The vibrational frequencies of forsterite Mg2SiO4: an all-electron ab initio study with the CRYSTAL code

The vibrational spectrum of Mg₂SiO₄ olivine was calculated at the Γ point by using the periodic ab initio CRYSTAL program. An all electron localized Gaussian-type basis set and the B3LYP Hamiltonian were employed. The full set of frequencies (35 IR active, 36 Raman active, 10 “silent” modes) was computed and compared to experimental data from different sources (four for IR and four for Raman). A generally good agreement is observed with experiment (the mean absolute difference ranging from 7 to 10 cm⁻¹ for the various sets), when some of the experimental frequencies, whose attribution is uncertain or appears to be affected by large errors, are not taken into account. A small number of observed peaks are not consistent with calculated frequencies, and a few theoretical peaks do not correspond to measured values. The implications are discussed in detail. The full set of modes are characterized using different tools, namely isotopic substitution, direct inspection of the eigenvectors and graphical representation, so as to obtain a consistent mode assignment.     

Mineralogy, geochemistry, and Nd isotope composition of the Rainbow hydrothermal field, Mid-Atlantic Ridge

Petrological, geochemical, and Nd isotopic analyses have been carried out on rock samples from the Rainbow vent field to assess the evolution of the hydrothermal system. The Rainbow vent field is an ultramafic-hosted hydrothermal system located on the Mid-Atlantic Ridge characterized by vigorous high-temperature venting (∼365°C) and unique chemical composition of fluids: high chlorinity, low pH and very high Fe, and rare earth element (REE) contents (Douville et al., Chemical Geology 184:37–48, 2002). Serpentinization has occurred under a low-temperature (<270°C) retrograde regime, later overprinted by a higher temperature sulfide mineralization event. Retrograde serpentinization reactions alone cannot reproduce the reported heat and specific chemical features of Rainbow hydrothermal fluids. The following units were identified within the deposit: (1) nonmineralized serpentinite, (2) mineralized serpentinite—stockwork, (3) steatite, (4) semimassive sulfides, and (5) massive sulfides, which include Cu-rich massive sulfides (up to 28wt% Cu) and Zn-rich massive sulfide chimneys (up to 5wt% Zn). Sulfide mineralization has produced significant changes in the sulfide-bearing rocks including enrichment in transition metals (Cu, Zn, Fe, and Co) and light REE, increase in the Co/Ni ratios comparable to those of mafic Cu-rich volcanic-hosted massive sulfide deposits and different ¹⁴³Nd/¹⁴⁴Nd isotope ratios. Vent fluid chemistry data are indicative of acidic, reducing, and high temperature conditions at the subseafloor reaction zone where fluids undergo phase separation most likely under subcritical conditions (boiling). An explanation for the high chlorinity is not straightforward unless mixing with high salinity brine or direct contribution from a magmatic Cl-rich aqueous fluid is considered. This study adds new data, which, combined with the current knowledge of the Rainbow vent field, brings compelling evidence for the presence, at depth, of a magmatic body, most likely gabbroic, which provides heat and metals to the system. Co/Ni ratios proved to be good tools used to discriminate between rock units, degree of sulfide mineralization, and positioning within the hydrothermal system. Deeper units have Co/Ni <1 and subsurface and surface units have Co/Ni >1.     

Equation of state of MgGeO3 perovskite to 65 GPa: comparison with the post-perovskite phase

The equation of state of MgGeO₃ perovskite was determined between 25 and 66 GPa using synchrotron X-ray diffraction with the laser-heated diamond anvil cell. The data were fit to a third-order Birch–Murnaghan equation of state and yielded a zero-pressure volume (V ₀) of 182.2 ± 0.3 Å³ and bulk modulus (K ₀) of 229 ± 3 GPa, with the pressure derivative (K′₀ = (?K ₀/?P) _T ) fixed at 3.7. Differential stresses were evaluated using lattice strain theory and found to be typically less than about 1.5 GPa. Theoretical calculations were also carried out using density functional theory from 0 to 205 GPa. The equation of state parameters from theory (V ₀ = 180.2 Å³, K ₀ = 221.3 GPa, and K′₀ = 3.90) are in agreement with experiment, although theoretically calculated volumes are systematically lower than experiment. The properties of the perovskite phase were compared to MgGeO₃ post-perovskite phase near the observed phase transition pressure (～65 GPa). Across the transition, the density increased by 2.0(0.7)%. This is in excellent agreement with the theoretically determined density change of 1.9%; however both values are larger than those for the (Mg,Fe)SiO₃ phase transition. The bulk sound velocity change across the transition is small and is likely to be negative [?0.5(1.6)% from experiment and ?1.2% from theory]. These results are similar to previous findings for the (Mg,Fe)SiO₃ system. A linearized Birch–Murnaghan equation of state fit to each axis yielded zero-pressure compressibilities of 0.0022, 0.0009, and 0.0016 GPa^?1 for the a, b, and c axis, respectively. Magnesium germanate appears to be a good analog system for studying the properties of the perovskite and post-perovskite phases in silicates.     

