ELNES spectroscopy of mixed Si coordination minerals

 Si K- and L-edge ELNES spectroscopy and multiple-scattering (MS) calculations are used to examine mixed Si coordination compounds varying in Si^VI:Si^IV ratio. As in previous studies, the edges are influenced mainly by silicon coordination (tetrahedral vs. octahedral), as supported by the MS calculations. We demonstrate two methods semi-quantitatively to extract the value of Si^VI/(Si^VI+Si^IV): (1) A linear relationship between the L_2,3-L₁ splitting and Si^VI/(Si^VI+Si^IV) is observed, (2) a fitting method based on the coaddition of reference tetrahedral and octahedral Si spectra is applied to both Si K- and L-edge ELNES spectra. Received: February 10, 1997 / Revised, accepted: May 23, 1997     

Object and Pixel-Based Reservoir Modeling of a Braided Fluvial Reservoir

To assess differences between object and pixel-based reservoir modeling techniques, ten realizations of a UK Continental Shelf braided fluvial reservoir were produced using Boolean Simulation (BS) and Sequential Indicator Simulation (SIS). Various sensitivities associated with geological input data as well as with technique-specific modeling parameters were analyzed for both techniques. The resulting realizations from the object-based and pixel-based modeling efforts were assessed by visual inspection and by evaluation of the values and ranges of the single-phase effective permeability tensors, obtained through upscaling. The BS method performed well for the modeling of two types of fluvial channels, yielding well-confined channels, but failed to represent the complex interaction of these with sheetflood and other deposits present in the reservoir. SIS gave less confined channels and had great difficulty in representing the large-scale geometries of one type of channel while maintaining its appropriate proportions. Adding an SIS background to the Boolean channels, as opposed to a Boolean background, resulted in an improved distribution of sheetflood bodies. The permeability results indicated that the SIS method yielded models with much higher horizontal permeability values (20–100%) and lower horizontal anisotropy than the BS versions. By widening the channel distribution and increasing the range of azimuths, however, the BS-produced models gave results approaching the SIS behavior. For this reservoir, we chose to combine the two methods by using object-based channels and a pixel-based heterogeneous background, resulting in moderate permeability and anisotropy levels.     

The transition from peraluminous to peralkaline granitic melts: Evidence from melt inclusions and accessory minerals

Fractional crystallization of peraluminous F- and H₂O-rich granite magmas progressively enriches the remaining melt with volatiles. We show that, at saturation, the melt may separate into two immiscible conjugate melt fractions, one of the fractions shows increasing peraluminosity and the other increasing peralkalinity. These melt fractions also fractionate the incompatible elements to significantly different degrees. Coexisting melt fractions have differing chemical and physical properties and, due to their high density and viscosity contrasts, they will tend to separate readily from each other. Once separated, each melt fraction evolves independently in response to changing T/P/X conditions and further immiscibility events may occur, each generating its own conjugate pair of melt fractions. The strongly peralkaline melt fractions in particular are very reactive and commonly react until equilibrium is attained. Consequently, the peralkaline melt fraction is commonly preserved only in the isolated melt and mineral inclusions.

We demonstrate that the differences between melt fractions that can be seen most clearly in differing melt inclusion compositions are also visible in the composition of the resulting ore-forming and accessory minerals, and are visible on scales from a few micrometers to hundreds of meters.     

Structure proof and significance of stereoisomeric 28,30-bisnorhopanes in petroleum and petroleum source rocks

Two C₂₈H₄₈-pentacyclic triterpanes were isolated from Monterey shale. X-ray crystallography of a crystal containing both compounds proved their structures as 17β,18α,21α(H)-28,30-bisnorhopane and 17β,18α,21β(H)-28,30-bisnorhopane. Several differences are found between 28,30-bisnorhopanes and the regular hopanes. Unlike the regular hopane epimers, for practical purposes the three epimeric 28,30-bisnorhopanes [17α,21β(H)-, 17β,21α(H)-, and 17β,21β(H)-]cannot be distinguished by their mass spectra. Special conditions are needed to separate them by gas chromatography. The diagenetically first-formed epimer is thought to be 17α,21β(H)- because it predominates in immature shales. The order of thermodynamic stability is 17β,2lα(H) < > 17α,21β(H) > 17β,21β(H), and all three epimers are present in petroleum. 25,28,30-Trisnorhopanes can be analyzed in similar fashion and are found to have similar thermodynamic characteristics. The percent of the ring D/E cis epimer of 28,30-bisnorhopane and/or 25,28,30-trisnorhopane is a useful maturation parameter similar to the 20S/20R sterane ratio. Evidence indicates 25-demethylation of 28,30-bisnorhopane to 25,28,30-trisnorhopane during advanced stages of biodegradation. Hence, percent ring $\text{D}\text{E}$cis 25,28,30-trisnorhopane has an application to maturation assessment in heavily biodegraded oils.     

