The mechanisms of reduction of hexavalent chromium by green rust sodium sulphate: Formation of Cr-goethite

The molecular-level processes that control green rust sodium sulphate (GR_Na,SO4) reaction with chromate were studied using high-resolution techniques. Changes in solid morphology, structure and composition were observed with atomic force microscopy, transmission electron microscopy and X-ray diffraction. The results suggest the following mechanisms: Chromate replaces sulphate in the GR interlayer and is reduced by Fe(II). Formation of sparingly soluble Cr(III)-solid blocks further chromate entry, but Cr(VI) reduction continues at the GR solid/solution interface. Electron transfer from the centre of the GR crystals to the surface facilitates rapid reaction. Less stable zones of the reacted GR_Na,SO4 dissolve and amorphous Cr(III),Fe(III)-solid forms. During equilibration, Cr-substituted goethite evolves in association with remaining GR_Na,SO4, fed by material from the amorphous phase and dissolving oxidised GR. In contrast, previous Cr(VI) experiments with the carbonate form of GR, GR_CO3, have suggested only reaction and deposition at the surface. From the perspective of environmental protection, these results have important implications. Goethite is sparingly soluble and the inclusion of Cr(III) as a solid-solution makes it even less soluble. Compared to Cr adsorbed at the surface of an Fe(III)-phase, Cr(III) incorporated in goethite is much less likely to be released back to groundwater.     

Geochronology of zircon megacrysts from nepheline-bearing gneisses as constraints on tectonic setting: implications for resetting of the U-Pb and Lu-Hf isotopic systems

Nepheline-bearing gneisses from the 75 km² Tambani body in the Mozambique Belt of southern Malawi, are miaskitic biotite-nepheline monzodiorites, reflecting an absence of K-feldspar, alkali amphiboles or pyroxenes, and contain euhedral zircon megacrysts up to 5 cm across. The zircons contain U = 1–1,860 ppm, Th = 0–2,170 ppm and Y = 400–1,100 ppm, and very low concentrations of all other measured trace elements except Hf (HfO₂ = 0.53–0.92 wt. %). Cathodoluminescence images reveal oscillatory sector growth zoning and no evidence for xenocrystic cores, indicating that the zircons represent primary magmatic crystallization products that have survived amphibolite grade metamorphism. U-Pb isotopic analyses (by TIMS) yield an upper intercept age of 730 ± 4 Ma (MSWD = 1.7), which we interpret as the time of magmatic crystallization of the zircons. This is coincident with 11 SHRIMP spot analyses, which yield a mean age of 729 ± 7 Ma (MSWD = 0.37). Metamorphism, at 522 ± 17 Ma as suggested by monazite, caused partial Pb-loss during local recrystallization of zircon. Lu-Hf isotopic data for three whole-rock samples of nepheline-bearing gneiss are collinear with those for zircon megacrysts, and correspond to an age of 584 ± 17 Ma (MSWD = 0.37. We interpret the Lu-Hf array to represent a mixing line defined by the Hf isotopic signature of primary zircon and that of the rock-forming minerals reset during metamorphic (re-)crystallization; hence the 584 Ma age is likely geologically meaningless. Given the well-defined association of nepheline syenites (and phonolitic volcanic equivalents) with continental rifting, we suggest that the Tambani body represents a magmatic product formed at 730 Ma during the break-up of the Rodinia supercontinent. The 522 Ma age is akin to other Pan-African metamorphic ages that record collisional suturing events during the final assembly of Gondwana. Zircon-bearing nepheline gneisses thus preserve a record of intra-continental rifting and of continental collision in southern Malawi.     

Petrology,geochemistry and geochronology of the Chilka Lake igneous complex,Orissa state,India

