Kokchetav Massif Research Articles

U–Pb Age and Mineral Inclusions in Zircon from Diamondiferous Garnet–Pyroxene Rocks of the Kumdy-Kol Microdiamond Deposit in Northern Kazakhstan

Abstract ––This paper describes the results of studying inclusions and determining the U–Pb age in zircon from the diamondiferous garnet–pyroxene rock of the Kumdy-Kol metamorphogenic diamond deposit, located in the Kokchetav subduction-collision zone. The distribution of rare earth elements in garnet and clinopyroxene is used as a basis for estimating the equilibrium pressure (5.5 ± 0.3 GPa) and temperature (993 ± 24 °C), which correspond to the diamond stability field. The composition of mineral inclusions in zircon indicates its formation at both the progressive and the regressive stage of metamorphism. The concordia diagram shows that the figurative points of zircon lie on a discordia with an upper intersection at 1953 ± 139 Ma and a lower intersection at 512 ± 4 Ma. The main peak on the graph of the probability density distribution of zircon ages corresponds to an age of 519 Ma. The presence of grossular–almandine garnet inclusions in zircon confirms the previous assumption that the basement rocks of the Kokchetav massif act as protoliths of garnet–pyroxene rocks.

The origin of calcite in calc‐silicate rocks from the Kokchetav ultrahigh‐pressure metamorphic complex

AbstractUnderstanding calcite genesis in ultrahigh‐pressure crustal rocks is a key to the reconstruction of the evolution of ultrahigh‐pressure metacarbonate rocks. Here, we present new data and a new model on the genesis and the P–T conditions of the formation of calcite found in the ultrahigh‐pressure calc‐silicate rocks from the Kokchetav massif. In the studied sample aragonite inclusions coexist with Type A calcite inclusions (previously interpreted as mineral inclusions) and the inclusions of Type B calcite (previously interpreted as derived from the crystallization of carbonatitic melt) in cores of garnet porphyroblasts. The most Mg‐rich calcite from Type A inclusions coexisting with aragonite inclusions in one garnet growth zone shows XCa = 0.935 implying their crystallization during a retrograde metamorphic stage at P ~ 2.3 GPa and T ~ 870°C along the P–T path. Type A calcite and aragonite inclusions were also found coexisting in one growth zone with K‐bearing clinopyroxene inclusion (ω[K2O] = 0.5 wt.%). Such a high K2O‐content in clinopyroxene testify that the pressure of inclusion capture exceeded 3.5 GPa, which contradicts the P–T conditions estimated by XCa in magnesian calcite. Thus, Type A calcite inclusions were initially captured as an aggregate of aragonite+ magnesian calcite at ultrahigh pressure metamorphic stage (P ≥ 3.5 GPa, T = 900–1,000°C) and then re‐equilibrated at lower conditions (P ≤ 2.3 GPa and T ≤ 870°C). The trace element composition of aragonite and Type A and Type B calcite from inclusions was also studied to clarify calcite genesis in these inclusions. Aragonite shows high LREE (5–57 ppm) and Sr‐content (600–800 ppm). Calcite from Type A inclusions shows low LREE (2.9–19.8 ppm) and Sr‐content (490–670 ppm). Calcite from Type B inclusions forms two groups according to the LREE and Sr content distribution (Type B1 and Type B2). Trace element distribution in Type B1 calcite is identical to that of Type A calcite, while Type B2 calcite shows high LREE (6.8–64.9 ppm) concentrations along with low Sr‐content (180–340 ppm). Type A and Type B1 calcite is interpreted to have been re‐equilibrated. Type B2 calcite inclusions crystallized from the hydrous carbonatitic melt.