Secular variations of the upper crust composition: Implication of geochemical data on the Upper Precambrian shales from the Southern Urals western flank and Uchur-Maya region

In the mid-1980s, it was concluded based on geochemical study that Th, Sc, La concentrations and ratios Th/Sc, La/Sc and Eu/Eu* did not wary significantly in the post-Archean time. It was impossible to judge about compositional variations of upper crust during the Riphean and Vendian, because data of that time characterized a limited number of samples from the post-Archean basins of Australia, New Zealand, and Antarctic. Considered in this work are variations of Eu/Eu*, LREE/HREE, Th/Sc, and La/Sc ratios in Upper Precambrian fine-grained siliciclastic rock of the Southern Urals western flank (Bashkirian meganticlinorium) and Uchur-Maya region (Uchur-Maya plate and Yudoma-Maya belt). As is established, only the Eu anomaly in the studied siliciclastic rocks is practically identical to this parameter of the average post-Archean shale. Three other parameters plot on the Riphean-Vendian variation curves with positive and negative excursions of diverse magnitude, which do not coincide always in time. It is assumed that these excursions likely mark stages of local geodynamic activity, destruction of pre-Riphean cratons, and progressing recycling of sedimentary material during the Riphean.     

论琅岐岛经济发展定位与开发建设

随着福州东扩南移的城市发展策略的推行,琅岐岛凭借独特的资源优势,经济地理位置日显重要,对其开发建设已成为大势所趋。本文在分析了琅岐岛区域经济发展的资源条件基础上,指出琅岐经济发展的合理定位,提出区域经济发展的若干对策,为琅岐经济持续、健康、稳定地发展提供意见。     

Evolution of the Bonneville shoreline scarp in west-central Utah: Comparison of scarp-analysis methods and implications for the diffusion model of hillslope evolution

Wave-cut pluvial shoreline scarps are ideal natural experiments in hillslope evolution because the ages of these scarps are often precisely known and because they form with a range of heights, alluvial textures, and microclimates (i.e., orientation). Previous work using midpoint-slope methods on pluvial scarps in the Basin and Range concluded that scarp evolution is nonlinear and microclimatically controlled. The purpose of this study was to further examine the influence of scarp height, texture and microclimate in an attempt to calibrate a nonlinear model of scarp evolution. To do this, over 150 profiles of the Bonneville shoreline in the adjacent Snake and Tule Valleys, west-central Utah were collected and analyzed by fitting the entire scarp profile to diffusion-equation solutions, taking into account uncertainty in the initial scarp angle. In contrast to previous studies, this analysis revealed no evidence for nonlinearity or microclimatic control. To understand the reason for this discrepancy, we undertook a systematic study of the accuracy of each scarp-analysis method. The midpoint-slope-inverse method was found to yield biased results, with systematically higher diffusion ages for young, tall scarps. The slope-offset method is unbiased but has limited resolution because it requires many scarp profiles to yield a single diffusion age. A method that incorporates the full scarp profile and uncertainty in the initial scarp angle was found to be the most accurate technique. The application of the full-scarp method to the Bonneville shoreline supports the use of a linear diffusion model for scarps up to 20 m in height. Scarp orientation had no discernable effect on diffusivity values. Soil texture was found to have a weak but significant inverse relationship with diffusivity values.     

Dissolved trace elements in river water: spatial distribution and the influencing factor, a study for the Pearl River Delta Economic Zone, China

Twenty-nine water samples were collected from different river channels of the Pearl River Delta Economic Zone, China. An inductively coupled plasma-mass spectromonitor (ICP-MS) was used to measure concentrations of the trace elements in these samples. The results suggest that the average concentrations of rare earth elements in river water show an increasing trend from the West River, the North River, the rivers of the Pearl River Delta, and the Shenzhen River to the East River. Relatively high concentrations of heavy metals appear in the East River, the rivers of the Pearl River Delta and the Shenzhen River, while the West River and the North River have relatively low heavy metal concentrations. Trace element concentrations in samples collected near urban or industrial areas are much higher than those of samples collected from distant areas, away from urban and industrial areas. After natural conditions, human activities have significant influence on the trace element concentrations in river water. This trace element concentration’s spatial distribution in the river water from the Pearl River Delta Economic Zone is actually an integrated effect of natural conditions and human activity.     

Formation of iron-containing colloids by the weathering of phyllite

The formation of colloids during the weathering of phyllite was investigated by exposing ground phyllite to Milli-Q water. Secondary mineral colloids of 10¹–10² nm were detected in significant concentrations. At pH of about 8.5, the solution concentration of these colloids reached up to 10 mg/L (however, acidification to pH 4.0 prevented the formation of the colloids). The mineralogical composition of the secondary mineral colloids is assumed to be a mixture of ferrihydrite, manganese oxyhydroxides, aluminosilicates, amorphous Al(OH)₃ and gibbsite with possible additions of iron silicates and␣iron-alumino silicates. The colloids were stable over longer periods of time (at least several weeks), even in the presence of suspended ground rock. Direct formation of iron-containing secondary mineral colloids at the rock–water interface by the weathering of rock material is an alternative to the well-known mechanism of iron colloid formation in the bulk of water bodies by mixing of different waters or by aeration of anoxic waters. This direct mechanism is of relevance for colloid production during the weathering of freshly crushed rock in the unsaturated zone as for instance crushed rock in mine waste rock piles. Colloids produced by this mechanism, too, can influence the transport of contaminants such as actinides because these colloids have a large specific surface area and a high sorption affinity.