The Chilka Lake igneous complex of Orissa, the largest known anortosite massif of the Indian Shield, occurs in a catazonal environment of high-grade metamorphics of the Eastern Ghats Precambrian Orogenic Province. The syntectonic massif consists of the anorthositic Balugaon dome, leuconoritic Rambha lobe and quartz-mangeritic Kallikota cover. A completely gradational suite comprising anorthosite-leuconorite-norite-minor jotunite (the anorthositic suite) constitutes most of the complex. The subordinate of suite of acid rocks spatially associated with this is of a broad quartz-mangeritic lithology with minor granitic rocks (the acidic suite). Geochemical evolution of the complex in the sequence anorthosite-leuconorite-norite-jotunite-acidic rocks shows moderate iron enrichment in the noritic-jotunitic stage and is marked by an overall decrease in Al₂O₃, CaO, MgO, Ni/Co, Sr/Ba, K/Rb and increase in SiO₂, K₂O, V/Ni, K/Ba and Rb/Sr. Such progressive variation in geochemical parameters appears (i) essentially gradual and frequently overlapping in rock members of the intergradational anorthositic suite and (ii) rather abrupt across transition zones between the anorthositic suite and the acidic suite due to near absence of intervening intermediate lithologies. RbSr whole rock isochron studies indicate that the complex was emplaced ca. 1400 Ma ago. The initial ⁸⁷Sr/⁶⁸Sr (0.70661) implies limited hybridisation of the parent magma prior to emplacement. A critical appraisal of all the available evidence suggests that (i) the anorthositic suite of rocks form a perfectly consanguinous and comagmatic assemblage and (ii) the spatially associated acidic suite emerged through a convergence of magmatic and metasomatic processes (the latter brought about by contact anatexis of the host rocks). The complex as well as the host metamorphics are intruded by an atectonic suite of noritic dykes emplaced ca 850 Ma ago.     

辽宁海城大房身稀有金属伟晶岩包裹体研究及找矿意义

大房身3号伟晶岩脉是含铀、铌、钽等稀有金属伟晶岩矿床,分异较好,可分为4个岩相带。经对各带石英中包裹体的研究,表明含矿带含挥发份H₂O和CO₂较高,流体包裹体丰度较大,富含纯CO₂包裹体及含液相CO₂包裹体。该伟晶岩与围岩接触界线清楚,其边缘相含有围岩的捕掳体。伟晶岩结晶分异好,矿物成分简单,以长石、石英为主,其核心带产有巨晶状黑云母和微斜长石。包裹体气相成分中不含游离氧（O₂）。这些特点说明该伟晶岩是由硅酸盐熔浆在埋深大、较封闭的环境下,缓慢结晶分异而成。     

Silicate globules in kyanite from grospydites of the Zagadochnaya kimberlite pipe,Yakutia: The problem of the origin

The results of complex study of silicate globules and α-quartz paramorphs after coesite in kyanite from grospydites from the Zagadochnaya kimberlite pipe, Yakutia, using optical and scanning electron spectroscopy, electron and ion microprobes, LA ICP MS and Raman spectroscopy, are presented. The existence of radial fractures diverging from silicate globules into the matrix (kyanite) attests to the fact that the content of the globules is extremely condensed. A zonal structure is usually typical for globules: a coat and a core, which can be explicitly distinguished under the electron microscope, can be differentiated in them. Compositionally, the coat of the globule corresponds to potassium feldspar (wt %: 66.4 SiO₂; 16.9 Al₂O₃; 0.4 FeO; 0.1 CaO; 0.2 Na₂O; 14.7 K₂O). The globules were also detected in which along with K, a high content of Na and Ca was also ascertained in the silicate coat. The globule coat is considerably enriched with Ba, La, Ce, Nb, and a number of other noncompatible elements as compared with xenolith minerals. The water content in globules is ∼0.6 wt %. As compared with the host mineral (kyanite), the core part of the globules is also enriched with Co, Ni, Zn, and Cu; their content in kyanite is negligibly low. The entire data collection attests to the fact that the formation of silicate globules could have been caused by interaction of the conservated fluid and/or water-silicate melt with the host mineral and crystalline inclusions of clinopyroxene and garnet with decreasing pressure during the transportation of grospydite xenoliths by the kimberlite melt to the Earth’s surface.     