Origin of potassium-bearing tourmalines of the Kumdy-Kolsky deposit (Kokchetav massif, Northern Kazakhstan): Study of Mineral inclusions

Research subject. Mineral inclusions in potassium-bearing tourmaline crystals of the Kumdy-Kol microdiamond deposit. Aim. To reconstruct PT conditions for the origin of potassium-bearing tourmalines. Materials and methods. Mineral analysis and element mapping were performed using an X-ray spectral microanalyzer. Raman spectroscopy was used to detect the C and SiO2 polymorphs. Results. For the first time, diamond inclusions were identified in tourmalines with the potassium content ranging from 1.0 to 1.6 wt %. In addition, diamond-bearing zircon was detected in tourmaline crystals, with the K2O content below the detection limit. Previously, diamond inclusions had been exclusively identified only within the most potassium-rich cores of tourmaline crystals, which were approved as a new end member referred to as maruyamaite. Similar to the previous studies, the Kfs inclusions were recognized in both marumaite crystals and tourmaline crystals, with a variable content of potassium. Conclusions. The obtained findings indicate that high-pressure conditions may not be necessary for the formation of potassium-rich tourmaline. The chemical composition of the fluid is most likely to be the main factor controlling the appearance of tourmalines with an unusual composition.

<sup>40</sup>Ar/<sup>39</sup>Ar DATING OF MARUYAMAITE (K-DOMINANT TOURMALINE) FROM DIAMOND-BEARING METAMORPHIC ROCKS OF THE KOKCHETAV MASSIF

40Ar/39Ar analyses were made on maruyamaite (potassium-dominant tourmaline) from tourmaline-quartz-feldspar rocks discovered within the Kumdy-Kol microdiamond deposit (Kokchetav massif, North Kazakhstan). Turmaline yielded well-defined 40Ar/39Ar plateau age spectra whose values coincide within the error - ages of 502.3±8.0, 502.2±8.0, 506.0±8.0 Ma. These ages are much younger than the age of 530±2 Ma determined for high-pressure metamorphism by different methods. Thus, the formation of tourmaline-rich rocks of the Kumdy-Kol deposit cannot be associated with the high-pressure metamorphic events, and, therefore, testifies in favor of the low-pressure nature of maruyamaite. Based on the coincidence of age data for tourmaline crystals with different potassium contents, it can be concluded that the K/Ar system in tourmaline can be used for dating metasomatic and metamorphic processes.

Methane in Carbonate Melt Inclusions in the Rock-Forming Minerals of Calc-Silicate Rocks of the Kokchetav Massif

Secondary inclusions of the carbonate melt in garnets and clinopyroxenes from ultrahigh-pressure calc-silicate rocks were studied. Secondary carbonate inclusions are located in the healed cracks confined to large (100 µm–3 mm) primary carbonate inclusions in garnet. In some cases, the healed cracks form plates that intersect both garnet and inclusions of potassium-bearing clinopyroxene in garnet. The high content of K2O (0.64 wt %) in the healed cracks in clinopyroxene inclusions suggests that their formation and healing took place during the stage of ultrahigh pressures. Interpretation of the Raman spectra of the secondary inclusions of the carbonate melt in garnet and clinopyroxene confirmed the presence of the following phases: methane, graphite, calcite, dolomite, muscovite, and phlogopite. The data obtained allowed us to recognize the stage of ultrahigh pressure metamorphism in the calc–silicate rocks of the Kokchetav massif, during which methane accumulation in the carbonate melt took place, for the first time.

METHANE IN CARBONATE MELT INCLUSIONS FROM THE ROCK-FORMING MINERALS OF CALC-SILICATE ROCKS FROM THE KOKCHETAV MASSIF

Secondary inclusions of carbonate melt were studied in garnets and clinopyroxenes from ultrahigh pressure calc-silicate rocks. Secondary inclusions are located in healed cracks associated with large (100 µm – 3 mm) carbonate inclusions in garnet. In some cases, healed cracks intersect inclusions of potassium-bearing clinopyroxene in garnet. Since the amount of K2O in healed cracks in clinopyroxene-inclusions reaches 0.64 wt. %, it was concluded that their formation and healing occurred at the ultrahigh pressure metamorphic stage. Raman spectra interpretation of secondary carbonate melt inclusions in garnet and clinopyroxene confirmed the presence of the following phases: methane, graphite, calcite, dolomite, muscovite, and phlogopite. The obtained results imply for the ultrahigh-pressure metamorphic stage in the evolution of calc-silicate rocks from the Kokchetav massif, corresponding to the methane accumulation in the carbonate melt.

