High-pressure single-crystal X-ray diffraction and synchrotron Mössbauer study of monoclinic ferrosilite

The phase and spin transitions in single-crystal monoclinic ferrosilite, FeSiO₃, were investigated using X-ray diffraction and Mössbauer spectroscopy up to lower-mantle pressures and room temperature in a helium pressure medium. Using single-crystal X-ray diffraction, we measured the equation of state of ferrosilite up to about 43 GPa. We observed a P2₁/c-to-C2/c phase transition between 1.5 and 1.7 GPa and a phase transition from C2/c to a distinct P2₁/c structure between 30 and 34 GPa. With time-domain Mössbauer spectroscopy, we determined the hyperfine parameters of ferrous iron up to 95 GPa. The phase transitions were correlated with discontinuities in Mössbauer spectral features. We observed the onset of high-spin-to-low-spin transitions in the M1 and M2 sites at ～37 GPa and ～74 GPa, respectively. Understanding the electronic structure of iron in a well-characterized single crystal of ferrosilite may help interpret the behavior of iron in complex dense silicate phases.     

Evaluation of the Effectiveness of Different Methods for the Remediation of Contaminated Groundwater by Determining the Petroleum Hydrocarbon Content

The effectiveness of different remediation procedures for decreasing the amount of TPH (total petroleum hydrocarbons) in contaminated groundwater was evaluated at the site of a former refinery. The investigations were carried out on samples taken from several gravel based HSSF (horizontal subsurface flow) constructed wetlands (CW) which differed in relation to their filter material additives (no additive, charcoal, and ferric oxides additives) and examined the potential effect of these additives on the overall treatment efficiency. Samples of the following gravel based HSSF CW were investigated. No filter additive (system A), 0.1% activated carbon (system B), 0.5% iron(III) hydroxide (system C), and the reference (system D). Systems A–C were planted with common reed (Phragmites australis), whereas system D remained unplanted. In addition, the influence of seasonal conditions on the reduction of these hydrocarbons and the correlation between the amounts of TPH and BTEX (benzene, toluene, ethylbenzene, and xylene isomers), on the one hand, and methyl tert‐butyl ether, on the other, was investigated. The study was carried out by using a modified GC‐FID approach and multivariate methods. The investigations carried out in the first year of operation demonstrated that the effectiveness of the petroleum hydrocarbon removal was highest and reached a level of 93 ± 3.5% when HSSF filters with activated carbon as a filter additive were used. This remediation method allowed the petroleum hydrocarbon content to be reduced independently of seasonal conditions. The correlation between the reduction of TPH and BTEX was found to be R = 0.8824. Using this correlation coefficient, the time‐consuming determination of the BTEX content was no longer necessary.     

Petrology and geochemistry of Early Cretaceous A-type granitoids and late Mesozoic mafic dikes and their relationship to adakitic intrusions in the lower Yangtze River belt,Southeast China

The relationship among magmatism, large-scale metallogenesis of Southeast China, and subduction of the Pacific plate has long been debated. The lower Yangtze River belt (LYRB) in the northeastern edge of Southeast China is characterized by intense late Mesozoic magmatism and associated polymetallic mineralization such as copper, gold, iron, tungsten, molybdenum, etc. The copper-related adakitic rocks (148–130 Ma) in this belt are the oldest episode of magmatism and intruded as small intermediate-acid intrusive bodies. The Huayuangong granitoids (HYG), located in the southern part of this belt, however, are copper-barren. Three granitoid samples from this pluton give zircon U–Pb ages of 126.4 ± 1.6 Ma, 125.9 ± 1.9 Ma, and 126.2 ± 1.2 Ma, respectively. The HYG has A-type affinity with metaluminous to weakly peraluminous, high FeO_T/(FeO_T+MgO) ratios, and high Zr+Nb+Ce+Yb contents. Meanwhile, 10 late Mesozoic mafic samples from the LYRB exhibit similar trace element characteristics to those of ‘continental arc andesite’ (CAA) and suggest an enriched lithospheric mantle source with depletion in high field strength elements (e.g. Nb, Ta, Zr, Hf, and Ti) and enrichment of large ion lithophile elements (e.g. Rb, Th, U, and Pb). Although the HYG exhibits similar Sr–Nd isotope composition with the mafic dikes, distinct whole-rock Pb isotope ratios imply that the granitoids and mafic magmas originated from heterogeneous mantle sources. Compared with coeval Baijuhuajian A-type rocks that are exposed along the Jiang–Shao fault of Southeast China, the HYG shows enriched Hf isotope ratios of zircon with ε_Hf(t) values ranging from ?4.8 to ?11.1. In the Yb/Ta versus Y/Nb diagram, being different from the major asthenospheric mantle-origin Baijuhuajian pluton, a large range of and high Y/Nb ratios as well as high Zr contents of the HYG pluton suggest a magmatic source of mixing between the asthenospheric and enriched crustal component in the LYRB. Compared with early-stage copper-related adakitic rocks (148–130 Ma) with subduction-related affinities and high oxygen fugacity, the copper-barren HYG has with-plate A-type affinities and lower oxygen fugacity. Summarizing, the production of early-stage (i.e. subduction related) adakitic rocks followed by late-stage A-type granitoids in the LYRB is ascribed to the rollback of the Palaeo-Pacific plate beneath Southeast China and associated with asthenospheric upwelling and lithospheric thinning during the late Mesozoic era.     