A modeling of the structure and favorable H-docking sites and defects for the high-pressure silica polymorph stishovite

Employing first-principles methods, the docking sites for H were determined and H, Al, and vacancy defects were modeled with an infinite periodic array of super unit cells each consisting of 27 contiguous symmetry nonequivalent unit cells of the crystal structure of stishovite. A geometry optimization of the super-cell structure reproduces the observed bulk structure within the experimental error when P1 translational symmetry was assumed and an array of infinite extent was generated. A mapping of the valence electrons for the structure displays mushroom-shaped isosurfaces on the O atom, one on each side of the plane of the OSi₃ triangle in the nonbonded region. An H atom, placed in a cell near the center of the super cell, was found to dock upon geometry optimization at a distance of 1.69 Å from the O atom with the OH vector oriented nearly perpendicular to the plane of the triangle such that the OH vector makes a angle of 91° with respect to [001]. However, an optimization of a super cell with an Al atom replacing Si and an H atom placed nearby in a centrally located cell resulted in an OH distance of 1.02 Å with the OH vector oriented perpendicular to [001] as observed in infrared studies. The geometry-optimized position of the H atom was found to be in close agreement with that (0.44, 0.12, 0.0) determined in an earlier study of the theoretical electron density distribution. The docking of the H atom at this site was found to be 330 kJ mol^–1 more stable than a docking of the atom just off the shared OO edge of the octahedra as determined for rutile. A geometry optimization of a super cell with a missing Si generated a vacant octahedra that is 20% larger than that of the SiO₆ octahedra. The valence electron density distribution displayed by the two-coordinate O atoms that coordinate the vacant octahedral site is very similar to those displayed by the bent SiOSi angles in coesite. The internal distortions induced by the defect were found to diminish rather rapidly with distance, with the structure annealing to that observed in the bulk crystal to within about three coordination spheres.     

A reappraisal of episodic burial metamorphism in the Andes of central Chile

The Jurassic to Miocene sequences of the central Andes, east of Santiago, reputedly show repeated cycles of episodic sub-greenschist facies, burial metamorphism that are identified by sharp breaks in metamorphic grade at major stratigraphic boundaries. This paper presents the first detailed petrochemical analysis of these low-grade metamorphic sequences by examining the progressive development of secondary minerals, reaction progress in mafic phyllosilicates, and topological variations in the low-grade assemblages as a means of testing this model. The results indicate a progressive increase from zeolite facies through to close to the onset of greenschist facies from Miocene to Jurassic rocks. Combined analysis of reaction progress in mafic phyllosilicates and petrochemical relationships of chlorite–pumpellyite–actinolite in metabasites provides no evidence for sharp metamorphic breaks at major stratigraphic boundaries. Integrating the results presented here with the most recent models of stratigraphic/tectonic development of the central Andes shows that the metamorphism took place in two episodes, and was not episodic on a 40-million-year cycle. An absence of sharp breaks in metamorphic grade in any part of the succession, as demonstrated here, shows that the original petrographic establishment of low-grade facies provided insufficient resolution of changes in metamorphic conditions to establish definitive evidence of such breaks. Accordingly, this study suggests that re-assessment of metamorphic breaks reputedly developed in other areas of the Andean Cordillera is imperative in order to resolve the questions raised here about the origin of the low-grade metamorphism.Editorial responsibility: B. Collins     

Residence, Resorption and Recycling of Zircons in Devils Kitchen Rhyolite, Coso Volcanic Field, California

Zircons from the Devils Kitchen rhyolite in the PleistoceneCoso Volcanic field, California have been analyzed by in situPb/U ion microprobe (SHRIMP-RG) and by detailed cathodoluminescenceimaging. The zircons yield common-Pb-corrected and disequilibrium-corrected²⁰⁶Pb/²³⁸U ages that predate a previously reported K–Arsanidine age by up to 200 kyr, and the range of ages exhibitedby the zircons is also approximately 200 kyr. Cathodoluminescenceimaging indicates that zircons formed in contrasting environments.Most zircons are euhedral, and a majority of the zircons areweakly zoned, but many also have anhedral, embayed cores, witheuhedral overgrowths and multiple internal surfaces that aretruncated by later crystal zones. Concentrations of U and Thvary by two orders of magnitude within the zircon population,and by 10–20 times between zones within some zircon crystals,indicating that zircons were transferred between contrastingchemical environments. A zircon saturation temperature of 750°Coverlaps within error a previously reported phenocryst equilibrationtemperature of 740 ± 25°C. Textures in zircons indicativeof repeated dissolution and subsequent regrowth are probablycaused by punctuated heating by mafic magma input into rhyolite.The overall span of ages and large variation in U and Th concentrations,combined with calculated zircon saturation temperatures andresorption times, are most compatible with crystallization inmagma bodies that were emplaced piecemeal in the crust at Cosoover 200 kyr prior to eruption, and that were periodically rejuvenatedor melted by subsequent basaltic injections. KEY WORDS: zircon geochronology; residence time; rhyolite; ion microprobe; California     