Thermobaric Conditions for Exhumation of Ti-clinohumite Garnetites of the Kokchetav Subduction-Collision Zone (Northern Kazakhstan)

Abstract —A new variety of Ti-clinohumite garnetites (‘garnet peridotites’) of the diamond-bearing Kumdy Kol terrane in the Kokchetav massif has been studied. An ultrahigh-pressure phase, Ti-chondrodite, orthopyroxene and contrast-zoned garnets of retrograde zoning have been found in these rocks for the first time. Ti-chondrodite and orthopyroxene were not described in these rocks earlier, and garnet composition was supposed to be homogeneous. Based on the character of chemical zoning of garnet and orthopyroxene, the peak and three retrograde parageneses for these minerals have been distinguished. Using the garnet–orthopyroxene geothermobarometry, for the Kumdy Kol terrane, based on the quantitative P–T estimates of Ti-clinohumite garnetites, a detailed retrograde P–T trend has been constructed for the first time; this trend includes the UHP peak stage (55–57 kbar, 1075–1120 °С), and three stages of retrograde metamorphism under UHP (32 kbar, 830 °С), HP (21 kbar, 750 °С), and MP (12 kbar, 740 °С) conditions. For the Kumdy Kol terrane this is the most detailed Р–Т trend indicating subisothermal decompression during crustal rock exhumation from the mantle depths (~170 km) to the lower-crust conditions (~36 km). The above-mentioned mineralogical findings allowed reconstructing all the described metamorphism stages, using the same rock and various generations of the same minerals (garnet and orthopyroxene) formed at different stages of tectono–metamorphic evolution of the Kumdy Kol terrane. Preservation of the relics for mineral zoning of the early metamorphic stages seemed to be due to high uplift velocities resulted in rapid decrease in P–T parameters and short duration of regressive metamorphism. The virtually complete identity of the obtained P–T trend for the Kumdy Kol terrane and the P–T trend for the Barchi terrane supports the idea of the common tectono–metamorphic evolution of the whole western (diamond-bearing) part of the Kokchetav massif.

ОСОБЛИВОСТІ МЕТАМОРФІЧНИХ ДІАМАНТІВ

For the first time a new type of diamond-bearing non-kimberlite rocks with microdiamonds was discovered in the Kokchetav massif of Kazakhstan – diamond microcrystals were found in rocks of ancient metamorphic complex and placers of different ages. Subsequently, similar microcrystals were found in the metamorphic rocks of the Dabie Shan massif (Central China), the Fjortoft Islands (Northern Norway), the Erzgebirge Massif (Germany) and the Bohemian Massif (Czech Republic), in metamorphic massifs of the Rhodopes (Greece and Bulgaria), the Western Alps (Italy) and the Eastern Alps (Slovenia), and in many other localities. The mineralogy of diamonds of the Kokchetav and the Erzgebirge massifs is studied in the most detail. We summarized original and literature data on the mineralogy of metamorphic diamonds. Information on the geology of their diamond-bearing rocks and their indicator minerals is briefly covered – distribution, age, geological position of ultrametamorphic rocks, indicators of their diamond-bearing capacity and minerals of diamond paragenesises. Peculiarities of metamorphic diamonds are characterized by often big content in rocks, their micron size and diversity of crystal shape, structural imperfection and normal growth mechanism of many crystals, dominant light isotopic composition of their carbon, high content of nitrogen impurities and their low type of aggregation, spectral types Ib–IaA, enrichment of impurities, the content of specific solid inclusions and the unusualness of mineral associations. There are many hypotheses about the formation of metamorphic diamond crystals, including their metastable growth. The hypothesis of their subduction origin in the mantle at rather high PT-parameters is considered to be the most probable. Kokchetav microdiamonds from metamorphic rocks of Kazakhstan and Samotkan microdiamonds from Neogene sands of the Middle-Dniprо area (Ukrainian Shield) are compared. According to the comparison indicators, Samotkan microdiamonds and Kokchetav microdiamonds differ markedly in crystal size and morphology, content of nitrogen impurities and degree of its aggregation, the ratio of spectral types, the ratio of helium isotopes 3He /4He and a set of mineral inclusions. Samotkan diamonds are larger, no skeletal forms have been identified among them, the range of their carbon isotope composition is wider, among them, there is quite a lot of nonnitrogen and low-nitrogen crystals, different spectral types of crystals represent them, and some of them contain mineral inclusions of peridotite association.

