Structure of Cu-bearing orthopyroxene, Mg(Cu.56,Mg.44)Si2O6, and behavior of Cu2+ in the orthopyroxene structure

Cu-bearing pyroxene, Mg(Cu.₅₆,Mg.₄₄)Si₂O₆, has been synthesized by a flux method and crystal structure refinement has been performed by single crystal X-ray diffraction. It is found that the crystal structure is orthorhombic (space group Pbca) with unit cell dimensions of a=18.221(4), b=8.890(1), c=5.2260(7)Å and the cell volume of 846.5( )3ų. In the M2-site one of the M-O bonds(M-O3B) is extremely expanded from 2.444(2) in enstatite to 2.732(2), thus the coordination polyhedron around M2-site is regarded as square pyramidal rather than square planar or octahedral. It is also found that the M1-site in the pyroxene structure is occupied almost exclusively by Mg, while the M2-site is almost evenly occupied by Mg and Cu. The observed extreme site preference shown by Cu²⁺ is unusual among the divalent cations with similar ionic sizes.     

STRESS-METAMORPHISM AND ISOTOPIC AGE OF SHEAR ZONE GRANITOID TECTONITES OF IRTYSH SHEAR ZONE (ALTAI REGION)

The Irtysh shear zone (ISZ) of Altai region is the lineament structure of the collision-suture type, where granites of Kalba complex and granodiorites of Zmeinogorsk complex are exposed to regional gneiss-formation and stress-metamorphic alterations. This study is based on detailed structural observations at special grounds using optical and electron microscopy, and on the behavior analysis of isotopic systems from altered granitoids.Within the ISZ area we have established the continuous rows of granitoid stress-metamorphism from initial recrystallization of protolite, its cataclasis and mechanical flaring up to complete recrystallization with alteration of mineral composition and formation of the streaky complexes of granite tectonites of blastomylonite and blastocataclasite types. The directed alteration of rocks has several impulse and is expressed by a change in morphology of mineral grains and their relations, magnification of deformation component in the rock structure, and formation of new mineral phases on the basis of initial ones without surface fluidization. At transformation of isotopic systems from granitoid, their feldspars,biotite and hornblende, we can observe “rejuvenation“ of the rock substrate from 270- 290 Ma for Kalba granitoids to 220-235 Ma for their tectonites, and for Rudny Altai granodiorites, their ages changes from 285-317 Ma to 232-257 Ma for their tectonites.     

The infrared dielectric properties of maghemite, γ-Fe2O3, from reflectance measurement on pressed powders

The infrared complex permittivity functions of three varieties of maghemite, γ-Fe₂O₃, having different degrees of vacancy ordering, have been determined from their IR reflectance spectra, measured at near to normal incidence on pressed powder pellets. The optical constants therefrom obtained have been verified by using them in the simulation of the corresponding absorption spectra for KBr-diluted pellets, and these are in excellent agreement with the experimental spectra. All calculations are based on a procedure for the estimation of the effective dielectric function of a mixture, which incorporates percolation features, recently developed by the authors.     

Constraints from Thorium/Lanthanum on Sediment Recycling at Subduction Zones and the Evolution of the Continents

Arc magmas and the continental crust share many chemical features,but a major question remains as to whether these features arecreated by subduction or are recycled from subducting sediment.This question is explored here using Th/La, which is low inoceanic basalts (<0·2), elevated in the continents(>0·25) and varies in arc basalts and marine sediments(0·09–0·34). Volcanic arcs form linear mixingarrays between mantle and sediment in plots of Th/La vs Sm/La.The mantle end-member for different arcs varies between highlydepleted and enriched compositions. The sedimentary end-memberis typically the same as local trench sediment. Thus, arc magmasinherit their Th/La from subducting sediment and high Th/Lais not newly created during subduction (or by intraplate, adakiteor Archaean magmatism). Instead, there is a large fractionationin Th/La within the continental crust, caused by the preferentialpartitioning of La over Th in mafic and accessory minerals.These observations suggest a mechanism of ‘fractionation& foundering’, whereby continents differentiate intoa granitic upper crust and restite-cumulate lower crust, whichperiodically founders into the mantle. The bulk continentalcrust can reach its current elevated Th/La if arc crust differentiatesand loses 25–60% of its mafic residues to foundering. KEY WORDS: arc magmatism; continental crust; delamination; thorium; sediment subduction     

