Diamond formation in sulfide pyrrhotite-carbon melts: Experiments at 6.0–7.1 GPa and application to natural conditions

Experiments at 6.0–7.1 GPa and 1500–1700°C were carried out to explore the boundary conditions of diamond nucleation and growth in pyrrhotite-carbon melt-solutions. Pyrrhotite is one of the main sulfide minerals of the pyrrhotite-pentlandite-chalcopyrite assemblage of mantle rocks and primary inclusions in diamond. Solutions of carbon in sulfide melts oversaturated with respect to diamond at the expense of the dissolution of starting graphite (thermodynamically unstable phase) are formed owing to the difference between the solubilities of graphite and diamond, which increases under the influence of temperature gradients in experimental samples. We determined the fields of carbon solutions in pyrrhotite melt showing labile and metastable oversaturation with respect to diamond, which correspond to the spontaneous nucleation of the diamond phase and diamond growth on seeds, respectively. The linear growth rate of diamond in sulfide-carbon melts is rather high (on average, 10 μ/min during the first 1–2 min from the onset of spontaneous crystallization). The nucleation density is estimated as 180 grains per cubic centimeter. Diamonds crystallized from sulfide melts show octahedral and spinel twin shapes. Diamond polycrystals were synthesized for the first time from a sulfide medium as intergrowths of skeletal (edge) or “cryptocrystalline” microdiamonds, from 1 to 100 μm in size, their spinel twins and, occasionally, polysynthetic (star-shaped) twins. During diamond growth from sulfidecarbon melts on smooth faces of cuboctahedral diamond seeds synthesized in metal systems, smooth-faced layer-by-layer step-like growth was observed on their octahedral (111) faces, whereas growth on the (100) cubic faces produced rough-surfaced layers of intergrown micropyramids, whose axes were oriented normal to the (100) face. The obtained experimental results were applied to the problem of diamond genesis under the conditions of the Earth’s mantle in the framework of the model of carbonate-silicate parental melts with blebs of immiscible sulfide melts.     

Experimental study of fluorine and chlorine contents in mica (biotite) and their partitioning between mica,phonolite melt,and fluid

This paper reports the results of a study of the composition of mica (biotite) crystallizing in the system of phonolite melt-Cl- and F-bearing aqueous fluid at T ～ 850°C, P = 200 MPa, and \(f_{O_2 } \) = Ni-NiO, as well as data on F and Cl partitioning between coexisting phases. It was established that Cl content in mica is significantly lower than in phonolite melt and, especially, in fluid. Fluorine shows a different behavior in this system: its content in mica is always higher than in phonolite melt but lower than in fluid. The mica-melt partition coefficients of Cl and F also behave differently. The Cl partition coefficient gradually increases from 0.17 to 0.33 with increasing Cl content in the system, whereas the partition coefficient of F sharply decreases from 3.0 to 1.0 with increasing total F content. The apparent partition coefficients of F between biotite and groundmass (melt) in various magmatic rocks are usually significantly higher than the experimental values. It was supposed that the higher ^Bt/glassD_F values in natural samples could be related to the influence of later oxidation reactions, reequilibration of biotite at continuously decreasing \(f_{H_2 O} \)/f _HF ratio, and an increase in this coefficients with decreasing total F content in the system.     

A strong temperature effect on U/Ca in planktonic foraminiferal carbonates

Three planktonic foraminiferal species Globigerina bulloides, Neogloboquadrina pachyderma (d), and Globorotalia inflata collected from core-tops spanning 35° to 65°N in the North Atlantic were used for U/Ca and Mg/Ca and foraminiferal shell weight analyses. Except for U/Ca in G. bulloides calcified under warm conditions (>∼13 °C), U/Ca ratios in all three studied species increase with decreasing latitude and show strong positive correlations with Mg/Ca ratios. A dissolution effect on planktonic U/Ca is suggested by decreased shell weight and U/Ca and Mg/Ca ratios for shells from very deep water depth (>4.4 km) along the latitudinal transect. G. bulloides from down core samples in the North Atlantic show low U/Ca ratios during the last glacial and high ratios during the Holocene, similar to the Mg/Ca evolution trend. In general, our data indicate that the U incorporation into planktonic foraminiferal carbonates is strongly influenced by calcification temperature, although U/Ca in G. bulloides may be affected by seawater carbonate ion concentration under warm conditions and/or other factors.     

The posthumous tectonics and mechanism of exhumation of granitic plutons: The case of the Transbaikal region and the Tien Shan

The study of granitic plutons of the Baikal Highland and the Tien Shan has made it possible to establish new features of their posthumous (after incorporation into the consolidated Earth’s crust) structural reworking and to understand the implications of the cataclastic flow for the exhumation of the crystalline basement in the studied regions. It is shown that granitic plutons undergo appreciable structural transformation at the stages of tectonic reactivation that is significantly separated in time from the moment of formation of plutons as geological bodies. The 3D cataclastic deformation is the main mode of structural reworking of granitic plutons, while the cataclastic flow is the main form of their mobility. Newly recognized slice structures characterize the volumetric deformation of granites.     