Solidus of carbonated phlogopite eclogite at 3–6 GPa: Implications for mantle metasomatism and ultra-high pressure metamorphism

The interaction of natural eclogite (Ecl) with synthetic hydrous carbonate melts with Na:K = 0:1 (KH2) and 1:1 (NKH2) was studied in multianvil experiments at 3–6 GPa and 850–1250 °C. The interaction with KH2 consumes garnet and clinopyroxene producing phlogopite and calcite-dolomite solid solution. Besides, the interaction yields a decrease in the jadeite component of clinopyroxene, evolving eclogite toward pyroxenite. This is consistent with a metasomatic alteration of eclogite xenoliths, manifested as Na-poor “spongy” clinopyroxene, replacing primary omphacite, and kelyphitic rims around garnet, containing phlogopite and carbonates. The interaction with NKH2 also produces phlogopite and carbonate, but the latter is more magnesian and represented by magnesite, above the solidus, and magnesite + dolomite below the solidus. The interaction with NKH2 increases the jadeite component in clinopyroxene and grossular component in garnet, evolving eclogite Group A to eclogite Group B.The studied systems have H2O/K2O = 2, like that in phlogopite, and therefore correspond to carbonated phlogopite eclogite under fluid-absent conditions. Based on the obtained results its solidus is situated near 1050 °C at 3 GPa and decreases to 950 °C at 6 GPa. Thus, hydrous K- and Na-K-carbonatite melts can coexist with eclogite in SCLM at depths exceeding 120–170 km, and solidify as temperature decreases below 950–1050 °C according to the following solidus reactions: pyrope + diopside + melt → phlogopite + dolomite, below 6 GPa, and pyrope + diopside + melt → phlogopite + magnesite + grossular, at 6 GPa.The melting reaction, involving phlogopite and dolomite, suggests the partial melting at the peak of ultrahigh-pressure metamorphism (UHPM) during continent–continent plate collision. The prograde P-T path of UHPM crosses the solidus of clinopyroxene + garnet + phlogopite + dolomite assemblage at 4.7–5.2 GPa and 970–990 °C and yields the formation of hydrous K-carbonatite melt-fluid in situ. This melt could be responsible for the formation of K-bearing clinopyroxenes and microdiamonds in the UHPM marbles in the Kokchetav massif, Kazakhstan. The retrograde P-T path intersects the solidus that has a negative Clapeyron slope in the diamond stability field. Thus, the hydrous K-carbonatite melt should disappear soon after the peak of metamorphism reacting with garnet to produce Ca-Mg carbonates and phlogopite.

