et Cosmochimica Acta, Vol. 232 pp. 206-224.
Technology
diamond - inclusions DFT
Abstract: Diffusivities of helium, deuterium and hydrogen have been characterized in diamond. Polished CVD diamond was implanted with either 3He, 2H, or 1H. Implanted samples were sealed under vacuum in silica glass capsules, and annealed in 1-atm furnaces. 3He, 2H and 1H distributions were measured with Nuclear Reaction Analysis. We obtain these Arrhenius relations: DHe = 4.00?×?10?15 exp(?138?±?14?kJ?mol?1/RT) m2?s?1. D2H = 1.02?×?10?4 exp(?262?±?17?kJ?mol?1/RT) m2?s?1. D1H = 2.60?×?10?4 exp(?267?±?15?kJ?mol?1/RT) m2?s?1. Diffusivities of 1H and 2H agree within experimental uncertainties, indicating little diffusive mass fractionation of hydrogen in diamond. To complement the experimental measurements, we performed calculations using a first-principles quantum mechanical description of diffusion in diamond within the Density Functional Theory (DFT). Differences in 1H and 2H diffusivities from calculations are found to be ?4.5%, reflected in differences in the pre-exponential factor. This small difference in diffusivities, despite the large relative mass difference between these isotopes, is due to the fact that the atomistic process involved in the transition along the diffusion pathway is dictated by local changes to the diamond structures rather than to vibrations involving 1H/2H. This finding is consistent with the experimental results given experimental uncertainties. In contrast, calculations for helium diffusion in diamond indicate a difference of 15% between diffusivities of 3He and 4He. Calculations of diffusion distances for hydrogen using our data yield a distance of 50??m in diamond in 300,000?years at 500?°C and ?30?min at 1400?°C. Diffusion distances for He in diamond are shorter than for H at all temperatures above ?350?°C, but differences increase dramatically with temperature because of the higher activation energy for H diffusion. For example, a 50??m diffusion distance for He would be attained in ?40 Myr at 500?°C and 400?yr at 1400?°C. For comparison, a 50??m diffusion distance for N in diamond would require nearly 1 billion years at 1400?°C. The experimental data indicate that diamonds equilibrate with ambient H and He in the mantle on timescales brief relative to most geological processes and events. However, He diffusion in diamond is slower than in any other mineral measured to date, including other kimberlite-hosted minerals. Under some circumstances, diamond may provide information about mantle He not recoverable from other minerals. One possibility is diamonds entrained in kimberlites. Since the ascent of kimberlite from the mantle to near-surface is very rapid, entrained diamonds may retain most or all of the H and He acquired in mantle environments. Calculations using reasonable ascent rates and T-t paths indicate that He diffusive loss from kimberlite-hosted diamonds is negligible for grains of 1.0-0.2?mm radius, with fractional losses <0.15% for all ascent rates considered. If the host kimberlite magma is effectively quenched in the near-surface (or is erupted), diamonds should contain a faithful record of [He] and He isotopes from the mantle source region. Preservation of H in kimberlite-hosted diamonds is less clear-cut, with model outcomes depending critically upon rates of ascent and cooling.
Abstract: A method for detecting large-size diamonds with low content in a complex mixture was described. Phase identification via conventional X-ray diffraction method is unsuitable because of the large-size and low-content characteristics of the diamonds. Thus, we proposed a convenient approach (i.e., rocking scan) for assessing the presence of low-content diamonds in a complex mixture. A thorough rocking scan of the (111), (220), and (311) planes revealed the presence of low-content diamonds prepared by reducing dense carbon dioxide with alkali metals. This procedure can be successfully applied to several standard mixture samples prepared by mixing ?-SiO2, ?-Al2O3, graphite, and pure diamond powders, which are commercially available. We estimated that the detection limit was at or below the 0.1?wt% level by using the proposed method under the current condition. This method is straightforward, routinized, and may be specifically developed to satisfy the requirements of public and private institutions for a rapid identification of other mixture phases, of which the large-size and low-content characteristics do not allow an instant phase identification by conventional X-ray diffraction methods.