Oxygen deficient perovskites in the system CaSiO3–CaAlO2.5 and implications for the Earth’s interior

Oxygen deficient perovskites of the system CaSiO₃–CaAlO_2.5 have been synthesised at high-pressure and -temperature conditions relevant to the Earth’s transition zone in order to investigate their stabilities in the Earth’s mantle and determine structural properties associated with vacancy incorporation. Two polysomes of thermodynamically stable defect perovskites with Ca(Al_0.4Si_0.6)O_2.8 and Ca(Al_0.5Si_0.5)O_2.75 stoichiometry have been identified. The ordering of oxygen defects into pseudo-cubic (111) layers results in well-ordered ten- or eightfold superstructures, respectively. At all other compositions examined, a metastable formation of perovskites has been observed instead, which are assumed to grow initially disordered. These are now characterised by tiny domains, formed due to subsequent ordering of vacancies along various pseudo-cubic {111} layers. Both ordered defect perovskites show a large P–T stability field ranging from about 9–18 GPa and 4–12 GPa, respectively. Microstructural TEM analyses revealed the presence of growth and ferroelastic twins, which indicate a phase transition from rhombohedral to monoclinic symmetry during quenching. Electron energy loss spectroscopy of Si and Al K edges point at the presence of tetrahedral, octahedral and maybe some pentacoordinated silicon, whereas aluminium is predominantly octahedrally coordinated with minor fractions in lower coordination. Observed properties are interpreted in terms of a new structural model, explaining the observed phase transition and formation of different twin laws as well as giving reasons for the development of such large superstructures. With respect to phase relations of the transition zone, the potential occurrence of such defect perovskites in the Earth’s interior is discussed.     

Ophiolites of the Eastern Peninsulas zone (Eastern Kamchatka): Age, composition, and geodynamic diversity

Abstract   The geological, geochemical and mineralogical data of dismembered ophiolites of various ages and genesis occurring in accretionary piles of the Eastern Peninsulas of Kamchatka enables us to discriminate three ophiolite complexes: (i) Aptian–Cenomanian complex: a fragment of ancient oceanic crust, composed of tholeiite basalts, pelagic sediments, and gabbroic rocks, presently occurring in a single tectonic slices (Afrika complex) and in olistoplaques in Pikezh complex of the Kamchatsky Mys Peninsula and probably in the mélange of the Kronotsky Peninsula; (ii) Upper Cretaceous complex, composed of highly depleted peridotite, gabbro and plagiogranite, associated with island arc tholeiite, boninite, and high-alumina tholeiitic basalt of supra-subduction origin; and (iii) Paleocene–Early Eocene complex of intra-island arc or back-arc origin, composed of gabbros, dolerites (sheeted dykes) and basalts produced from oceanic tholeiite melts, and back-arc basin-like dolerites. Formation of the various ophiolite complexes is related to the Kronotskaya intra-oceanic volcanic arc evolution. The first ophiolite complex is a fragment of ancient Aptian–Cenomanian oceanic crust on which the Kronotskaya arc originated. Ophiolites of the supra-subduction zone affinity were formed as a result of repeated partial melting of peridotites in the mantle wedge up to the subduction zone. This is accompanied by production of tholeiite basalts and boninites in the Kamchatsky Mys segment and plagioclase-bearing tholeiites in the Kronotsky segment of the Kronotskaya paleoarc. The ophiolite complex with intra-arc and mid-oceanic ridge basalt geochemical characteristics was formed in an extension regime during the last stage of Kronotskaya volcanic arc evolution.     

The restricted stability of osumilite under hydrous conditions in the system K2O-MgO–Al2O3–SiO2–H2O

Osumilite_ss was synthesized as a single phase product in the model system K₂O-MgO-Al₂O₃-SiO₂ at 800° C/ 0.5 Kbar water pressure and at 800° to 840° C/1.0 Kbar total pressure with 0.3 in the gas phase. The experimentally determined solid solubility range of synthetic osumilites can be expressed by the formula KMg₂(Al_3-xMg_x) (Al_2–xSi_10+x)O₃₀ with 0x0.4. A survey of sixteen chemical analyses of natural osumilites from eleven occurrences shows a solid solubility characterized by 0x0.6. Reversed stability experiments for the synthetic osumilite KMg₂(Al_2.75Mg_0.25)(Al_1.75Si_10.25)O₃₀ determined at water pressure equal to total pressure demonstrate its restriction to water pressures below 0.8 Kbar (at 0.5 Kbar, the stability range is between 765° and 800° C). At the lower thermal stability limit osumilite+H₂O vapor break down to cordierite+K feldspar+phlogopite_ss+quartz, at the higher one to cordierite+K feldspar+phlogopite+liquid. Reduction of water fugacity will expand the stability field largely by shifting the lower and higher thermal stability limits to lower and higher temperatures, respectively. The dependence of osumilite stability on water fugacity makes osumilite a sensitive indicator mineral for dry conditions in rocks formed at total pressures higher than about 0.8 Kbar.     