Isotope-Geochemical Evidence of the Nature of the Protoliths of Diamondiferous Rocks of the Kokchetav Subduction–Collision Zone (Northern Kazakhstan)

Abstract —The isotope-geochemical features of diamondiferous metamorphic rocks of the Kokchetav subduction–collision zone (KSCZ) show that both the basement rocks and the sediments of the Kokchetav massif were their protoliths. A whole-rock Sm–Nd isochron from the diamondiferous calc-silicate, garnet–pyroxene rocks and migmatized granite-gneisses of the western block of the KSCZ yielded an age of 1116 ± 14 Ma, while an age of 1.2–1.1 Ga was obtained by U–Pb dating of zircons from the granite-gneiss basement of the Kokchetav microcontinent. Based on these data, we assume that the protoliths of the calc-silicate, garnet–pyroxene rocks and the granite-gneisses of the KSCZ were the basement rocks sharing an initially single Nd source, which was not influenced by high- to ultrahigh-pressure metamorphism (~530 Ma). Therefore, their geochemical features are probably not directly related to ultrahigh-pressure metamorphism. The corresponding rock associations lack isotope-geochemical evidence of partial melting that would occur during ultrahigh-pressure metamorphism, which suggesting that they were metamorphosed under granulite-facies conditions. At the same time, the high-alumina diamondiferous rocks of the Barchi area (garnet–kyanite–mica schists and granofelses), which were depleted to different degrees in light rare-earth elements (REE) and K, have yielded a Sm–Nd whole-rock isochron age of 507 ± 10 Ma indicating partial melting of these rocks during their exhumation stage. The close ɛNd (1100) values of the basement rocks and garnet–kyanite–mica schist with geochemical characteristics arguing against its depletion during high-pressure metamorphism indicate that the basement rocks were a crustal source for high-alumina sediments.

Formation of Polycrystalline Graphite Aggregates in High-Pressure Metamorphic Rocks from the Kokchetav Massif, Northern Kazkhstan

An inclusion of graphite in zircon from the diamond- and tourmaline-bearing rocks of the Kokchetav massif (Northern Kazakhstan) has been studied. The inclusion, associated with diamond crystals, was identified within the marginal part of the zircon grain. The Raman spectrum of the graphite inclusion is characterized by the presence of an intense band at 1350 cm–1, which is indicative of a high degree of disorder in its structure. An investigation of this inclusion by means of transmission electron microscopy (TEM) allowed us to identify nine randomly oriented high-ordered submicron grains of graphite without relics of diamond. Thus, the presence of the intense band at 1350 cm–1 in the Raman spectra of graphite is not a necessary evidence of its low degree of crystallinity and particularly its formation as a result of diamond graphitization. The formation of the polycrystalline aggregates, consisting of submicron grains of well-ordered graphite, might have been related to rapid crystallization from a high-density C–O–H fluid.

Silicate Inclusions in Metamorphic Diamonds from the Ultra-High Pressure Kokchetav Complex (Kazakhstan)

Mineral inclusions in cubic diamonds from garnet–clinopyroxene rock of the Kokchetav massif were studied. The coexistence of fluid and silicate inclusions in the central part of the diamond of the G0 sample was revealed by means of transmission electron microscopy. Silicate inclusions are represented by intergrowths of garnet and mica, which are spatially related with the carbonate and fluid inclusions. The first finding of silicate inclusions in the cubic diamonds from the UHP complex discovered over 50 years of their study is apparently due to a selective capture of the silicate minerals in the process of the diamond crystallization from the carbonate-bearing C–O–H fluid. The processes of diamond crystallization in the metamorphic deeply subducted rocks and upper mantle rocks, which are carried to the surface as xenoliths by kimberlite melts, have much in common.

Ubiquitous post‐peak zircon in an eclogite from the Kumdy‐Kol, Kokchetav UHP‐HP Massif (Kazakhstan): Significance of exhumation‐related zircon growth and modification in continental‐subduction settings