Abstract: We document an exceptionally large, 25.85 ct diamond that shows a slight colour change but exhibits some atypical properties for chameleon diamonds, including white luminescence to long- and short-wave UV radiation, as well as a network-like pattern seen in most orientations with the DiamondView. In considering whether to call this a chameleon diamond, we undertook a review of available data to compile the properties that are commonly exhibited by these gems. We found that, in addition to their defining photochromic and thermochromic behaviour, nine characteristics all must be present: long-lasting yellow phosphorescence, a zoned DiamondView growth pattern showing yellow-green/blue/inert areas, the presence of dominant A aggregates and also some hydrogen in the infrared spectrum, a continuum of absorption in the visible range related to a very weak type Ib character, a 480 nm absorption band that is possibly related to trace amounts of oxygen, a 425 nm absorption band, a weaker absorption band in the red to near-infrared region consistent with hydrogen-related defects, and traces of nickel detected with photoluminescence spectroscopy.
Abstract: Engineering coherent systems is a central goal of quantum science. Color centers in diamond are a promising approach, with the potential to combine the coherence of atoms with the scalability of a solid-state platform. We report a color center that shows insensitivity to environmental decoherence caused by phonons and electric field noise: the neutral charge state of silicon vacancy (SiV0). Through careful materials engineering, we achieved >80% conversion of implanted silicon to SiV0. SiV0 exhibits spin-lattice relaxation times approaching 1 minute and coherence times approaching 1 second. Its optical properties are very favorable, with ~90% of its emission into the zero-phonon line and near -transform-limited optical linewidths. These combined properties make SiV0 a promising defect for quantum network applications.
Abstract: In October 2017, a natural diamond overgrown by a thick layer of CVD synthetic diamond was identified at the Beijing laboratory of the National Gemstone Testing Center (NGTC). The round-brilliant-cut sample was near-colourless and weighed 0.11 ct. No sign of the overgrowth was observed with magnification. However, DiamondView images showed a distinct boundary in the pavilion separating layers of different luminescence: The upper layer displayed red fluorescence with greenish blue phosphorescence, while the lower portion showed deep blue fluorescence and no phosphorescence. Infrared spectroscopy revealed that the upper layer was type IIa and the lower portion was type Ia. Ultraviolet-visible-near infrared (UV-Vis-NIR) spectroscopy recorded an unusual co-existence of the N3 centre at 415 nm together with absorption due to [Si-V]-defects at 737 nm. The photoluminescence (PL) spectrum confirmed a high level of [Si-V]-defects. The approximate thickness of the CVD synthetic layer was ~740 µm, which is much thicker than previously reported for such overgrowths. The presence of the N3 centre in the natural diamond layer caused this sample to be passed as natural by various screening instruments. Luminescence imaging is key to identifying such overgrowths, and should be relied upon more heavily in the screening procedures used by gemmological laboratories in the future.
Abstract: The Carlsbad laboratory recently examined a 0.70 ct, E-color round brilliant. Infrared spectroscopy showed this to be a type IIa diamond, so we performed a variety of additional spectroscopy and imaging to verify its natural origin. This diamond also had I1 clarity due to a large inclusion under the table (figure 1). Raman analysis of the inclusions verified that this crystal was a metastable composite of the minerals wollastonite (CaSiO3) and CaSiO3-breyite (E.M. Smith et al., “The very deep origin of the world’s biggest diamonds,” Winter 2017 G&G, pp. 388-403), which indicates a sublithospheric origin. These minerals are believed to be the lower-pressure phases of CaSiO3-perovskite. Around these minerals were large disk-like graphitic fractures indicating inclusion expansion as pressures on the diamond reduced during exhumation from the mantle. The other inclusion present was unidentifiable due to its graphitic casing. Recent research of inclusions in other type II diamonds shows that many, if not most, have a superdeep origin (again, see Smith et al., 2017). This stone is one more example of diamonds forming at incredible depths of 360-750 km before being transported to near the surface.
Abstract: Inclusions can tell us a great deal about a diamond’s formation history. Inclusions such as olivine, garnet, and chromite are more common, while others such as kyanite, zircon, and corundum (Al2O3) can be quite rare. Regardless of their rarity, diamond inclusions are often quite fascinating as they trap a small bit of the deep earth that cannot otherwise be sampled.