A komatiite component in Apollo 16 highland breccias: implications for the nickel-cobalt systematics and bulk composition of the moon

The lunar crust at the Apollo 16 landing site contains substantial amounts of a “primitive component” in which the ferromagnesian group of elements is concentrated. The composition of this component can be retrieved via an analysis of mixing relationships displayed by lunar breccias. It is found to be a komatiite which is compositionally similar to terrestrial komatiites both in major and minor elements. The komatiite component of the lunar crust is believed to have formed by extensive degrees of melting of the lunar interior at depths greater than were involved in the formation of the lunar magma ocean which was parental to the crust. After formation of the anorthositic crust, it was invaded by extensive flows and intrusions of komatiite magma from these deeper source regions. The komatiites became intimately mixed with the anorthosite by intensive meteoroid impacts about 4.5 b.y. ago, thereby accounting for the observed mixing relationships displayed by the crust. The compositional similarity between lunar and terrestrial komatiites strongly implies a corresponding similarity between the compositions of their source regions in the lunar interior and the Earth's upper mantle. The composition of the lunar interior can be modelled more specifically by combining the komatiite composition with its liquidus olivine composition (as determined experimentally) in proportions chosen so as to produce a cosmochemically acceptable range of Mg/Si ratios for the bulk Moon. Except for higher FeO and lower Na₂O, the range of compositions thereby obtained for the bulk moon is very similar to the composition of the Earth's upper mantle.The effects of meteoritic contamination on the abundances of cobalt and nickel in lunar highland breccias were subtracted on the assumption that the contaminating projectiles were chondritic. The cobalt and nickel residuals thereby obtained were found to correlate strongly with the (Mg + Fe) content of the breccias, demonstrating that the Co and Ni are associated with the ferromagnesian component of the breccias and are genuinely indigenous to the Moon. The lunar highland Co and Ni residuals also display striking Ni/Co versus Ni correlations which follow a similar trend to those displayed by terrestrial basalts, picrites and komatiites. The lunar trends provide further decisive evidence of the indigenous nature of the Co and Ni residuals and suggest the operation of extensive fractionation controlled by olivine-liquid equilibria in producing the primitive component of the lunar breccias. Indigenous nickel abundances at the Apollo 14, 15 and 17 sites are much lower than at the Apollo 16 site, although rocks from all sites follow the same Ni/Co versus Ni trends. It is suggested that the primitive component at the Apollo 14, 15 and 17 sites was generally of basaltic composition, in contrast to the komatiitic nature of the Apollo 16 primitive component.     

An in situ investigation of the preservation and alteration of presolar silicates in the Miller Range 07687 chondrite

Dust grains that formed around ancient stars and in stellar explosions seeded the early solar protoplanetary disk. While most of such presolar grains were destroyed during solar system formation, a fraction of such grains were preserved in primitive materials such as meteorites. These grains can provide constraints on stellar origins and secondary processing such as aqueous alteration and thermal metamorphism on their parent asteroids. Here, we report on the nature of aqueous alteration in the Miller Range (MIL) 07687 chondrite through the analysis of four presolar silicates and their surrounding material. The grains occur in the Fe-rich and Fe-poor lithologies, reflecting relatively altered and unaltered material, respectively. The O-isotopic compositions of two grains, one each from the Fe-rich and Fe-poor matrix, are consistent with formation in the circumstellar envelopes of low-mass Asymptotic Giant Branch (AGB)/Red Giant Branch (RGB) stars. The other two grains, also one each from the Fe-rich and Fe-poor matrix, have O-isotopic compositions consistent with formation in the ejecta of type-II supernovae (SNe). The grains derived from AGB/RGB stars include two polycrystalline pyroxene grains that contain Fe-rich rims. The SNe grains include a polycrystalline Ca-bearing pyroxene and a polycrystalline assemblage consistent with a mixture of olivine and pyroxene. Ferrihydrite is observed in all focused ion beam sections, consistent with parent-body aqueous alteration of the fine-grained matrix under oxidizing conditions. The Fe-rich rims around presolar silicates in this study are consistent with Fe-diffusion into the grains resulting from early-stage hydrothermal alteration, but such alteration was not extensive enough to lead to isotopic equilibration with the surrounding matrix.     

Application and validation of FLEMOcs – a flood-loss estimation model for the commercial sector

Abstract

The estimation of flood loss is difficult, especially in the commercial sector, because of its great inhomogeneity. However, the reliability of loss modelling is fairly unknown, since flood-loss models are scarcely validated. The newly developed Flood Loss Estimation MOdel for the commercial sector (FLEMOcs) was validated on the micro-scale using a leave-one-out cross-validation procedure. Additionally, different meso-scale loss functions were compared. Meso-scale model application was undertaken in 19 municipalities which were affected during the 2002 flood in Germany. Model results were compared with the results of three other loss models, as well as with official loss records. The micro-scale validation shows very good results, with no bias and mean absolute errors between 23 and 31%. The meso-scale validation indicates that FLEMOcs provides good results, especially in large areas with many affected companies where high losses are expected.

Citation Seifert, I., Kreibich, H., Merz, B. & Thieken, A. H. (2010) Application and validation of FLEMOcs – a flood-loss estimation model for the commercial sector. Hydrol. Sci. J. 55(8), 1315–1324.