AbstractU–Pb geochronological, trace‐element and Lu–Hf isotopic studies have been made on zircons from ultrahigh‐pressure (UHP) mafic eclogite from the Kumdy‐Kol area, one of the diamond‐facies domains of the Kokchetav Massif (northern Kazakhstan). The peak eclogitic assemblage equilibrated at > 900 °C, whereas the bulk sample composition displays light rare‐earth element (LREE) and Th depletion evident of partial melting. Zircons from the eclogite are represented by exclusively newly formed metamorphic grains and have U–Pb age spread over 533–459 Ma, thus ranging from the time of peak subduction burial to that of the late post‐orogenic collapse. The major zircon group with concordant age estimates have a concordia age of 508.1 ±4.4 Ma, which corresponds to exhumation of the eclogite‐bearing UHP crustal slice to granulite‐ or amphibolite‐facies depths. This may indicate potentially incoherent exhumation of different crustal blocks within a single Kumdy‐Kol UHP domain. Model Hf isotopic characteristics of zircons (εHf(t) +1.5 to +7.8, Neoproterozoic model Hf ages of 1.02–0.79 Ga) closely resemble the whole‐rock values of the Kumdy‐Kol eclogites and likely reflect in situ derivation of HFSE source for newly formed grains. The ages coupled with geochemical systematics of zircons confirm that predominantly late zircon growth occurred in Th–LREE‐depleted eclogitic assemblage, that experienced incipient melting and monazite dissolution in melt at granulite‐facies depths, followed by amphibolite‐facies rehydration during late‐stage exhumation‐related retrogression.

Zircon from diamondiferous kyanite gneisses of the Kokchetav massif: Revealing growth stages using an integrated cathodoluminescence, Raman spectroscopy and electron microprobe approach

AbstractZircon crystals from diamondiferous kyanite gneisses of the Barchi-Kol area (Kokchetav massif, Northern Kazakhstan) have been investigated by a combined application of cathodoluminescence (CL), Raman spectroscopy and electron probe microanalysis (EPMA). The zircon crystals exhibit up to four distinct domains characterised by significantly different CL signatures and parameters of the ν3(SiO4) (1008 cm–1) Raman band (i.e. full width at half maximum, position and intensity). Extremely metamict zircon cores (Domain I) host inclusions of low-pressure minerals (quartz and graphite) and the outer mantles (Domain III) are populated by ultrahigh-pressure relicts (diamond and coesite), whereas inner mantles (Domain II) and overgrowth rim zones (Domain IV) are inclusion free. Both the zircon cores and rims have very low Ti concentrations, implying formation temperatures below 760°C. The Ti content in the inner mantles (up to 40 ppm) is indicative of temperatures in the 760–880°C range. The temperature estimates for the outer mantles are 900–940°C, indicating a pronounced overlap with the peak metamorphic values yielded by the Zr-in-rutile geothermometer for the same rocks (910–950°C). The internal textures of the zircons and the occurrence of index minerals within the distinct domains allow us to unravel the stages of the complex metamorphic history recorded in the zircon. Our data show that the zircon cores are inherited seeds of pre-metamorphic (magmatic?) origin, the inner mantles were formed on the prograde metamorphic stage, the outer mantles record ultrahigh-pressure metamorphism and the outermost rims mark the retrograde metamorphic stage. The observed zircon internal textures are thus clearly correlated with distinct growth events, and in some examples reflect a major part of the metamorphic history. It is concluded that the combined application of the CL, Raman spectroscopy and EPMA techniques to zircon offers significant potential for deciphering the metamorphic evolution of deeply-subducted rocks.

The Northern Kazakhstan Uranium Province, Kokchetav Massif: U–Pb (ID-TIMS) and Rb–Sr Geochronology of Rocks of Ore-Hosting Volcanotectonic Depressions

Geochronological studies have been conducted for ore-hosting rocks (quartz rhyolites, felsitic rhyolites, porphyry granites) of some U deposits of the Yakshi-Yangistau complex within the Balkashino ore center of the Northern Kazakhstan uranium province. According to geological maps of various scales, the rocks were traditionally ascribed to the Early–Middle Devonian (quartz and felsitic rhyolites) and Middle–Late Devonian (porphyry granites). The results of U–Pb, Rb–Sr, and K–Ar dating have shown that, according to the current version of the Geochronological Chart, the age of quartz rhyolites is Early–Late Silurian and that of felsitic rhyolites and porphyry granites is Late Silurian. The features of the chemical composition and different initial Sr isotopic composition of these rocks suggest that quartz rhyolites, felsitic rhyolites, and porphyry granites of the Yakshi-Yangistau complex are hardly comagmatic. They are characterized by different ages and formed from independent magmatic sources. Our data indicate the minimum possible age of the formation of primary U ores within the Balkashino ore center.