Synchronism in compression of the lithosphere in the central Atlantic and Western Tethys at the Tortonian-Messinian transition

The structure of anomalously uplifted areas in transverse ridges of the Vema, S o Paulo, and Romanche fracture zones is considered. It is concluded that their formation and eventual development in the present-day structure of the central Atlantic bottom proceeded during two stages. The first stage that corresponds to a short period at the Tortonian-Messinian transition (10 Ma ago) was marked by transportation of deep-seated rocks into the upper part of the lithosphere along thrust faults with mass motion in the meridional direction along the axis of the Mid-Atlantic Ridge. The second stage was characterized by contrasting highamplitude vertical movements from 10 to 3 Ma ago. It is suggested that near-meridional compression in the domains surrounding the Western Tethys in the Tortonian-Messinian resulted in deformation of the upper lithosphere within large transform fracture zones of the central Atlantic. The deformation that occurred 10 Ma ago was a manifestation of the global neotectonic epoch of the Earth.     

Sorption of Ni on Na-rectorite studied by batch and spectroscopy methods

Sorption of Ni²⁺ on Na-rectorite as a function of contact time, temperature, pH and fulvic acid (FA)/humic acid (HA) was studied under ambient conditions. A pseudo-second-order rate equation was used to simulate the kinetic sorption. The removal of Ni²⁺ increased with increasing pH. The presence of FA/HA enhanced the sorption of Ni²⁺ at low pH values, whereas no drastic effect of FA/HA on Ni²⁺ uptake to rectorite was found at high pH values. The diffuse layer model (DLM) fitted the experimental data of Ni²⁺ sorption in the absence and presence of FA/HA very well with the aid of FITEQL 3.2. The Langmuir, Freundlich and Dubinin–Radushkevich (D–R) models were used to simulate the sorption isotherms of Ni²⁺ at different temperatures. The thermodynamic data (ΔH⁰, ΔS⁰, ΔG⁰) were calculated from the temperature dependent sorption isotherms and the results suggested that the sorption process of Ni²⁺ on rectorite was spontaneous and endothermic. The sorption and species of Ni²⁺ on rectorite in the presence and absence of FA/HA was also investigated and characterized by XPS. The spectroscopic analysis indicated no drastic structural changes of Na-rectorite and the sorption of Ni²⁺ mainly occurred on the surface and at the edge position of Na-rectorite.     

The Ruiga intrusion: A typical example of a shallow-facies paleoproterozoic peridotite-gabbro-komatiite-basaltic association of the Vetreny Belt,Southeastern Fennoscandia

The Ruiga differentiated mafic-ultramafic intrusion in the northwestern part of the Vetreny Belt paleorift was described for the first time based on geological, petrological, geochronological, and geochemical data. The massif (20 km² in exposed area) is a typical example of shallow-facies peridotite-gabbro-komatiite-basalt associations and consists of three zones up to 810 m in total thickness (from bottom to top): melanogab-bronorite, peridotite, and gabbro. In spite of pervasive greenschist metamorphism, the rocks contain locally preserved primary minerals: olivine (Fo _75–86), bronzite, augite of variable composition, labradorite, and Cr-spinels. A mineral Sm-Nd isochron on olivine melanogabbronorite from the Ruiga Massif defines an age of 2.39 ± 0.05 Ga, while komatiitic basalts of the Vetreny Belt Formation were dated at 2.40–2.41 Ga (Puchtel et al., 1997). The rocks of the Ruiga intrusion and lava flows of Mt. Golets have similar major, rare-earth, and trace element composition, which suggests their derivation from a single deep-seated source. Their parent magma was presumably a high-Mg komatiitic basalt. In transitional crustal chambers, its composition was modified by olivine-controlled fractionation and crustal contamination, with the most contaminated first portions of the ejected melt. In terms of geology and geochemistry, the considered magmatic rocks of the Vetreny Belt are comparable with the Raglan Ni-PGE komatiite gabbro-peridotite complex in Canada (Naldrett, 2003).     