Spin state of ferric iron in MgSiO3 perovskite and its effect on elastic properties

Recent studies have indicated that a significant amount of iron in MgSiO₃ perovskite (Pv) is Fe³⁺ (Fe³⁺/ΣFe = 10–60%) due to crystal chemistry effects at high pressure (P) and that Fe³⁺ is more likely than Fe²⁺ to undergo a high-spin (HS) to low-spin (LS) transition in Pv in the mantle. We have measured synchrotron Mössbauer spectroscopy (SMS), X-ray emission spectroscopy (XES), and X-ray diffraction (XRD) of Pv with all iron in Fe³⁺ in the laser-heated diamond-anvil cell to over 100 GPa. Fe³⁺ increases the anisotropy of the Pv unit cell, whereas Fe²⁺ decreases it. In Pv synthesized above 50 GPa, Fe³⁺ enters into both the dodecahedral (A) and octahedral (B) sites approximately equally, suggesting charge coupled substitution. Combining SMS and XES, we found that the LS population in the B site gradually increases with pressure up to 50–60 GPa where all Fe³⁺ in the B site becomes LS, while Fe³⁺ in the A site remains HS to at least 136 GPa. Fe³⁺ makes Pv more compressible than Mg-endmember below 50 GPa because of the gradual spin transition in the B site together with lattice compression. The completion of the spin transition at 50–60 GPa increases bulk modulus with no associated change in density. This elasticity change can be a useful seismic probe for investigating compositional heterogeneities associated with Fe³⁺.     

Pines and other conifers in Thailand – a Quaternary relic?

In the forests of Thailand there are a number of conifer species from various families. Those growing in mountains have disjunct areas which cannot explain their present occurrence. Fossil evidence is scarce but indicates that in Quaternary the areas were larger. Some species immigrated from the north, others from the south. © 1997 John Wiley & Sons, Ltd.     

Accurate and stablised time integration strategy for saturated porous media dynamics

Acta Geotechnica - When applying equal-order monolithic schemes for the solution of incompressible fluid saturated porous media dynamics, the resulting pressure field often exhibit spurious...     

Vorkommen natürlicher und synthetischer östrogener Steroide in Wässern des süd‐ und mitteldeutschen Raumes

Distribution of Natural and Synthetic Estrogenic Steroid Hormones in Water Samples from Southern and Middle Germany Natural and synthetic hormones can reach surface waters via domestic sewage effluents. For drinking water production, bank filtration of river waters is a common procedure and hormone contaminations can potentially reach groundwater levels and drinking water sources. In order to analyse steroid hormones in the different aquatic compartments (raw sewage and effluent, surface water, groundwater, raw and drinking water) of South and Middle Germany, a sensitive analytical method was developed and employed to detect the natural steroid hormones estradiol (E2) and estrone and the synthetic estrogen ethinylestradiol (EE2). Samples which were taken in two subsequent series were subjected to clean‐up and enrichment procedure and subsequently analysed by HPLC‐MS. The limit of quantitation for the method was determined to be 0.05 to 0.5 ng/L, depending on the matrix. By treating the samples with glucuronidases/arylsulfatases, conjugates were amenable to analysis and the sum of conjugates and unconjugated steroids was calculated. In raw sewage, the median of the concentrations of the unconjugated steroids was 7 ng/L for EE2, 1.5 ng/L for E2, and 5.5 ng/L for estrone. After cleavage of conjugates, the medians of total steroids were 9.5 ng/L (EE2), 3 ng/L (E2), and 13 ng/l (estrone). Conjugates therefore contributed up to 50 % of the total steroid concentration in raw sewage. In treated effluents, the concentrations of steroids were much lower than in the raw sewage. The medians of free steroids were determined to be 0.3 ng/L for EE2, 0.2 ng/L for E2, and 2.5 ng/L for estrone. Overall the medians in the effluent were thus less than 10% of those in the influent. Conjugates still contributed significantly (40% and more) to the steroid concentrations (medians: EE2: 0.5 ng/L, E2: 0.8 ng/L, and estrone: 8 ng/L).     

On equilibrium rotation of the central object of an accretion disc

The hydrodynamic interaction of an accretion disc with its central object is reanalysed within the framework of the slim-disc approximation. Arguments are presented against an interpretation of the total angular momentum flux as an eigenvalue of the system. A simple intuitive consideration is provided, which shows that the central object may be in a state of stationary rotation even if the disc imposes the constraint of a finite angular momentum flux into it. It is argued that equilibrium rotation is characterized by vanishing viscous torque rather than by zero total angular momentum flux. As a consequence, the central object can be in a state of stationary rotation below the break-up limit, although its angular momentum increases. Despite accretion, even for positive total angular momentum flux and subcritical rotation, central objects are spun down within a considerable range of their parameters. The results are illustrated by application to FU Orionis systems.