新疆西天山菁布拉克基性杂岩体闪长岩锆石SHRIMP定年及其地质意义

文章对新疆西天山特克斯县菁布拉克基性杂岩体中辉石闪长岩样品中的锆石进行了SHRIMP U-Pb定年研究,获得了(434.4±6.2)Ma的和谐年龄,该结果表明菁布拉克岩体的侵位时间为早志留世。结合岩石地球化学分析所揭示的形成环境信息和最新的区域地质资料,认为菁布拉克岩体的形成与早志留世到早石炭世发生的南天山洋向北与中天山板块的俯冲作用密切相关,岩浆显现出的岛弧岩浆特点可能是由于洋壳向亏损地幔的俯冲所引起的。     

Mineral inclusions and geochemical characteristics of microdiamonds from the DO27, A154, A21, A418, DO18, DD17 and Ranch Lake kimberlites at Lac de Gras, Slave Craton, Canada

A mineral inclusion, carbon isotope, nitrogen content, nitrogen aggregation state and morphological study of 576 microdiamonds from the DO27, A154, A21, A418, DO18, DD17 and Ranch Lake kimberlites at Lac de Gras, Slave Craton, was conducted. Mineral inclusion data show the diamonds are largely eclogitic (64%), followed by peridotitic (25%) and ultradeep (11%). The paragenetic abundances are similar to macrodiamonds from the DO27 kimberlite (Davies, R.M., Griffin, W.L., O'Reilly, S.Y., 1999. Diamonds from the deep: pipe DO27, Slave craton, Canada. In: Gurney, J.J., Gurney, J.L., Pascoe, M.D., Richardson, S.H. (Eds.), The J. B. Dawson Vol., Proc. 7th Internat. Kimberlite Conf., Red Roof Designs, Cape Town, pp. 148–155) but differ to diamonds from nearby kimberlites at Ekati (e.g., Lithos (2004); Tappert, R., Stachel, T., Harris, J.W., Brey, G.P., 2004. Mineral Inclusions in Diamonds from the Panda Kimberlite, S. P., Canada. 8th International Kimberlite Conference, extended abstracts) and Snap Lake to the south (Dokl. Earth Sci. 380 (7) (2001) 806), that are dominated by peridotitic stones.

Eclogitic diamonds with variable inclusion compositions and temperatures of formation (1040–1300 °C) crystallised at variable lithospheric depths sometimes in changing chemical environments. A large range to very ¹³C-depleted C-isotope compositions (δ¹³C=−35.8‰ to −2.2‰) and an NMORB bulk composition, calculated from trace elements in garnet and clinopyroxene inclusions, are consistent with an origin from subducted oceanic crust and sediments. Carbon isotopes in the peridotitic diamonds have mantle compositions (δ¹³C mode −4.0‰). Mineral inclusion compositions are largely harzburgitic. Variable temperatures of formation (garnet T_Ni=800–1300 °C) suggest the peridotitic diamonds originate from the shallow ultra-depleted and deeper less depleted layers of the central Slave lithosphere. Carbon isotopes (δ¹³C av.=−5.1‰) and mineral inclusions in the ultradeep diamonds suggest they formed in peridotitic mantle (670 km). The diamonds may have been entrained in a plume and subcreted to the base of the central Slave lithosphere.

Poorly aggregated nitrogen (IaA without platelets) in a large number of eclogitic (67%) and peridotitic (32%) diamonds, with similar nitrogen contents, indicates the diamonds were stored in the mantle at low temperatures (1060–<1100 °C) following crystallisation in the Archean. Type IaA diamonds have largely cubo-octahedral growth forms, and Type II and Type IaAB diamonds, with higher nitrogen aggregation states, mostly have octahedral morphologies. However, no correlation between these groups and their mineral inclusion compositions, C-isotopes, and N-contents rules out the possibility of unique source origins and suggests eclogitic and peridotitic diamonds experienced variable mantle thermal states. Variation in mineral inclusion chemistries in single diamonds, possible overgrowths of ¹³C-depleted eclogitic diamond on diamonds with peridotitic and ultradeep inclusions, and Type I ultradeep diamond with low N-aggregation is consistent with diamond growth over time in changing chemical environments.