The molecular-level processes that control green rust sodium sulphate (GRNa,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 GRNa,SO4 dissolve and amorphous Cr(III),Fe(III)-solid forms. During equilibration, Cr-substituted goethite evolves in association with remaining GRNa,SO4, fed by material from the amorphous phase and dissolving oxidised GR. In contrast, previous Cr(VI) experiments with the carbonate form of GR, GRCO3, 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. 相似文献
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. 相似文献
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. RbSr 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. 相似文献
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. 相似文献
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. 相似文献
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 相似文献
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 KArsanidine 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 1020 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相似文献
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 TNi=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. 相似文献