Zr/Hf ratio as an indicator of fractionation of rare-metal granites by the example of the Kukulbei complex,eastern Transbaikalia

The concept of granitic melt fractionation as the main process in the concentration of rare elements in granites calls for the development of a reliable method to determine the evolutionary sequences of granite series. We propose to use for this purpose a zirconium-hafnium indicator, the Zr/Hf weight ratio in granitic rocks (Zaraisky et al., 1999, 2000). By the example of three classic regions of rare-metal deposits, eastern Transbaikalia, central Kazakhstan, and Erzgebirge (Czech Republic and Germany), it was empirically shown that the Zr/Hf ratio of granites decreases during the fractional crystallization of granite magmas in the sequence granodiorite → biotite granite → leucogranite → lithium-fluorine granite. The reason is the higher affinity of Hf compared with Zr to a granite melt. This implies that the crystallization and settling of accessory zircon will cause the progressive enrichment of Hf relative to Zr in the residual melt. As a result, the Zr/Hf ratio decreases regularly in the series of sequential phases of granite intrusion related to a single magma chamber from granodiorite to biotite granite, leucogranite, and Li-F granite (from 45-30 to 10-2). Our experimental investigations supported the preferential enrichment of haplogranite melt in Hf and zircon crystals in equilibrium with melt in Zr (T= 800°C and P = 1 kbar). The Zr/Hf indicator was tested by the example of the wellknown Kukulbei rare-metal granite complex of eastern Transbaikalia (J3), which is unique in the degree of fractionation of initial granite melt with the formation of three phases of granite emplacement and vein derivatives. An important feature of the complex is its “short” differentiation trend. It was supposed that the granite magma of the first phase is parental, and the later phases forming small intrusive bodies in large massifs of biotite granites of the first phase are sequential products of its crystallization differentiation in a magma chamber. The biotite granites of the first phase are barren. The leucocratic granites of the second phase are accompanied by tin-tungsten greisen deposits (e.g., Spokoininskoe), and the upper part of cupola-like stocks of Li-F amazonite granites of the third phase host apogranite-type tantalum deposits (Orlovka, Etyka, and Achikan). In addition to three granite phases, the Kukulbei complex includes dikes of ongonites, elvans, amazonite granites, and chamber miarolitic pegmatites. All of the granitic rocks of the complex have similar isotopic ages of 142± 0.6 Ma. The Zr/Hf ratio decreases systematically from phase 1 (40–25), to phase 2 (20–10), and phase 3 (10–2). The ongonites, elvans, and pegmatites have similar Zr/Hf ratios (15-5), falling between the ranges of leucocratic muscovite granites and Li-F granites. Compared with other granite series, the granitic rocks of the Kukulbei complex show specific petrographic and geochemical features: they are strongly enriched in Rb, Li, Cs, Be, Sn, W, Mo, Ta, Nb, Bi, and F but depleted in Mg, Ca, Fe, Ti, P, Sr, Ba, V, Co, Ni, Cr, Zr, REE, and Y. From the early to late intrusion phases, the degree of enrichment and depletion in these element groups increases regularly. This is accompanied by a significant decrease (from 40 to 2) in Zr/Hf, which can be used as a reliable indicator of genetic relations, degree of fractionation, and rare-metal potential of granites. Granites with Zr/Hf values lower than 25 are promising for prospecting for Sn, W, Mo, and Be greisen deposits, whereas the formation of Ta deposits requires Zr/Hf values lower than 10.     

Opacitization conditions of hornblende in Bezymyannyi volcano andesites (March 30, 1956 eruption)

The paper is devoted to the conditions under which opacite rims developed around hornblende grains in andesite of the catastrophic eruption (March 30, 1956) of Bezymyannyi volcano, Kamchatka. The opacite rims were produced by a bimetasomatic reaction between hornblende and melt with the development of the following zoning: hornblende → Px + Pl + Ti-Mag → Px + Pl → Px → melt. Biometasomatic reaction was accompanied by the active removal of CaO from the rim, addition of SiO₂, and more complicated behavior of other components. The hornblende also shows reactions of its volumetric decomposition under near-isochemical conditions. The opacite rims developed under isobaric conditions, at a pressure of approximately 6 kbar. The main reason for the instability of the hornblende was the heating of the magma chamber from 890 to 1005°C due to new hot magma portion injection. The time interval between the injection and the start of eruption was estimated from the thickness of the opacite rims and did not exceed 37 days. Hence, the March 30, 1956, eruption was not related to the volcanic activity in November of 1955 but to the injection of a fresh magma portion in February–March of 1956.     

黔东震旦系—下寒武统黑色岩系稀土元素地球化学特征

：通过对黔东丹寨南皋剖面和三都渣拉沟剖面的稀土元素分析发现：两条剖面的梅树村期与筇竹寺期 分界处大量稀土元素明显富集,黑色页岩中存在明显的Ｃｅ负异常和Ｅｕ、Ｙ 正异常,表明为缺氧和热水沉积的产物。 这套黑色岩系总体沉积于缺氧和具热水注入的环境中,但发生缺氧和热水注入的时间和强度在不同地方会有不同 的表现。