A combined Raman spectroscopy, cathodoluminescence, and electron backscatter diffraction study of kyanite porphyroblasts from diamondiferous and diamond‐free metamorphic rocks (Kokchetav massif)

AbstractA series of precise nondestructive analytical methods (Raman spectroscopy, cathodoluminescence, and EBSD—electron backscatter diffraction) has been employed to investigate the internal textures of kyanite porphyroblasts from diamondiferous and diamond‐free ultrahigh‐pressure metamorphic rocks (Kokchetav massif, Northern Kazakhstan). Such internal kyanite characteristics as twinning, radial fibrous pattern, and spotty zoning were identified by means of Raman and cathodoluminescence imaging, whereas an intergrowth of two kyanite crystals was distinguished only by Raman imaging. The EBSD analysis recorded an ~10–25° changing of orientations along the elongation in the investigated kyanite porphyroblasts. The absence of a radial fibrous pattern and a spotty zoning on the EBSD maps indicates that these textures are not related to variations in crystallographic orientation. The absence of clear zoning patterns (cores, mantles, and rims) on the Raman, cathodoluminescence, or EBSD maps of the kyanite porphyroblasts indicates the rapid single‐stage formation of these porphyroblasts near the peak metamorphic conditions and the lack of recrystallization processes. The obtained results provide important implications for deciphering of mineral internal textures, showing that the data obtained by cathodoluminescence mapping can be clearly reproduced by Raman imaging, with the latter method occasionally being even more informative. This observation is of significant importance for the study of minerals that are unexposed on a thin section surface or Fe‐ and Ni‐rich minerals that do not show luminescence emission. The combination of the Raman spectroscopic, cathodoluminescence, and EBSD techniques may provide better spatial resolution for distinguishing different domains and textural peculiarities of mineral than the selective application of individual approaches.

New insights on Raman spectrum of K‐bearing tourmaline

AbstractRaman spectroscopy allows for semiquantitative analyses of major elements of tourmaline supergroup minerals. However, the new K‐bearing tourmaline (maruyamaite) species has not been calibrated yet and the effects of K in the X site of tourmaline on the Raman spectrum are still unclear. We investigated maruyamaite and K‐bearing dravite to test their Raman spectrum parameters, as a proxy for chemical composition of the X site. This study uses Raman imaging to obtain spectral data from the studied area of the zoned natural tourmaline crystals from Kumdy‐Kol (Kokchetav massif, Northern Kazakhstan). These data are correlated with chemical composition determined by electron probe microanalysis. Raman peak intensity best correlates with the K apfu at the X site. Peaks in the interval 100–250 cm−1 are aligned to the X‐site cation vibrations, and thus, their intensity positively correlates with K content. However, also, the more intensive peaks in the 650 to 850 cm−1 interval, which are controlled by the Si6O18 ring and AlO6 vibrations, show a positive correlation with the amount of K. The latter peak region is thus chosen here for the calibration due to its much higher intensity respect to the 100 to 250 cm−1 region. Furthermore, we discuss the influence of large K cations on the structure of Si6O18 rings in tourmaline. Our study demonstrates that Raman spectroscopy can be used as a reconnaissance tool for a semiquantitative discrimination of dravitic tourmalines with different X‐site occupation.