Bizarre geochemistry of komatiites from the Crixás greenstone belt,Brazil

Komatiite lava flows in the Crixás greenstone belt, Goiás, Brazil, have textures and volcanic structures typical of Archean komatiites, but are geochemically most unusual. The flows are porphyritic and massive, or layered with spinifex upper parts and olivine cumulate lower parts. MgO contents range from 18 to 40%. In such lavas, only olivine (and minor chromite) can have crystallized, but neither major nor trace elements fall on olivine control lines. In MgO variation diagrams, CaO and Sr fall on lines with slopes steeper than olivine control lines; SiO₂, FeO, Na₂O, K₂O and Y show little systematic variation; Zr shows a large variation that does not correlate with MgO; and Al₂O₃ decreases markedly with decreasing MgO. The aberrant behaviour is highlighted by the REE (rare earth elements) in spinifex and olivine cumulate layers from three flows: in the spinifex layers, chondrite-normalized REE patterns are hump-shaped with maxima at Nd or Sm ((La/Sm)_N=0.6, (Gd/Yb)_N=1.6–2.3), whereas cumulate zones in the same flows have steadily sloping patterns, with LREE enriched relative to HREE ((La/Sm)_N=1.3, (Gd/Yb)_N=1.4). Neither normal magmatic processes acting during emplacement of the komatiites, nor thermal erosion and wall-rock assimilation can explain these effects, and we speculate that elements commonly thought of as “immobile” (e.g. Al, Zr, REE) migrated during hydrothermal alteration or metamorphism. A Pb-Pb whole rock isochron gave an age of 2,728±140 Ma and selected Sm-Nd analyses an apparent isochron age of 2,825±98 Ma (ɛ_Nd≈0). The Pb-Pb age is believed to be the approximate time of emplacement. Interpretation of the Sm-Nd data is complicated by the evidence of mobility of REE.     

Stabilization of clayey soils with Tunisian phosphogypsum: effect on geotechnical properties

Phosphogypsum and cement have been reported to improve the physicochemical properties of clayey soils. The present study aimed to investigate the behavior of various soils with different particle sizes and chemical and mineralogical compositions in the presence of phosphogypsum and cement mixed at various proportions. These hydraulic binders were assayed on three different soil samples, and their effects were examined using a battery of standardized tests, including the Atterberg limit, uniaxial compressive strength, Californian Bearing Rate (CBR) test, thermogravimetric analysis (TGA), microstructure observation (SEM), and X-ray diffraction tests. The results revealed a significant effect associated with the variation of phosphogypsum content in the soils. Keeping the cement content constant in the mixture, the continuous addition of phosphogypsum was noted to allow shifting the domain of plasticity to the highest water contents, which reduces the sensitivity of the soil to water and to increase the strength of soil. An increase of CBR index with the addition of phosphogypsum and cement is obtained. This treatment could have positively influenced the optimum moisture content and the maximal dry density. The mixture of soil-phosphogypsum and cement could give new forms such as ettringite and hydrate indicators of the improvement of the mechanical properties of the soil. This improvement varies from one soil to another, depending on its granularity and its mineralogy. The mineralogical composition of the soil, particularly kaolinite, amount, and size grading, have direct effects on the physical and mechanical properties of the soils under investigation.     

Geochronological and isotopic records of crustal storage and assimilation in the Wolverine Creek–Conant Creek system,Heise eruptive centre,Snake River Plain

Understanding the processes of differentiation of the Yellowstone–Snake River Plain (YSRP) rhyolites is typically impeded by the apparent lack of erupted intermediate compositions as well as the complex nature of their shallow interaction with the surrounding crust responsible for their typically low O isotopic ratios. A pair of normal-δ¹⁸O rhyolitic eruptions from the Heise eruptive centre in eastern Idaho, the Wolverine Creek Tuff and the Conant Creek Tuff, represent unique magmatic products of the Yellowstone hotspot preserving abundant vestiges of the intermediate differentiation steps leading to rhyolite generation. We address both shallow and deep processes of magma generation and storage in the two units by combining high-precision ID–TIMS U–Pb zircon geochronology, trace element, O and Hf isotopic studies of zircon, and Sr isotopic analyses of individual high-Mg# pyroxenes inherited from lower- to mid-crustal differentiation stages. The zircon geochronology confirms the derivation of both tuffs from the same rhyolitic magma reservoir erupted at 5.5941 ± 0.0097 Ma, preceded by at least 92 ± 14 ky of continuous or intermittent zircon saturation approximating the length of pre-eruptive magma accumulation in the upper crust. Some low-Mg# pyroxenes enclosing zircons predate the eruption by at least 45 ± 27 ky, illustrating the co-crystallisation of major and accessory phases in the near-liquidus rhyolitic melts of the YSRP over a significant period of time. Coeval zircon crystals are isotopically heterogeneous (two populations at εHf ~?5 and ?13), requiring the assembly of isotopically distinct melt pockets directly prior to, or during, the eruption. The primitive Mg# 60–90 pyroxenes are out of isotopic equilibrium with the host rhyolitic melt (⁸⁷Sr/⁸⁶Sr_i = 0.70889), covering a range of ⁸⁷Sr/⁸⁶Sr_i = 0.70705–0.70883 corresponding to ratios typical of the most radiogenic YSRP basalts to the least radiogenic YSRP rhyolites. Together with the low εHf in zircon, the Sr isotopic ratios illustrate limited assimilation dominated by radiogenic Archean crustal source materials incorporated into variably evolved YSRP melts as they progress towards rhyolitic compositions by assimilation–fractional crystallisation.     

Mean flow-transient perturbation interaction in the Southern Hemisphere: a simulation using a variable-resolution GCM

The ability of an atmospheric general circulation model to reproduce fundamental features of the wintertime extratropical Southern Hemisphere (SH) circulation is evaluated with emphasis on the daily variability of the SH mean flow and the mean flow-transient perturbations interaction. Two 10-year simulations using a new version of the LMDZ GCM with a stretched grid scheme centered at 45 °S and forced by climatological SST are performed: a high (144Ꮡ) and low (64Ꭹ) horizontal resolution runs. The performance of both simulations was determined by comparing several simulated fields (zonal wind, temperature, kinetic energy, transient eddy momentum and heat fluxes, Eliassen-Palm fluxes, Eady growth rate and baroclinic conversion term) against the European Centre for Medium Range Weather Forecast reanalyses (ERA). High and low-resolution simulations are similar in many respects; in particular, both experiments reproduce the main patterns of the southern extratropical large-scale circulation satisfactorily. Increasing resolution does not improve universally some spurious aspects of the low resolution simulation (e.g. the cold bias in the high polar troposphere, the debilitated subtropical jet, the low baroclinic conversion rate). Those aspects present little sensitivity to the model resolution. The interaction between transient eddies and zonal mean flow are examined. The low-resolution experiment is able to qualitatively represent the acceleration/deceleration of the mean flow by transient perturbations, south/north of 30 °S with an accuracy similar to that of the high-resolution experiment. Although both experiments represent the baroclinic structure of the mean flow satisfactorily, the model underestimates some transient properties due to the underestimation of the baroclinic conversion term in middle latitudes. Such misrepresentation does not improve with increasing resolution and is related to the relatively weak meridional temperature gradient and the inadequate geographical distribution of the eddy heat fluxes. In particular, the eddy kinetic energy is always underestimated. Eddy kinetic energy does not improve convincingly with increasing resolution, suggesting that the adequate representation of the storm tracks is highly influenced by the physical parametrizations.     

Analysis of the surface temperature and wind forecast errors of the NCAR-AirDat operational CONUS 4-km WRF forecasting system

Investigating the characteristics of model-forecast errors using various statistical and object-oriented methods is necessary for providing useful guidance to end-users and model developers as well. To this end, the random and systematic errors (i.e., biases) of the 2-m temperature and 10-m wind predictions of the NCAR-AirDat weather research and forecasting (WRF)-based real-time four-dimensional data assimilation (RTFDDA) and forecasting system are analyzed. This system has been running operationally over a contiguous United States (CONUS) domain at a 4-km grid spacing with four forecast cycles daily from June 2009 to September 2010. In the result an exceptionally useful forecast dataset was generated and used for studying the error properties of the model forecasts, in terms of both a longer time period and a broader coverage of geographic regions than previously studied. Spatiotemporal characteristics of the errors are investigated based on the 24-h forecasts between June 2009 and April 2010, and the 72-h forecasts between May and September 2010. It was found that the biases of both wind and temperature forecasts vary greatly seasonally and diurnally, with dependency on the forecast length, station elevation, geographical location, and meteorological conditions. The temperature showed systematic cold biases during the daytime at all station elevations and warm biases during the nighttime above 1,000 m above sea level (ASL), while below 600 m ASL cold biases occurred during the nighttime. The forecasts of surface wind speed exhibited strong positive biases during the nighttime, while the negative biases were observed in the spring and summer afternoons. The surface wind speed was mostly over-predicted except for the stations located between 1,000 and 2,100 m ASL, for which negative biases were identified for most forecast cycles. The highest wind-speed errors were found over the high terrain and near sea-level stations. The wind-direction errors were relatively large at the high-terrain elevation in the Rocky and Appalachian mountain ranges and the western coastal areas and the error structure exhibited notable diurnal variability.