Dumortierite and tourmaline from the Barchi‐Kol diamond‐bearing kyanite gneisses (Kokchetav massif): A Raman spectroscopic study and petrological implications

AbstractTwo minerals of boron, dumortierite and tourmaline, have been studied in a diamondiferous kyanite gneiss (Barchi‐Kol area, Kokchetav massif, Northern Kazakhstan) by Raman spectroscopy and electron microprobe (EMP) analysis. Dumortierite and tourmaline (almost pure schorl end‐member) coexist within the sample, with blue/purple dumortierite inclusions hosted by kyanite porphyroblasts and blue tourmaline crystals occurring as inclusions in garnet. Optically, dumortierite appears almost identical to kyanite host and can be easily overlooked in thin sections during optical and scanning electron microscopic observations. Both boron minerals show a very strong anisotropy, and the most prominent Raman spectra can be obtained if the electric field vector E is parallel to the c axis of the dumortierite and tourmaline crystals. The Raman spectra of the investigated dumortierite are very similar to those of the synthetic dumortierite with a pronounced excess of boron (up to 0.26 [4]B), although the EMP examination revealed only one grain of the natural dumortierite studied here to have a very low boron surplus (up to 0.03 [4]B). Neither Raman spectroscopic study nor EMP analysis detected [4]B in tourmaline. The findings of dumortierite and tourmaline in the diamondiferous gneisses provide important implications for the presence of a boron‐rich fluid or melt during subduction/exhumation processes.

Compressibility and structure behaviour of maruyamaite (K-tourmaline) from the Kokchetav massif at high pressure up to 20 GPa

The structural behaviour of maruyamaite (K-dominant tourmaline) X(K0.54Na0.28Ca0.19)Y(Mg1.3Al1.17Fe0.39Ti0.14)Z(Al5Mg)[Si5.95Al0.05O18](BO3)3V,W[O1.69(OH)2.31] from the ultrahigh-pressure metamorphic rocks of Kokchetav massif was studied using synchrotron based single-crystal diffraction up to 20 GPa. Within the whole pressure range the compression is regular and anisotropic, with the c direction being more compressible than the a direction. Fitting the V/P data with the 2nd and 3rd order Birch-Murnaghan equations of state gives: V0 = 1587.2(7) A3, K0 = 115.6(9) GPa at fixed K′ = 4, and V0 = 1588(1) A3, K0 = 112(3) GPa, K′ = 4.5(4). The bulk modulus values are slightly higher as compared to those found for dravite and cation-deficient synthetic K-dravite. The pressure evolution of the main structural parameters of K-tourmaline is similar to those of dravite. However, a minor change in the rigidity of local contacts of the X site with 6-membered ring, due to the presence of K, is apparently critical for stabilization of tourmaline structure within 15–20 GPa, which is evinced by the absence of the phase transition observed in dravite near 15.4 GPa. The stabilizing function of K becomes apparent at P > 15 GPa. The comparison of the HP structural behaviour of maruyamaite and dravite supports the recent suggestion that the large X site plays a secondary role in the elastic behaviour of tourmaline, compared to the octahedral framework. In addition, the present study reveals several new features of polyhedra distortions, which demonstrate their complex interaction on compression.

The mechanism of disordered graphite formation in uph diamond-bearing complexes

Kyanite gneiss from the "New Barchinsky" locality (Kokchetav Massif) was studied in detail. This rock is characterized by zonal distribution of the C and SiO2 polymorphs in kyanite porphyroblasts: (1) porphyroblast cores with graphite and quartz inclusions; (2) clean overgrowth zone with inclusions of cuboctahedral diamond crystals. The Raman mapping of SiO2 polymorphs originally showed the presence of an association of disordered graphite + coesite “prohibited” in HT diamond-bearing rocks. Graphitization of diamond is the only likely mechanism of the disordered graphite formation in HT diamond-bearing rocks. However, the absence of disordered graphite in association with diamond in kyanite porphyroblasts from kyanite gneiss from the "New Barchinsky" locality eliminates the process of diamond graphitization at the retrograde stage. Most likely, crystallization of disordered graphite occurred at the retrograde stage from the UHP C-O-H fluid.